CN112121814A - 一种钙钛矿催化剂的制备方法和应用 - Google Patents
一种钙钛矿催化剂的制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种改性钛矿催化剂应用于CO或CO2加氢制备乙烯、丙烯、丁烯，经乙醇钾、叔丁醇钾的处理改性后，催化剂表现出良好的CO加氢性能，低碳烯烃选择性保持在50%以上，烯烷比（O/P）可达5.6。具有潜在的经济价值。
Description
技术领域
本发明涉及催化剂制备技术领域，涉及一种钛矿催化剂的改性，应用于CO或CO2加氢制备乙烯、丙烯、丁烯。
背景技术
低碳烯烃是重要的化工基础原料，用途十分广泛。在CO加氢过程中，受活性组分相态变化影响，伴随发生包含烯烃、烷烃的合成、CO的转化在内的主反应，以及甲烷、含氧化物的生成、CO歧化反应、表面积碳在内的副反应。
钙钛矿型氧化物是一种具有独特物理性质、化学性质的新型无机非金属材料，在大量研究中发现，钙钛矿型氧化物由于其结构稳定可控、热稳定性好、催化效率高、成本较低等优点，其作为一种新型的催化剂被广泛的研究和利用。由于在钙钛矿型氧化物 ABO3中，A 位离子主要起到稳定钙钛矿晶体骨架结构的作用，不直接参与反应。但 A 位离子的掺杂能够影响晶体结构的变化、B 位离子价态及催化剂内不同种类的氧含量的变化，从而间接影响氧化物的反应活性。从钙钛矿氧化物的结构特征可知，在不破坏基体结构的前提下，当 A 位离子被离子部分取代时，由于离子的半径不同，使得钙钛矿的晶体结构产生一定程度的畸变，影响其氧化物熔点、导电性等物理性质。A 位离子被高价离子取代将在 A位形成空位及引起 B 位离子价态的降低，而 A 位离子被低价离子取代时，掺杂能使 B 位阳离子的化合价升高及结构中氧空位的产生以维持氧化物的电中性。而钙钛矿型氧化物的催化循环性能依赖于 B 位离子的氧化还原性能，同时晶格氧的脱附受到到氧空位的含量的影响，较高的氧空位的含量有助于晶格氧的脱附，进一步提升钙钛矿的氧化还原性能，因此 A 位掺杂离子的选择对于钙钛矿的改性有重大的意义。
钙钛矿催化剂在低碳烯烃合成中的应用并不多见，Velle等发现SrCe1-xYbxO3-0.5x系列催化剂在x=0-0.5时对乙烷催化氧化反应有活性。Takehira等研究了La1-xSrxFeO3-δ（0≤x≤1.0）对乙烷氧化脱氢反应的催化性能，结果发现当Sr全部取代La后催化剂显示出最好的催化活性。绝大多数对于钙钛矿型氧化物催化剂的研究集中于通过A、B位阳离子的取代来调变氧空位的密度和B位阳离子的价态。
以Fe、Co或Ni作为活性组分。这类催化剂在使用前必须还原活化，也就是在金属状态下才具有初始活性。由于合成气制低碳烯烃过程中为了得到低碳产物，通常操作温度较高，这些金属活性组分会发生结构变化。金属Fe在反应过程中会被碳化形成碳化铁，虽然碳化铁的形成不影响活性，甚至对选择性有利，但催化剂结构的变化会导致催化剂积碳、破碎和粉化的现象，因此催化剂稳定性差。Co催化剂不适合在高温下使用，因为形成碳化钴会导致催化剂失活；而Ni催化剂在高温下也很容易积碳，而且主要产物是甲烷，低碳烯烃选择性低。
国内外相关实验研究和理论计算的结果证明，除了低碳烯烃选择性，Fe基FTO催化剂上的电子特性、产物的吸脱附以及积炭类型等均依赖于助剂的种类(K, Na和S等)、浓度及其与金属之间的作用方式。为了有效改善产物分布、提高低碳烯烃选择性，催化剂的开发设计是重点。
发明内容
本发明针对现有技术中存在的缺点，从钙钛矿催化剂为出发点，通过乙醇钾、叔丁醇钾处理LaFeMnO3，增加催化剂碱性位点，较大程度上促进CO的吸附和解离。
本发明催化剂具有适宜的CO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。
为了实现本发明的上述目的，本发明采用的技术方案如下：
本发明催化剂经乙醇钾、叔丁醇钾的至少一种处理；处理方式是将乙醇钾、叔丁醇钾的至少一种引入催化剂前驱体或催化剂前驱体凝胶中；催化剂前驱体凝胶是镧、铁、锰的硝酸盐溶液与柠檬酸在80℃水浴后形成的凝胶；催化剂前驱体是凝胶经105-120℃干燥12h以上后形成的蓬松物；被处理后的催化剂前驱体在600-900℃焙烧获得目标催化剂。技术方案中，乙醇钾、叔丁醇钾的引入时，以乙醇和超声助溶，引入过程要在催化剂前驱体或催化剂前驱体凝胶处于受热状态下进行。催化剂中按摩尔比计：La：Fe=0.3-0.6，Fe：Mn=1-2， La ：K=0.2-5本发明催化剂应用于CO加氢或CO2加氢制备低碳烯烃。
技术方案中通过浸渍如钾、镁、锆、钠等元素到催化剂上，催化剂低碳烯烃选择性还会有所提高。镧元素可以由锶元素代替。
附图说明
图1是样品1的XRD图。
具体实施方式
实施例1
称取6.5g硝酸镧、10.1g硝酸铁、6.25g硝酸锰，19.2g柠檬酸，蒸馏水溶解后，溶液在 75℃水浴锅中搅拌蒸干至凝胶状后将其放于 105℃烘箱 10h 中以进一步干燥。向受热状态下干燥粉末加入0.8g乙醇钾。在70℃烘箱中干燥 10h。再将干燥粉末研磨，置于马弗炉中，自室温以 10℃/min 的速率升温至450℃并恒温 1h ，随后继续以 5℃/min 的速率升温至780℃，保温 4h 后取出冷却收集，研磨后即获得催化剂样品。记为样品1。图1是样品1的XRD图，谱图说明成功制备得到了钙钛矿型LaFeMnO3。
实施例2
称取6.5g硝酸镧、10.1g硝酸铁、6.25g硝酸锰，19.2g柠檬酸，蒸馏水溶解后，溶液中加入1.6g乙醇钾。于75℃水浴锅中搅拌蒸干至凝胶状后将其放于 105℃烘箱 10h 中以进一步干燥。干燥粉末研磨，置于马弗炉中，自室温以 10℃/min 的速率升温至450℃并恒温 1h，随后继续以 5℃/min 的速率升温至 850℃，保温 4h 后取出冷却收集，研磨后即获得催化剂样品。记为样品2。
实施例3
称取6.5g硝酸镧、10.1g硝酸铁、6.25g硝酸锰，19.2g柠檬酸，蒸馏水溶解后，溶液中加入1.2g叔丁醇钾。于80℃水浴锅中搅拌蒸干至凝胶状后将其放于 105℃烘箱 10h 中以进一步干燥。干燥粉末研磨，置于马弗炉中，自室温以 10℃/min 的速率升温至450℃并恒温1h ，随后继续以 5℃/min 的速率升温至 850℃，保温 4h 后取出冷却收集，研磨后即获得催化剂样品。记为样品3。
实施例4
称取3.2g硝酸镧、10.1g硝酸铁、6.25g硝酸锰，19.2g柠檬酸，蒸馏水溶解后，溶液中加入1.2g叔丁醇钾。于80℃水浴锅中搅拌蒸干至凝胶状后将其放于 105℃烘箱 10h 中以进一步干燥。干燥粉末研磨，置于马弗炉中，自室温以 10℃/min 的速率升温至450℃并恒温1h ，随后继续以 5℃/min 的速率升温至900℃，保温 4h 后取出冷却收集，研磨后即获得催化剂样品。记为样品4。
实施例5
称取10.82g硝酸镧、5g硝酸铁、12g硝酸锰，19.2g柠檬酸，蒸馏水溶解后，溶液在 85℃水浴锅中搅拌蒸干至凝胶状后将其放于 105℃烘箱 10h 中以进一步干燥。向受热状态下干燥粉末加入2.4g叔丁醇钾。在120℃烘箱中干燥 10h。再将干燥粉末研磨，置于马弗炉中，自室温以 10℃/min 的速率升温至400℃并恒温 1h ，随后继续以 5℃/min 的速率升温至800℃，保温 4h 后取出冷却收集，研磨后即获得催化剂样品。记为样品5。
实施例6
称取10.82g硝酸镧、5g硝酸铁、12g硝酸锰，19.2g柠檬酸，蒸馏水溶解后，溶液在 85℃水浴锅中搅拌蒸干至凝胶状后将其放于 105℃烘箱 10h 中以进一步干燥。向受热状态下干燥粉末加入2.4g叔丁醇钾。在120℃烘箱中干燥 10h。置于马弗炉中，自室温以 10℃/min的速率升温至400℃并恒温 1h ，随后继续以 5℃/min 的速率升温至 800℃，保温 4h 后取出冷却收集，研磨后，按照2%质量分数称取碳酸镁，浸渍到样品中，得2%Mg改性的催化剂样品。得催化剂样品。记为样品6。
实施例7
称取10.82g硝酸镧、5g硝酸铁、12g硝酸锰，19.2g柠檬酸，蒸馏水溶解后，溶液在 85℃水浴锅中搅拌蒸干至凝胶状后将其放于 105℃烘箱 10h 中以进一步干燥。向受热状态下干燥粉末加入2.4g叔丁醇钾。在120℃烘箱中干燥 10h。置于马弗炉中，自室温以 10℃/min的速率升温至400℃并恒温 1h ，随后继续以 5℃/min 的速率升温至 800℃，保温 4h 后取出冷却收集，研磨后，按照2%质量分数称取碳酸钠，浸渍到样品中，得2%Na改性的催化剂样品。记为样品7。
实施例8
称取10.82g硝酸镧、10.1gg硝酸铁、12g硝酸锰，19.2g柠檬酸，蒸馏水溶解后，溶液在85℃水浴锅中搅拌蒸干至凝胶状后将其放于 105℃烘箱 10h 中以进一步干燥。向受热状态下干燥粉末加入2.4g叔丁醇钾。在120℃烘箱中干燥 10h。置于马弗炉中，自室温以 10℃/min 的速率升温至400℃并恒温 1h ，随后继续以 5℃/min 的速率升温至 800℃，保温4h 后取出冷却收集，研磨后，按照2%质量分数称取碳酸钾，浸渍到样品中， 得2%K改性的催化剂样品。记为样品8。
实施例9
称取10.82g硝酸镧、10.1g硝酸铁、12g硝酸锰，19.2g柠檬酸，蒸馏水溶解后，溶液在 85℃水浴锅中搅拌蒸干至凝胶状后将其放于 105℃烘箱 10h 中以进一步干燥。向受热状态下干燥粉末加入2.4g叔丁醇钾。在120℃烘箱中干燥 10h。置于马弗炉中，自室温以 10℃/min 的速率升温至400℃并恒温 1h ，随后继续以 5℃/min 的速率升温至 800℃，保温 4h后取出冷却收集，研磨后，按照5%质量分数称取碳酸钾，浸渍到样品中，得5%K改性的催化剂样品。记为样品9。
实施例10
称取10.82g硝酸镧、10.1g硝酸铁、12g硝酸锰，19.2g柠檬酸，蒸馏水溶解后，溶液在 85℃水浴锅中搅拌蒸干至凝胶状后将其放于 105℃烘箱 10h 中以进一步干燥。向受热状态下干燥粉末加入2.4g叔丁醇钾。在120℃烘箱中干燥 10h。干燥后将粉末置于管式炉，氮气保护下，按10℃/min 的速率升温，400℃保温1h后，在升至800℃保温4h，冷却后研磨，按照10%质量分数称取碳酸钾，浸渍到样品中，得10%K改性的催化剂样品。记为样品10。
催化剂性能测试与表征：
为了使催化剂更好地反应，不堵塞反应管，将本发明上述实施例1～10制备的催化剂均制成20～40目的催化剂颗粒。
本发明采用微型固定床反应器对催化剂进行评价，工艺条件为20～40目催化剂0.5～5 mL，反应温度280～400°C，反应压力0.5～8 MPa，原料气H2/CO=1或2，空速为500～5000·h-1。
例如，在微型固定床反应器中对实施例1制备的催化剂进行性能评价，具体操作步骤如下：称取1.0 mL 实施例1制备的样品催化剂装入反应管中部恒温区，原料气H2/CO=2，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。利用《煤基费托合成尾气中H2、N2、CO、CO2和C1～C8烃的测定和气相色谱法》甲烷关联法，计算出CO转化率于各组份物质选择性。
表1为本发明上述实施例1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1可以看出所制样品使CO转化率提高，在产物分布中，烃类产物变化明显。本发明各实施例制备催化剂中，均表现出良好的CO加氢性能，低碳烯烃选择性保持在50%以上，烯烷比（O/P）可达5.6。
表1实施例1～10制备的样品加氢催化反应工艺参数及性能测试结果对比表
| 催化剂 | CO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 | 10.54 | 21.45 | 20.12 | 47.22 | 11.21 | 0.43 |
| 样品2 | 19.25 | 26.41 | 40.21 | 16.54 | 16.84 | 2.43 |
| 样品3 | 15.45 | 25.54 | 41.68 | 20.66 | 12.12 | 2.02 |
| 样品4 | 17.67 | 24.98 | 40.53 | 16.08 | 18.41 | 2.52 |
| 样品5 | 18.54 | 21.54 | 40.24 | 26 | 12.22 | 1.55 |
| 样品6 | 20.68 | 26.24 | 48.54 | 8.82 | 16.4 | 5.50 |
| 样品7 | 24.78 | 25.37 | 50.45 | 9.07 | 15.11 | 5.56 |
| 样品8 | 26.41 | 24.58 | 52.58 | 9.62 | 13.22 | 5.47 |
| 样品9 | 27.82 | 20.34 | 54.45 | 10.73 | 14.48 | 5.07 |
| 样品10 | 26.88 | 21.12 | 57.63 | 10.27 | 10.98 | 5.61 |
Claims (4)
1.一种钙钛矿催化剂的制备方法和应用，其特征在于：
所述催化剂经乙醇钾、叔丁醇钾的至少一种处理；处理方式是将乙醇钾、叔丁醇钾的至少一种引入催化剂前驱体或催化剂前驱体凝胶中；
所述催化剂前驱体凝胶是镧、铁、锰的硝酸盐溶液与柠檬酸在80℃水浴后形成的凝胶；所述催化剂前驱体是凝胶经105-120℃干燥12h以上后形成的蓬松物；
被处理后的催化剂前驱体在600-900℃焙烧获得目标催化剂。
2.根据权利要求1所述的一种钙钛矿催化剂的制备方法，其特征在于所述方法在于乙醇钾、叔丁醇钾的引入时，以乙醇和超声助溶，引入过程要在催化剂前驱体或催化剂前驱体凝胶处于受热状态下进行。
3.根据权利要求1所述的一种钙钛矿催化剂的应用，其特征在于所述催化剂应用于CO加氢或CO2加氢制备低碳烯烃。
4.根据权利要求1所述的一种钙钛矿催化剂的制备方法，其特征在于所述催化剂中按摩尔比计：La：Fe=0.3-0.6，Fe：Mn=1-2， La ：K=0.2-5。
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| CN102039130A (zh) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | 一种用于含氧气的烯烃物料的选择加氢催化剂、其制备方法及其应用 |
| CN103599788A (zh) * | 2013-11-01 | 2014-02-26 | 中国石油化工股份有限公司 | 一种用于co加氢的钴基催化剂及其制备方法和应用 |
| CN103611540A (zh) * | 2013-11-01 | 2014-03-05 | 中国石油化工股份有限公司 | 一种用于co加氢的催化剂及其制备方法和应用 |
| CN104437504A (zh) * | 2014-11-14 | 2015-03-25 | 宁夏大学 | 一种co2高效转化制低碳烯烃的催化剂 |
| CN108993466A (zh) * | 2018-08-07 | 2018-12-14 | 中国科学院地球环境研究所 | 一种三维有序大孔钛酸盐及其原位自牺牲制备方法 |
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