CN113398925B - 一种负载铱多相催化剂及其制备方法和应用 - Google Patents
一种负载铱多相催化剂及其制备方法和应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 16
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Abstract
本发明公开了一种负载铱多相催化剂及其制备方法和应用,所述催化剂由铱和载体组成,所述载体为氧化物或水滑石。所述负载铱多相催化剂可通过浸渍法制备,制得的多相催化剂可应用于乙醇碳‑碳偶联制高级醇生物燃料。本发明制备的负载铱多相催化剂,铱分散性好;所述催化剂应用在乙醇偶联制备高级醇中反应条件温和,在较低的反应温度和反应压力条件下,获得高选择性的高级醇,丁醇选择性最高可达68.5%,高级醇的选择性最高可达88.4%。
Description
技术领域
本发明涉及一种催化剂,尤其涉及一种负载铱多相催化剂及其制备方法和应用。
背景技术
清洁高效转化可再生生物质资源制液体燃料及大宗或高值精细化学品已成为许多国家的重要发展战略。乙醇作为最重要的大宗生物质化工产品之一,可由纤维素或木薯等非粮生物质发酵获得,其在全球超过40个国家实现了工业化生产,并且以每年5%的生产速度递增。乙醇作为一种清洁的燃料,已被许多国家推广用于汽油调和组分。乙醇经催化偶联制备的高级醇,如正丁醇及更长链脂肪醇的高级醇生物燃料,与乙醇相比,这些高级醇的水溶性低、能量密度高、蒸气压力低、腐蚀性小,性质更接近烃类,与汽油的配伍性好,是更理想的汽油调和组分或单独作为汽油内燃机燃料,被认定是继乙醇之后的一种极具发展前景的新一代液体生物燃料。
尽管高级醇为更优质生物燃料,但目前尚缺乏绿色高效催化生物质平台化合物制备此类生物燃料的方法。目前正丁醇的常用生产方法为羰基合成法和发酵法。羰基合成法是工业生产正丁醇的主要方法,先用钴或铑的络合物催化丙烯、氢甲酰化反应得到正丁醛、再经加氢得正丁醇。羰基合成法催化剂价格昂贵、反应条件苛刻、工艺路线长。生物发酵法制正丁醇,将碳水化合物转化为丙酮(Acetone)、正丁醇(Butanol)和乙醇(Ethanol)等的溶剂生产技术(简称ABE技术)取得了很大的进步,但要真正实现具有经济竞争力的工业化生产,还需要进一步解决原料利用率低下、产物分离成本高等问题。催化乙醇偶联制备高级醇生物燃料,原料乙醇可由成熟的生物发酵技术和已经迈向大规模工业化的合成气制乙醇生产技术获得,工艺流程短,反应过程清洁,生产成本低,符合“绿色化学”要求,是一条可持续的生物燃料合成途径。
目前,催化乙醇偶联制备正丁醇的催化体系,前期的气固反应体系,采用碱性分子筛、碱金属氧化物、羟基磷灰石等固体酸碱催化剂,反应温度高,正丁醇选择性低,且存在高碳链有机物副产物导致催化剂易结焦失活等问题。后期发展为金属负载、掺杂或包覆的多相催化体系,采用Ni-MgAlO、Ru/MgO、Ru(Pd)/MgAlO、Cu-CeO2/AC、Cu/MgAlO、Pd@UiO等催化材料,此类体系可降低反应温度到240~300℃,提高反应初始阶段的正丁醇选择性到50~86%,但随着乙醇转化率提高,正丁醇的选择性仍处于较低水平,致使正丁醇收率较低,小于30%。可见,通过该技术无法将乙醇经济高效地定向转化为正丁醇。
钌、锰、铱等金属有机配合物和氮磷配合物等均相催化剂的开发,将正丁醇选择性提高至90%以上。但均相液相催化体系,需添加NaOH、NaOEt等强碱,且受限于贵金属配体均相催化体系中催化剂难以分离回收的限制,其实用性较低。
发明内容
发明目的:本发明的目的提供一种分散性高、反应选择性好、转化率高的负载铱多相催化剂;本发明的另一目的提供一种负载铱多相催化剂的制备方法;本发明的另一目的提供一种负载铱多相催化剂的应用。
技术方案:本发明的负载铱多相催化剂,所述催化剂由铱和载体组成,所述载体为氧化物或水滑石。
优选地,所述铱为铱盐,所述铱盐为氯化铱、氯铱酸、醋酸铱和氯铱酸钠六水合物中的一种。
优选地,所述氧化物为固体碱氧化物,所述固体碱氧化物为氧化铝、氧化镁和氧化铈中的一种。
优选地,铱的负载量为0.05%~2.0%。
优选地,铱为金属单质或多价态形态。
上述的负载铱多相催化剂的制备方法,将铱溶液滴加到载体中,超声后,研磨至干燥,然后经过真空中干燥、还原剂还原,得到负载铱多相催化剂。
上述负载铱多相催化剂在乙醇偶联制备高级醇中的应用。
进一步地,将乙醇、所述负载铱多相催化剂、磁子放入釜式反应器中,在0~2MPaN2、180~240℃条件下反应,冷凝分析得到产物。
乙醇偶联制正丁醇等高级醇的反应历程复杂,涉及亲核反应完成碳-碳偶联,需调控酸碱活性位和氢转移能力来稳定碳负或碳正中间过渡态物种,从而实现可控地获得正丁醇等高级醇类优质生物燃料。本发明的负载铱多相催化剂,通过高分散铱、载体调控催化剂酸碱活性位和金属-载体相互作用提供合适的酸碱活性位及氢转移能力,从而在低的反应温度和反应压力条件下,获得高选择性的高级醇。
有益效果:与现有技术相比,本发明具有如下显著优点:铱分散性好,丁醇选择性最高可达68.5%,高级醇的选择性最高可达88.4%;应用在乙醇偶联制备高级醇中,反应条件温和,在低的反应温度和反应压力条件下,获得高选择性的高级醇。
附图说明
图1为实施例1制备的催化剂的TEM图;
图2为实施例1制备的催化剂的粒径统计图。
具体实施方式
下面结合附图对本发明的技术方案作进一步说明。
实施例1
负载铱多相催化剂,其中铱为IrCl3,载体为镁铝水滑石载体。
制备方法:将IrCl3水溶液滴加入装有镁铝水滑石载体(MgAl-HT,Mg/Al=4)的试管中,超声0.5h;将试管中的样品转移至研钵中研磨至干燥;用硼氢化钠室温还原、洗涤、干燥,即得相应Ir/HT催化剂。
应用方法:将2%Ir/HT催化剂0.3g、4ml乙醇加入釜式反应器中,缓慢充放N2排出反应器中空气,最终充入1MPa N2,放入磁力加热装置上,在200℃搅拌加热10h,停止反应。冰水浴冷却。
应用效果:通过气相色谱分析转化率和产物选择性。乙醇转化率为32.7%,丁醇选择性为57.6%,高碳醇(C4-8脂肪醇)选择性为80.1%。
实施例2
负载铱多相催化剂,其中铱为IrCl3,载体为镁铝水滑石载体。
制备方法:将IrCl3水溶液滴加入装有镁铝水滑石载体(MgAl-HT,Mg/Al=4)的试管中,超声1h;将试管中的样品转移至研钵中研磨至干燥;用H2还原、洗涤、干燥,即得相应Ir/HT催化剂。
应用方法:将2%Ir/HT催化剂0.3g、2ml乙醇加入釜式反应器中,缓慢充放N2排出反应器中空气,最终充入1MPa N2,放入磁力加热装置上,在200℃搅拌加热10h,停止反应。冰水浴冷却。
效果测定:通过气相色谱分析转化率和产物选择性。乙醇转化率为42.3%,丁醇选择性为54.6%,高级醇选择性为79.2%。
实施例3
负载铱多相催化剂,其中铱为Na3IrCl6,载体为镁铝水滑石载体。
制备方法:将IrCl3水溶液滴加入装有镁铝水滑石载体(MgAl-HT,Mg/Al=4)的试管中,超声1h;将试管中的样品转移至研钵中研磨至干燥;用硼氢化钠室温还原、洗涤、干燥,即得相应Ir/HT催化剂。
应用方法:将2%Ir/HT催化剂0.3g、2ml乙醇加入釜式反应器中,缓慢充放N2排出反应器中空气,最终充入1MPa N2,放入磁力加热装置上,在200℃搅拌加热10h,停止反应。冰水浴冷却。
效果测定:通过气相色谱分析转化率和产物选择性。乙醇转化率为32.4%,丁醇选择性为51.4%,高级醇选择性为74.0%。
实施例4
负载铱多相催化剂,其中铱为氯铱酸,载体为镁铝水滑石载体。制备方法、应用方法和效果测定方法与实施例2相同。乙醇转化率为6.1%,丁醇选择性为48.9%,高级醇选择性为60.3%。
实施例5
负载铱多相催化剂,其中铱为氯铱酸,载体为Mg/Al为5的HT。制备方法、应用方法和效果测定方法与实施例4相同。乙醇转化率为12.5%,丁醇选择性为68.8%,高级醇选择性为81.6%。
实施例6
负载铱多相催化剂,其中铱为氯铱酸,载体为镁铝水滑石载体。与实施例4的不同之处在于,制备方法中乙醇为3ml、反应方法中充入2MPa N2,其他步骤同实施例4。乙醇转化率为30.6%,丁醇选择性为48.5%,高级醇选择性为74.8%。
实施例7
负载铱多相催化剂,其中铱为氯铱酸,载体为CeO2。制备方法、应用方法和效果测定方法与实施例4相同。乙醇转化率为6.5%,丁醇选择性为50.6%,高级醇选择性为65.8%。
实施例8
负载铱多相催化剂,其中铱为氯铱酸,载体为Mg/Al为2的HT。制备方法、应用方法和效果测定方法与实施例1相同。乙醇转化率为6.1%,乙醇转化率为12.1%,丁醇选择性为53.9%,高级醇选择性为68.9%。
实施例9
负载铱多相催化剂,其中铱为氯铱酸,载体为Mg/Al为3的HT。制备方法、应用方法和效果测定方法与实施例1相同。乙醇转化率为20.9%,丁醇选择性为49.9%,高级醇选择性为73.1%。
实施例10
负载铱多相催化剂,其中铱为氯铱酸,载体为Mg/Al为6的HT。制备方法、应用方法和效果测定方法与实施例1相同。乙醇转化率为16.1%,丁醇选择性为52.4%,高级醇选择性为72.0%。
实施例11
负载铱多相催化剂,其中铱为氯铱酸,载体为Mg2AlOx载体。制备方法、应用方法和效果测定方法与实施例1相同。乙醇转化率为24.2%,丁醇选择性为63.5%,高级醇选择性为79.1%。
实施例12
负载铱多相催化剂,其中铱为氯铱酸,载体为Mg2AlOx载体。应用方法中的反应温度改为180℃,其他制备方法、应用方法和效果测定方法的步骤与实施例11相同。乙醇转化率为17.6%,丁醇选择性为60.6%,高级醇选择性为82.5%。
实施例13
负载铱多相催化剂,其中中铱为IrCl3,载体为镁铝水滑石载体。制备方法中将铱的负载量改为0.05%,其他制备方法、应用方法和效果测定方法与实施例2相同。乙醇转化率为12.2%,丁醇选择性为50.7%,高级醇选择性为62.0%。
实施例14
负载铱多相催化剂,其中铱为氯铱酸,载体为镁铝水滑石载体。制备方法中将铱的负载量改为4%,其他制备方法、应用方法和效果测定方法与实施例4相同。乙醇转化率为21.3%,丁醇选择性为68.5%,高级醇选择性为88.4%。
实施例15
负载铱多相催化剂,其中铱为氯铱酸,载体为镁铝水滑石载体。应用方法中将反应温度改为240℃,其他制备方法、应用方法和效果测定方法与实施例4相同。乙醇转化率为31.5%,丁醇选择性为58.7%,高级醇选择性为82.4%。
实施例16
负载铱多相催化剂,其中铱为IrCl3,载体为钴铝水滑石。制备方法、应用方法和效果测定方法与实施例2相同。乙醇转化率为22.5%,丁醇选择性为46.6%,高级醇选择性为53.2%。
实施例17
负载铱多相催化剂,其中铱为IrCl3,载体为镍铝水滑石。制备方法、应用方法和效果测定方法与实施例2相同。乙醇转化率为19.5%,丁醇选择性为60.0%,高级醇选择性为90.7%。
实施例18
负载铱多相催化剂,其中铱为IrCl3,载体为镍锰水滑石。制备方法、应用方法和效果测定方法与实施例2相同。乙醇转化率为18.8%,丁醇选择性为60.9%,高级醇选择性为72.3%。
Claims (1)
1.一种负载铱多相催化剂在乙醇偶联制备高级醇中的应用,其特征在于,所述催化剂由铱和载体组成,所述载体为氧化铈或水滑石;所述铱为多价态状态;负载铱多相催化剂的制备方法为将铱溶液滴加到载体中,超声后,研磨至干燥,然后经过真空干燥、还原剂还原,得到负载铱多相催化剂;其中,铱溶液中铱源为氯化铱、氯铱酸、醋酸铱和氯铱酸钠六水合物中的一种;应用方法为:将乙醇、所述负载铱多相催化剂、磁子放入釜式反应器中,在1MPa、N2、180 或200 ℃条件下反应,冷凝分析得到高级醇。
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