CN108837834B - 一种co2加氢直接制低碳烯烃的催化剂及其制备方法 - Google Patents
一种co2加氢直接制低碳烯烃的催化剂及其制备方法 Download PDFInfo
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Abstract
本发明涉及CO2加氢直接制乙烯、丙烯、丁烯的层状结构催化剂。本发明催化剂的制备，采用九水合硝酸铁、碳酸钾、二氧化钛在一定条件混合后，采用高温固相法在一定温度下经过两次煅烧制备得到层状结构催化剂。本发明催化剂具有稳定的层状结构，在CO2加氢直接制乙烯、丙烯、丁烯反应前后层状结构能够稳定保持，在一定程度抑制了初级烯烃再吸附而引发的烯烃二次反应，在CO2加氢直接制低碳烯烃反应得到了高烯烃选择性。该制备方法简单，对环境友好，具有潜在的应用价值。
Description
技术领域
本发明涉及CO2加氢高选择性合成乙烯、丙烯、丁烯的催化剂及其制备方法，具体涉及一种具有稳定层状结构金属复合氧化物催化剂，用于CO2加氢制乙烯、丙烯、丁烯的催化剂及其制备。
背景技术
CO2加氢制低碳烯烃是目前CO2利用的潜在途径之一，该过程可通过CO2费托合成过程（CO2–FTS）选择性合成低碳烯烃。该过程在活化稳定CO2同时能实现其高附加值利用，在科学研究和实际应用中将具有重要意义。由于费托过程产物受（Anderson-Schulz-Flory）ASF分布限制，其产物分布较宽，同时在传统Fe基催化剂上得到的产物烷烃附加值低，如能将产物分布调控至高附加值的低碳烯烃，低碳烯烃是费托（F–T）合成的主要初级产物，也是重要的化工基础原料，用途十分广泛。因此，如能开发出一种高低碳烯烃选择性催化剂将对CO2利用将产生重要意义。
考虑到Fe基催化剂廉价易得，具有良好的催化活性，被广泛应用于二氧化碳加氢反应中但仍存在产物分布宽、催化剂稳定性差等问题。而在典型的费托合成反应中，初级烯烃易在催化剂表面再吸附引发二次加氢反应致使烯烃选择性降低，是该过程副产物选择性较高的主要影响因素之一。目前，抑制初级烯烃二次反应活性、提高催化剂烯烃选择性、降低CO选择性、调控产物分布还存在关键性技术难题。因此，设计一种能够抑制烯烃二次反应的催化剂至关重要。
发明内容
本发明针对现有技术中存在的难点提供一种多层级ABCOx复合体系结构催化剂，提供一种简单、环保、快速的制备方法；通过元素的调配，达到相态和电荷平衡，以分段煅烧的方法获得催化剂层状叠加，从而具备较短的原料传输孔道、易于原料和产物快速吸脱附，能在一定程度抑制扩散限制，降低烯烃再吸附而引发的二次反应。最大限度的抑制初级烯烃二次加氢反应，从而提高烯烃选择性调控出附加值高的产物分布。
本发明层状催化剂可应用于CO2加氢制低碳烯烃反应中，效果明显，烯烃与烷烃比值在9以上。
本发明以高温固相反应方法制备得到层状结构催化剂，其结构以铁锌（钛、锆）氧为负电性板层，层间填充金属阳离子（Li、Na、K、Rb、Cs）来达到电荷平衡。
本发明催化剂的制备方法，首先采用煅烧法得到金属混合氧化物作为原料，在高温下按一定温度、升温速率达到设定温度，通过高温固相反应，得到层状结构催化剂，该制备方法简单，重复性好，对环境友好，反应寿命长，具有潜在的经济价值。
将这种层状结构催化剂应用于CO2加氢直接制乙烯、丙烯、丁烯反应，由于催化剂表面具有较弱的烯烃二次吸附能力，反应过程中生成的初级烯烃会及时脱离催化剂表面，抑制了初级烯烃的再吸附，一定程度地抑制了烯烃二次反应；在CO2加氢反应中获得良好的烯烃选择性和结构稳定性。
本发明通过以下技术方案实现：
催化剂为多层级ABCOx复合体系结构，其中A为碱性助剂，是锂、钠、钾、铷、铯元素的一种，占催化剂总量的0.1~10 %；B为铁、锌、锆元素的一种及以上，C为钛元素，O为氧元素，x代表氧原子数，BCOx占催化剂总量的5–90 %；BCOx为催化剂提供催化活性位，呈正八面体结构，B中元素与C中元素位于正八面体中心，氧原子位于正八面体顶点；BCOx为层状排列，显负电性；A中元素为离子态，呈正电性，以平衡电荷的方式填充在BCOx层状序列中，A与BCOx间互相作用，平衡电荷，增加碱性位；催化剂层与层间距在0.2–10 nm，优选0.5-3nm。
催化剂的制备步骤在于：
（1）A和B中元素源于A、B元素的化合物，C中元素源于C元素的化合物，按摩尔比计A :B : C= 0.6~11：1~48 ：1~17称取投料，研磨充分混合，于120°C干燥24 h得到煅烧前ABCOx前驱体；
（2）充分研磨后在500 °C下焙烧1–3 h，焙烧后研磨均匀；
（3）取上述煅烧后所得粉末样品，在空气气氛下保持气体流速≤ 50 mL·min–1，在管式炉中设施分段焙烧，以10–30 °C/min升至500 °C，维持0.5 h；以5–10 °C/min升至800°C，维持0.5–2 h；以5–10 °C/min升至1000 °C，维持0.5–2 h；以2–10 °C/min升至1100 °C，保持3–12 h；
（4）自然冷却降温，研磨均匀，得催化剂粉末。
催化剂制备步骤（1）中投料是先将含有A元素的化合物研磨至大于100目后，添加C元素的化合物研磨至大于150目后，再加入B元素的化合物研磨至大于100目后，最后于120°C干燥24 h得到煅烧前ABCOx前驱体。
催化剂制备步骤（1）中原料除A、B元素化合物可以是A、B元素的碳酸盐、硝酸盐、磷酸盐、次磷酸盐、氧化物，优选碳酸盐。
催化剂制备步骤（3）中空气流速须控制在≤ 50 mL·min–1，气体气氛可以为空气、氮气、合成气、氧气。
本发明催化剂在于层状结构，块状形貌，以及经碱性助剂调控后的表面酸碱度，在高温煅烧后制备得到的多级孔道，制备获得的层状结构催化剂与颗粒状及多孔材料相比，具有较短的孔道，物料传输距离短，易于原料CO2、H2和产物的快速吸附和扩散，改善产物吸脱附能力，可在一定程度上降低扩散限制，抑制烯烃二次加氢反应，进一步调控产物分布，获得高的烯烃收率。
本发明催化剂为层状结构、块状形貌。本发明催化剂应用于CO2加氢直接制乙烯、丙烯、丁烯反应，采用固定床做催化活性评价，反应条件为H2/CO2 = 1–4，280 ~ 350 °C、1~3MPa，1000~4000 h–1。
催化剂在经XRD测试，其在2θ = 11.2 °、28.96 °、34.2 °、37.9 °出现层状结构特征衍射峰，该催化剂具有典型的层状结构。
附图说明
图1是层状催化剂的SEM图。
图2是层状催化剂的TEM图。
图 3 是煅烧法制备的非层状结构催化剂SEM图。
具体实施方式
一、催化剂制备
（1）煅烧法合成混合氧化物
以K2CO3（KNO3）、Fe(NO3)3·9H2O、TiO2为原料按一定配比分别称取不同质量的样品于研钵中混合均匀，充分研磨后在500 °C下焙烧3 h。焙烧好的试样研磨均匀。
（2）高温固相法制备层状K–Fe–Ti催化剂
取（1）煅烧后所得粉末样品2 g，在空气气氛下保持气体流速50 mL·min–1，经充分研磨后在管式炉中（15 °C–500 °C，5 °C/min；500 °C–800 °C，10 °C/min；800 °C–1000 °C，5 °C/min；1000 °C–1100 °C，2 °C/min）经1100 °C焙烧10 h，自然冷却降温。焙烧好的试样研磨均匀。
二、催化剂表征
经XRD表征测试，催化剂样品在2θ = 11.2 °、28.96 °、34.2 °、37.9 °等处出现层状特征衍射峰，主要物相为K2.3Fe2.3Ti5.7O16。煅烧法制备样品在2θ = 25.3 °、37.0 °、37.8°、48.2 °等处出现TiO2特征衍射峰，同时在2θ = 24.3 °、33.3 °、35.7 °、49.6 °、54.1 °处出现Fe2O3特征衍射峰。对于层状催化剂，除观察到以上特征衍射峰外，还发现其它物相特征衍射峰，表明催化剂物相随催化剂原料配比关系密切；随着Fe含量增多，对应于XRD结果发现，Fe的相关氧化物物相增多，且催化剂催化活性提高。
图1为层状结构催化剂的SEM图。图1显示，层状结构催化剂为块状结构的催化剂，块状结构达到微米级别，催化剂表面平滑。
图2是催化剂的TEM图。由图2可以清晰的看到催化剂为明显且完整的层状。
三、催化活性
表1为催化剂的CO2加氢催化性能。由表1可以看出，相比较非层状结构催化剂，层状结构催化剂烯烃选择性明显高。1K–3Fe–1Ti催化剂的C2 =–C4 =占总烃分布的60.2%，O/P值为9.1，CO2转化率达41.0 %。增大Fe含量，催化剂其CO2转化率升高，该催化剂同时具有高的烯烃选择性，通过层状催化的设计，一定程度上降低了二次加氢的能力，经测试催化剂在202 h内运行稳定。
表1 催化剂CO2加氢反应活性
反应条件：a: H2/CO2 = 3, 320 ºC, 1.0 MPa, 1000 h–1.
b: H2/CO2 = 3, 320 ºC, 2.0 MPa, 1000 h–1.
c: H2/CO2 = 3, 320 ºC, 2.0 MPa, 3000 h–1.
d: H2/CO2 = 3, 320 ºC, 3.0 MPa, 1000 h–1.
四、数据小结
（1）1K–3Fe–1Ti层状结构催化具有高烯烃选择性达到60.2 %，O/P = 9.1。
（2）在催化剂中Fe含量增加后，催化剂CO2转化率明显提升，此时催化剂仍具有高的烯烃选择性达57 %以上。
（3）层状结构催化剂具有具有较短的孔道传输距离，能够抑制烯烃再吸附，能在一定程度抑制烯烃二次加氢反应，因此在提高低碳烯烃选择性的同时具有高的CO2转化率。
Claims (2)
1.一种催化剂用于CO2加氢直接制低碳烯烃的应用，其特征在于，
所述催化剂应用于CO2加氢反应制备乙烯、丙烯、丁烯反应，反应条件为H2/CO2 =1~4，280~350℃、1~3 MPa，1000~4000 h–1；
所述催化剂为多层级ABCOx复合体系结构，其中A为碱性助剂，是锂、钠、钾、铷、铯元素的一种，占催化剂总量的0.1~10%；B为铁、锌元素的一种及其组合，C为钛元素，O为氧元素，x代表氧原子数，BCOx占催化剂总量的5–90%，上述组份的总量之和为100%；BCOx为催化剂提供催化活性位，呈正八面体结构，B中元素与C中元素位于正八面体中心，氧原子位于正八面体顶点；BCOx为层状排列，显负电性；A中元素为离子态，呈正电性，以平衡电荷的方式填充在BCOx层状序列中，A与BCOx间互相作用，平衡电荷，增加碱性位；所述催化剂层与层间距在0.2–10nm；所述催化剂的制备步骤在于：
（1）A和B中元素源于A、B元素的化合物，C中元素源于C元素的化合物，按摩尔比计A : B :C= 0.6~11：1~48 ：1~17称取投料，研磨充分混合，于120℃干燥24 h得到煅烧前ABCOx前驱体；其中A、B元素的化合物为碳酸盐或硝酸盐化合物；C元素的化合物为氧化物；所述催化剂制备步骤（1）中投料是先将含有A元素的化合物研磨至大于100目后，添加C元素的化合物研磨至大于150目后，再加入B元素的化合物研磨至大于100目后，最后于120℃干燥24 h得到煅烧前ABCOx前驱体；
（2）充分研磨后在500℃下焙烧1–3 h，焙烧后研磨均匀；
（3）取上述煅烧后所得粉末样品，在空气、氮气、氧气之一的气氛下，在气体流速≤ 50mL·min–1的条件下进行；在管式炉中实施分段焙烧，以10–30℃/min升至500℃，维持0.5 h；以5–10℃/min升至800℃，维持0.5–2 h；以5–10℃/min升至1000℃，维持0.5–2 h；以2–10℃/min升至1100℃，保持3–12 h；
（4）自然冷却降温，研磨均匀，得催化剂粉末。
2.根据权利要求1所述的应用，其特征在于，所述催化剂为层状结构、块状形貌。
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