CN112934230B - 低Pt型长链烷烃脱氢催化剂、其制备方法及应用 - Google Patents
低Pt型长链烷烃脱氢催化剂、其制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种低Pt型长链烷烃脱氢催化剂、其制备方法及应用。其中,该催化剂包括载体及负载在载体上的Pt、Ni、Fe和碱金属或其氧化物,其中,以元素质量计,Pt的负载量为0.05~0.6%。本发明的催化剂采用Pt‑Ni‑Fe作为复合活性组分,碱金属为助剂,可有效降低Pt的负载量,同时具有良好的长链正构烷烃脱氢催化活性和稳定性。
Description
技术领域
本发明涉及催化技术领域,具体而言,涉及一种低Pt型长链烷烃脱氢催化剂、其制备方法及应用。
背景技术
长链烷基苯是生产洗涤剂和阴离子表面活性剂烷基苯磺酸盐的主要原料,同时也可作为润滑油和导热油的基础油。在工业生产上,长链烷基苯主要通过长链烷烃脱氢-烷基化工艺生产,其占全球烷基苯产量的70%以上。该技术路线的关键步骤是长链烷烃脱氢制备直链单烯烃,其中长链烷烃脱氢催化剂是这一步骤的核心。直链烷基苯磺酸盐最早由美国UOP公司在20世纪60年代开发的基于Pt催化剂的长链烷烃催化脱氢工艺合成生产。
目前,广泛研究和使用的长链烷烃脱氢催化剂主要为Pt-Sn双金属及Pt-Sn改性的多金属催化剂。如美国专利:US3843560,US3903191,US3531544,US3647719,US4000210,US4046715,US4133842描述的烷烃脱氢催化剂为Pt-Sn双金属体系,并以碱金属为酸度调节剂,其中Pt负载量约为0.5%。
欧洲专利EP0248130A1描述的脱氢催化剂以铂族金属为活性组分、IVA族金属和碱金属为助剂。
英国专利GB1456820描述的C6~C16直链烷烃脱氢制单烯烃催化剂以MgO为载体,通过浸渍法负载贵金属Pt、Pd、Au、Ir、Ru、Rh或Os。
中国专利CN87101513A公开的可用于C10~C13正构烷烃脱氢催化剂由双孔分布的大孔γ-Al2O3负载Pt-Sn-Li-S制得。
中国专利CN1088482A公开了饱和烷烃脱氢催化剂,以大孔径γ-Al2O3为载体,铂、锡、钠为负载组分,该催化剂可用于C6~C16正构烷烃的脱氢制单烯烃的反应过程。
中国专利CN1031946A公开了一种脱氢催化剂,该催化剂由多孔固态颗粒载体形成,载体上沉积有铂、锡、铊,以及一种碱金属,占催化剂总重量的比例分别为:0.05~1%,0.1~1%,0.1~1%和0~1%,这种催化剂可用于含有9至20个碳原子的直链烷烃脱氢制烯烃的反应过程。
中国专利CN1201715A公开的饱和烷烃脱氢催化剂的组分为0.2~0.6%的Pt、0.4~1.0%的Sn和0.1~1.0%的K,其余为γ-Al2O3,该催化剂用于C10~C14正构烷烃的脱氢反应。
已见报道的长链烷烃脱氢制单烯烃的催化剂主要以贵金属Pt为活性组分,Sn及其他金属为助剂,其中Pt含量较高,使得催化剂成本较高。目前为止,还没有低Pt载量、高活性的长链烷烃脱氢催化剂的有关报道。
牛津大学的Jie等(Angew.Chem.Int.,Ed.2017,56:10170)报道了NiFe/SiC催化剂在微波条件下具有使液态烷烃快速脱氢的性能,但主要发生深度脱氢,形成积炭,因此该催化剂不适用于长链烷烃脱氢制备单烯烃的反应过程。
发明内容
本发明旨在提供一种低Pt型长链烷烃脱氢催化剂、其制备方法及应用,以提供一种成本较低的长链烷烃脱氢催化剂。
为了实现上述目的,根据本发明的一个方面,提供了一种低Pt型长链烷烃脱氢催化剂。该催化剂包括载体及负载在载体上的Pt、Ni、Fe和碱金属或其氧化物,其中,以元素质量计,Pt的负载量为0.05~0.6%。
进一步地,载体为大孔氧化铝载体。
进一步地,大孔氧化铝载体的总孔容为1.0~2.5mL/g、堆积密度为0.2~0.5g/mL、比表面积为100~300m2/g。
进一步地,以元素质量计,Ni的含量为0.5~10.0%,Fe的含量为0.25~5.0%,碱金属的含量为0.25~2.0%。
进一步地,碱金属为钾。
根据本发明的另一方面,提供了一种上述低Pt型长链烷烃脱氢催化剂的制备方法。该制备方法包括以下步骤:S1,将载体浸渍于含有Pt、Ni、Fe和碱金属的可溶性盐的水溶液,然后烘干、焙烧,得到初级催化剂;S2,对初级催化剂进行水洗,得到次级催化剂;以及S3,将次级催化剂在氢气中进行还原,得到低Pt型长链烷烃脱氢催化剂。
进一步地,S1中,将载体浸渍于含有Pt、Ni、Fe和碱金属的可溶性盐的水溶液为:将载体分别浸渍于含有Pt、Ni、Fe和碱金属的可溶性盐的水溶液,或含有两种或两种以上金属对应的可溶性盐的混合溶液中;优选的,S1中焙烧的温度为300~600℃。
进一步地,S2中的水洗包括:将初级催化剂在水蒸气-空气混合气中300~600℃水洗1~8小时;优选的,水蒸气在水蒸气-空气混合气中的体积百分含量为10~50%。
进一步地,S3中还原包括:将次级催化剂在含水量小于20ppm、含氧量小于10ppm的氢气中400~600℃还原1~8小时。
根据本发明的再一方面,提供了一种低Pt型长链烷烃脱氢催化剂在长链正构烷烃脱氢制取单烯烃的反应中的应用。
进一步地,长链正构烷烃为C10~C20的正构烷烃。
本发明的催化剂采用Pt-Ni-Fe作为复合活性组分,碱金属为助剂,可有效降低Pt的负载量,同时具有良好的长链正构烷烃脱氢催化活性和稳定性。
具体实施方式
需要说明的是,在不冲突的情况下,本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
根据本发明一种典型的实施方式,提供一种低Pt型长链烷烃脱氢催化剂。该催化剂包括载体及负载在载体上的Pt、Ni、Fe和碱金属或其氧化物,其中,以元素质量计,Pt的负载量为0.05~0.6%。其中,负载量是指某成分占整个催化剂的比例。本发明的催化剂采用Pt-Ni-Fe作为复合活性组分,碱金属为助剂,可有效降低Pt的负载量,同时具有良好的长链正构烷烃脱氢催化活性和稳定性。
在本发明中,常规的催化剂载体可用于本发明的激素方案中,优选的,大孔氧化铝载体与本发明中的活性组分配合使用,性能最优。更优选的,大孔氧化铝载体的总孔容为1.0~2.5mL/g、堆积密度为0.2~0.5g/mL、比表面积为100~300m2/g。具有此性能指标的大孔氧化铝的反应物的扩散阻力小、容炭能力强、催化剂稳定性好,特别适合于本发明的技术方案。
根据本发明一种典型的实施方式,以元素质量计,Ni的含量为0.5~10.0%,Fe的含量为0.25~5.0%,碱金属的含量为0.25~2.0%。Pt-Ni-Fe作为复合活性组分,碱金属作为助剂,进一步讲,碱金属的作用为调节催化剂酸碱性,在此范围内催化剂具有适于低Pt型长链烷烃脱氢的最优酸碱性。
在本发明中,所有碱金属均可以作为助剂,但钾作为助剂性能较优,酸碱调节作用明显,且可起到Pt原子的几何隔离作用,抑制Pt烧结。
根据本发明一种典型的实施方式,提供一种上述低Pt型长链烷烃脱氢催化剂的制备方法。该制备方法包括以下步骤:S1,将载体浸渍于含有Pt、Ni、Fe和碱金属的可溶性盐的水溶液,然后烘干、焙烧,得到初级催化剂;S2,对初级催化剂进行水洗,得到次级催化剂;以及S3,将次级催化剂在氢气中进行还原,得到低Pt型长链烷烃脱氢催化剂。
优选的,S1中,将载体浸渍于含有Pt、Ni、Fe和碱金属的可溶性盐的水溶液为:将载体分别浸渍于含有Pt、Ni、Fe和碱金属的可溶性盐的水溶液,或含有两种或两种以上金属对应的可溶性盐的混合溶液中;更优选的,S1中焙烧的温度为300~600℃。此温度范围内催化剂具有最佳活性,温度过低活性组分难以完全分解为氧化物,不能稳定固载于载体上;温度过高,活性组分烧结。
优选的,S2中的水洗包括:将初级催化剂在水蒸气-空气混合气中300~600℃水洗1~8小时;以洗氯,降低催化剂酸性。更优选的,水蒸气在水蒸气-空气混合气中的体积百分含量为10~50%。因为水蒸气含量对洗氯结果有重要影响,将水蒸气含量控制在此范围内能够达到优良的效果。
本发明的催化剂使用条件为还原性气氛,催化剂使用前需要还原,还原温度由活性组分的还原温度区间决定。在本发明一实施方式中,S3中还原包括:将次级催化剂在含水量小于20ppm、含氧量小于10ppm的氢气中400~600℃还原1~8小时。
根据本发明一种典型的实施方式,提供上述低Pt型长链烷烃脱氢催化剂在长链正构烷烃脱氢制取单烯烃的反应中的应用,其中,长链正构烷烃为C10~C20的正构烷烃。
下面将结合实施例进一步说明本发明的有益效果。
实施例1
催化剂制备1
催化剂的载体是根据中国专利CN104907103A制备的球形γ-Al2O3,其技术规格为:
比表面积:205m2/g
总孔体积:1.71mL/g
堆积密度:0.28g/mL
吸水率:2.0mL/g
颗粒尺寸:1.5~2.5mm
将10g这种γ-Al2O3真空等体积浸渍于20mL含有0.08g氯铂酸、0.43g氯化镍和0.29g氯化铁的混合溶液中,经干燥后,于500℃焙烧2小时。冷却后,进一步真空等体积浸渍于20mL含有0.14g氯化钾的水溶液中,经干燥后,于500℃焙烧2小时,之后在水蒸气含量为10%的水蒸气-空气混合气中500℃水洗8h。经氢气气氛下400℃还原2小时后,得到组分含量为Pt0.3%、Ni 2.0%、Fe 1.0%和K 0.75%的长链烷烃脱氢催化剂,记为Cat-1。
实施例2
催化剂制备2
将10g实施例1中所述的γ-Al2O3真空等体积浸渍于20mL含有0.14g氯化钾、0.43g氯化镍和0.29g氯化铁的混合溶液中,经干燥后,于500℃焙烧2小时。冷却后,进一步真空等体积浸渍于20mL含有0.08g氯铂酸的水溶液中,经干燥后,于500℃焙烧2小时,之后在水蒸气含量为10%的水蒸气-空气混合气中500℃水洗8h。经氢气气氛下490℃还原2小时后,得到组分含量为Pt 0.3%、Ni 2.0%、Fe 1.0%和K 0.75%的长链烷烃脱氢催化剂,记为Cat-2。
实施例3
催化剂制备3
将10g实施例1中所述的γ-Al2O3真空等体积浸渍于20mL含有0.43g氯化镍和0.29g氯化铁的混合溶液中,经干燥后,于600℃焙烧2小时。冷却后,进一步真空等体积浸渍于20mL含有0.08g氯铂酸的水溶液中,经干燥后,于520℃焙烧2小时。冷却后,进一步真空等体积浸渍于20mL含有0.14g氯化钾的水溶液中,经干燥后,于300℃焙烧2小时,之后在水蒸气含量为50%的水蒸气-空气混合气中300℃水洗8h。经氢气气氛下400℃还原2小时后,得到组分含量为Pt 0.3%、Ni 2.0%、Fe 1.0%和K 0.75%的长链烷烃脱氢催化剂,记为Cat-3。
实施例4
催化剂制备4
将10g实施例1中所述的γ-Al2O3真空等体积浸渍于20mL含有0.053g氯铂酸、0.33g氯化镍和0.44g氯化铁的混合溶液中,经干燥后,于500℃焙烧2小时。冷却后,进一步真空等体积浸渍于20mL含有0.093g氯化钾的水溶液中,经干燥后,于500℃焙烧2小时,之后在水蒸气含量为20%的水蒸气-空气混合气中600℃水洗3h。经氢气气氛下600℃还原2小时后,得到组分含量为Pt 0.2%、Ni 1.5%、Fe 1.5%和K 0.5%的长链烷烃脱氢催化剂,记为Cat-4。
实施例5
催化剂制备5
将10g实施例1中所述的γ-Al2O3真空等体积浸渍于20mL含有0.013g氯铂酸、2.2g氯化镍和0.073g氯化铁的混合溶液中,经干燥后,于500℃焙烧2小时。冷却后,进一步真空等体积浸渍于20mL含有0.37g氯化钾的水溶液中,经干燥后,于600℃焙烧2小时,之后在水蒸气含量为50%的水蒸气-空气混合气中600℃水洗1h。经氢气气氛下490℃还原2小时后,得到组分含量为Pt 0.05%、Ni 10.0%、Fe 0.25%和K 2.0%的长链烷烃脱氢催化剂,记为Cat-5。
实施例6
催化剂制备6
将10g实施例1中所述的γ-Al2O3真空等体积浸渍于20mL含有0.013g氯铂酸、0.11g氯化镍和1.47g氯化铁的混合溶液中,经干燥后,于500℃焙烧2小时。冷却后,进一步真空等体积浸渍于20mL含有0.047g氯化钾的水溶液中,经干燥后,于500℃焙烧2小时,之后在水蒸气含量为10%的水蒸气-空气混合气中500℃水洗3h。经氢气气氛下490℃还原2小时后,得到组分含量为Pt 0.05%、Ni 0.5%、Fe 5.0%和K 0.25%的长链烷烃脱氢催化剂,记为Cat-6。
实施例7
催化剂制备7
将10g实施例1中所述的γ-Al2O3真空等体积浸渍于20mL含有0.156g氯铂酸、0.11g氯化镍和1.47g氯化铁的混合溶液中,经干燥后,于500℃焙烧2小时。冷却后,进一步真空等体积浸渍于20mL含有0.047g氯化钾的水溶液中,经干燥后,于500℃焙烧2小时,之后在水蒸气含量为10%的水蒸气-空气混合气中500℃水洗3h。经氢气气氛下490℃还原2小时后,得到组分含量为Pt 0.6%、Ni 0.5%、Fe 5.0%和K 0.25%的长链烷烃脱氢催化剂,记为Cat-7。
实施例8
催化剂制备8
将10g实施例1中所述的γ-Al2O3真空等体积浸渍于20mL含有0.013g氯铂酸、0.11g氯化镍和1.47g氯化铁的混合溶液中,经干燥后,于500℃焙烧2小时。冷却后,进一步真空等体积浸渍于20mL含有0.064g氯化钠的水溶液中,经干燥后,于500℃焙烧2小时,之后在水蒸气含量为10%的水蒸气-空气混合气中500℃水洗3h。经氢气气氛下490℃还原2小时后,得到组分含量为Pt 0.05%、Ni 0.5%、Fe 5.0%和Na 0.25%的长链烷烃脱氢催化剂,记为Cat-8。
实施例9
催化剂评价
将10mL实施例1~8中制得的催化剂Cat-1~8进行长链烷烃脱氢催寿评价试验。试验以经过加氢精制的C10~C13直链烷烃为原料。试验选择较苛刻的反应条件,加速催化剂失活,以便短时间内比较催化剂性能。反应温度为490℃,反应压力0.14MPa,烷烃液时空速为20h-1,氢烃摩尔比为2.0。反应结果显示,所有催化剂的烷烃转化为单烯烃的选择性均为90~92%,具体转化率如表1所示。
表1 Cat-1~4催化长链烷烃脱氢转化率。
实施例10
对比试验1
将实施例1中所述的γ-Al2O3真空等体积浸渍于20mL含0.13g氯铂酸、锡0.17g氯化亚锡和0.14g氯化钾的混合溶液中。经烘干后,于520℃焙烧4h。经氢气气氛下490℃还原2小时后,得到组分含量为Pt 0.5%、Sn 1.0%和K 0.75%的长链烷烃脱氢催化剂,记为Cat-db1。该催化剂的长链烷烃脱氢催寿评价条件与实施例9中完全一致。催化剂的烷烃转化为单烯烃的选择性为91%,具体转化率如表2所示。
实施例11
对比试验2
将实施例1中所述的γ-Al2O3真空等体积浸渍于20mL含0.053g氯铂酸、锡0.068g氯化亚锡和0.093g氯化钾的混合溶液中。经烘干后,于520℃焙烧4h。经氢气气氛下490℃还原2小时后,得到组分含量为Pt 0.2%、Sn 0.4%和K 0.5%的长链烷烃脱氢催化剂,记为Cat-db2。该催化剂的长链烷烃脱氢催寿评价条件与实施例9中完全一致。催化剂的烷烃转化为单烯烃的选择性为90%,具体转化率如表2所示。
表2 Cat-db1~2催化长链烷烃脱氢转化率。
对比表1和表2中长链烷烃脱氢反应结果可知,与传统的Pt-Sn系脱氢催化剂相比,本发明的催化剂具有Pt负载量更低、活性更高,且稳定性好的优点。本发明提供的长链烷烃脱氢催化剂的技术具有良好的应用前景。
以上所述仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种低Pt型长链烷烃脱氢催化剂,其特征在于,包括载体及负载在所述载体上的Pt、Ni、Fe和碱金属或其氧化物,其中,以元素质量计,Pt的负载量为0.05~0.3%;Ni的含量为0.5~10.0%,Fe的含量为0.25~5.0%,碱金属的含量为0.25~2.0%;所述载体为大孔氧化铝载体;所述大孔氧化铝载体的总孔容为1.0~2.5mL/g、堆积密度为0.2~0.5g/mL、比表面积为100~300m2/g。
2.根据权利要求1所述的低Pt型长链烷烃脱氢催化剂,其特征在于,所述碱金属为钾。
3.一种如权利要求1至2中任一项所述的低Pt型长链烷烃脱氢催化剂的制备方法,其特征在于,包括以下步骤:
S1,将载体浸渍于含有Pt、Ni、Fe和碱金属的可溶性盐的水溶液,然后烘干、焙烧,得到初级催化剂;
S2,对所述初级催化剂进行水洗,得到次级催化剂;以及
S3,将所述次级催化剂在氢气中进行还原,得到所述低Pt型长链烷烃脱氢催化剂。
4.根据权利要求3所述的制备方法,其特征在于,所述S1中,所述将载体浸渍于含有Pt、Ni、Fe和碱金属的可溶性盐的水溶液为:将所述载体分别浸渍于含有Pt、Ni、Fe和碱金属的可溶性盐的水溶液,或含有两种或两种以上金属对应的可溶性盐的混合溶液中。
5.根据权利要求4所述的制备方法,其特征在于,所述S1中焙烧的温度为300~600℃。
6.根据权利要求3所述的制备方法,其特征在于,所述S2中的水洗包括:将所述初级催化剂在水蒸气-空气混合气中300~600℃水洗1~8小时。
7.根据权利要求6所述的制备方法,其特征在于,所述水蒸气在所述水蒸气-空气混合气中的体积百分含量为10~50%。
8.根据权利要求3所述的制备方法,其特征在于,所述S3中还原包括:将所述次级催化剂在含水量小于20ppm、含氧量小于10ppm的氢气中400~600℃还原1~8小时。
9.如权利要求1至2中任一项所述的低Pt型长链烷烃脱氢催化剂在长链正构烷烃脱氢制取单烯烃的反应中的应用。
10.根据权利要求9所述的应用,其特征在于,所述长链正构烷烃为C10~C20的正构烷烃。
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