CN116116453A - 一种用于丙烷脱氢制丙烯的工业分子筛限域金属催化剂的制备方法和应用 - Google Patents
一种用于丙烷脱氢制丙烯的工业分子筛限域金属催化剂的制备方法和应用 Download PDFInfo
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 78
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
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Abstract
一种用于丙烷脱氢制丙烯的工业分子筛限域金属催化剂的制备方法和应用。该催化剂以选择性脱铝的工业分子筛为载体,利用分子筛的有序孔道分布和独特笼结构以及良好的离子交换性的特点,将助剂和贵金属引入到分子筛骨架中,并引入碱金属调节催化剂表面酸碱性,再还原将活性中心引入分子筛孔道或者笼内部,制备活性中心高度分散的分子筛限域催化剂,从而实现丙烷高效脱氢制丙烯。所得催化剂反应活性及选择性高,克服现有技术中分子筛限域丙烷脱氢催化剂原位合成过程中水热时间长、水热温度高、活性中心易团聚、模版剂用量大、烧出模板剂造成环境污染等缺陷。本发明分子筛限域催化剂在丙烷脱氢制丙烯的反应中具有良好的转化率、选择性及稳定性。
Description
技术领域
本发明涉及烷烃催化转化领域,尤其涉及一种用于丙烷脱氢制丙烯的工业分子筛限域金属催化剂的制备方法和应用。
背景技术
丙烯是世界上仅次于乙烯的第二大化工原料,主要用于生产聚丙烯、丙烯腈、环氧丙烷、乙丙橡胶、尼龙66和ABS树脂等高附加值产品,被广泛应用于塑料、涂料、医药、电器、汽车等生产领域,成为我国国民经济的重要组成部分。随着经济全球化和人类现代化进程的快速发展,近年来全球丙烯需求量持续增长,使得丙烷脱氢制丙烯这一符合目标化生产理念的技术得到重视。
目前,针对丙烷直接脱氢,主要有两种催化体系。一种是以Oleflex工艺为代表的Pt基催化剂,其活性及选择性高,但易烧结失活、价格昂贵,且催化剂需频繁再生。另一种是以Cr、V、Zn、Ga等元素为代表的非贵金属催化剂,其价格低廉但活性及选择性较低、易失活,代表工艺是Catofin工艺,但Cr系催化剂有毒,需频繁再生,能耗大。因此,解决丙烷脱氢制丙烯的关键在于开发活性高、稳定性好、选择性高的催化剂。
贵金属催化剂以其良好的反应活性、选择性以及稳定性而备受重视,在精细化工、石油精制、环保、新能源等催化反应中应用广泛,近年来通过分子筛和活性中心的强金属-载体强相互作用及载体的限域作用相结合可以改善贵金属本身易烧结、亚纳米尺寸下难以稳定的劣势,但在原位合成的分子筛封装催化剂中,存在复配前驱盐较为复杂,制备过程中需要烧除有机配体的缺点,而且因其较长的水热合成时间和较大的模板剂用量导致了催化剂大批量合成成本较高,且烧除模板剂过程中会造成大量的能源消耗以及废水废气污染。
因此,开发一种制备工艺简单的通过向选择性改性的分子筛骨架中引入活性组分以优化分子筛催化剂制备过程从而提高贵金属基催化剂的催化反应活性的方法十分必要。
发明内容
本发明的目的在于解决现有技术中的上述问题,提供一种用于丙烷脱氢制丙烯的工业分子筛限域金属催化剂的制备方法和应用,制备方法简单,催化性能优异;利用分子筛比表面积大、稳定性好、离子交换性好等特点,将分子筛在维持拓扑结构的基础上进行改性预处理,将金属助剂、贵金属组分、碱金属前驱盐分别引入分子筛拓扑结构后直接还原,通过改性后的分子筛骨架缺陷锚定和分散活性组分,同时通过限域作用提高催化剂金属与载体之间的相互作用,将所述工业分子筛限域催化剂应用于低碳烷烃脱氢制烯烃优化反应性能。
为达到上述目的,本发明采用如下技术方案:
一种用于丙烷脱氢制丙烯的工业分子筛限域金属催化剂的制备方法,包括以下步骤:
1)分子筛载体改性预处理:将工业分子筛在加热搅拌下进行酸处理改性,过滤、洗涤、干燥、焙烧,得到选择性脱铝分子筛;
2)将步骤1)所得脱铝分子筛与第一金属前驱体溶液混合,搅拌、过滤、干燥;所述第一金属采用Zn、Sn、Ga、Cu、In、Na、K、Cs、Sr中的至少一种;
3)将步骤2)所得样品研磨,加入第二金属前驱体溶液,搅拌、过滤、干燥;所述第二金属采用Pt、Pd、Rh、Ir中的至少一种;
4)将步骤3)所得样品研磨,与碱金属前驱体溶液混合,加热搅拌,过滤、干燥、还原,得到用于丙烷脱氢制丙烯的工业分子筛限域金属催化剂,按质量比计,第一金属的含量为0.2%~10%,第二金属的含量为0.1%~5%,其余为选择性脱铝分子筛。
步骤1)中,所述工业分子筛采用ZSM-5、Y或Beta工业分子筛;所述ZSM-5分子筛的原始硅铝摩尔比为20~200;所述Y分子筛的原始硅铝摩尔比为5~40;所述Beta分子筛的原始硅铝摩尔比为10~150。
步骤1)中,所用酸为硝酸、硫酸、盐酸、磷酸中的至少一种,浓度为1~30M;加热温度为40~220℃;酸处理时间为2~16h。
步骤1)中,所述焙烧的温度为500~700℃,时间为2~10h。
步骤2)中,所用第一金属前驱体为硝酸盐、盐酸盐、硫酸盐、醋酸盐、氧化物、氢氧化物中的至少一种。
步骤3)中,所用第二金属前驱体为硝酸盐、盐酸盐、硫酸盐、醋酸盐、氧化物、氢氧化物中的至少一种。
步骤4)中,所用碱金属前驱体为硝酸盐、盐酸盐、硫酸盐、醋酸盐、氧化物、氢氧化物中的至少一种。
步骤4)中,加热温度为30~100℃,时间为1~5h;还原温度为400~700℃,时间为4~10h。
所述工业分子筛限域金属催化剂用于丙烷脱氢制丙烯,在微分固定床反应器中进行,反应前用还原性气体或保护性气体对催化剂进行预处理,预处理温度为400~600℃,处理时间为0.5~4h,然后通入原料气进行丙烷脱氢实验,反应温度为500~650℃,反应压力为0~0.2MPa;所述原料气中,氮气和丙烷的摩尔比为0.5~2,丙烷的质量空速为1~100h-1。
相对于现有技术,本发明技术方案取得的有益效果是:
硅铝分子筛具有丰富拓扑结构的同时,也具有良好的离子交换性,根据本发明方法通过在改性分子筛上构建缺陷后引入活性组分制备工业分子筛限域的丙烷脱氢催化剂,与原位合成的方法相比,因其避免了较长的水热合成过程而采用离子交换的方法,通过无需复配有机模板剂的简单前驱盐进行离子交换,一方面提高了活性组分和催化剂间的相互作用,且一定程度上延缓了活性中心的团聚;另一方面催化剂制备过程中直接还原无需焙烧也降低了催化剂合成过程中的能源消耗,减轻了环境污染,所合成的工业分子筛限域催化剂也具有良好的丙烷脱氢性能。
附图说明
图1为实施例1中Sn1Pt0.5@ZSM-5催化剂的丙烷脱氢性能测试结果;
图2为实施例1Sn1Pt0.5@ZSM-5催化剂的TEM表征图;
图3为实施例2Zn4Pt0.5@Y催化剂的TEM表征图;
图4为实施例3Ga2Ir0.4@Beta催化剂的TEM表征图;
图5为实施例2Zn4Pt0.5@Y催化剂的切片样品制备及TEM表征图。
具体实施方式
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚、明白,以下结合附图和实施例,对本发明做进一步详细说明。
实施例1
本实施例的分子筛限域金属催化剂为Sn1Pt0.5@ZSM-5,Sn负载量为1%,Pt负载量为0.5%,ZSM-5分子筛脱铝前硅铝摩尔比为62。
本实施例中工业分子筛限域金属催化剂的制备方法及应用,包括以下步骤:
1)称取工业ZSM-5分子筛5g于250mL圆底烧瓶中,加入150g 13M的浓硝酸进行酸处理脱铝,140℃油浴搅拌,使ZSM-5分子筛在浓硝酸中回流4h;回流结束后冷却至室温,抽滤、洗涤、干燥、焙烧,得脱铝ZSM-5分子筛;
2)称取1.5g脱铝ZSM-5分子筛于500mL烧杯中,加入300mL去离子水室温搅拌30min,后加入0.0445g SnCl4.5H2O,室温搅拌12h,抽滤,60℃干燥;
3)将步骤2)中所得样品研磨后加入300mL去离子水中,室温搅拌30min,加入0.015g硝酸四氨合铂,室温搅拌12h,抽滤,60℃干燥;
4)将步骤3)中所得样品研磨,与0.04M的硝酸钠溶液混合,80℃水浴搅拌2h,抽滤,干燥。
5)取0.3gSn1Pt0.5@ZSM-5催化剂装入石英反应管中,20mL/min的纯氢气进行500℃1h还原处理,结束后,关闭氢气,继续在15mL/min氮气气氛下10℃/min升温至550℃,后通入20mL/min的丙烷原料气,其中按体积比计,C3H8:N2=1:3,反应压力为0.1MPa,进行丙烷脱氢制丙烯的催化性能评价,催化剂评价结果见表1。
表1
时间/h | 0.5 | 1 | 1.5 | 2 | 3 | 4 | 5 | 6 |
丙烷转化率/% | 43 | 42.5 | 42.2 | 42.0 | 41.7 | 41.3 | 41.1 | 40.9 |
丙烯选择性/% | 98 | 98.2 | 98.4 | 98.5 | 98.8 | 98.9 | 98.9 | 98.9 |
如图1所示为Sn1Pt0.5@ZSM-5催化剂的丙烷脱氢测试结果,可以看出该催化剂活性高,稳定性好,反应50h未发现失活现象。结合图2中Sn1Pt0.5@ZSM-5催化剂的TEM表征图,发现其金属活性位点高度分散于ZSM-5分子筛骨架中,这使得金属在高温条件下不易发生团聚,从而提高了催化剂的活性及稳定性。
实施例2
本实施例的分子筛限域金属催化剂为Zn4Pt0.5@Y,Zn负载量为4%,Pt负载量为0.5%,Y分子筛脱铝前硅铝摩尔比为13。
本实施例中工业分子筛限域金属催化剂的制备方法及应用,包括以下步骤:
1)称取工业Y分子筛5g于250mL圆底烧瓶中,加入150g 11M的浓硝酸进行酸处理脱铝,110℃油浴搅拌,使Y分子筛在浓硝酸中回流4h;回流结束后冷却至室温,抽滤、洗涤、干燥、焙烧,得脱铝Y分子筛;
2)称取1g脱铝Y分子筛于500mL烧杯中,加入200mL去离子水室温搅拌30min,之后加入0.23gZn(NO3)2,室温搅拌12h,抽滤,60℃干燥;
3)将步骤2)中所得样品研磨后加入200mL去离子水中,室温搅拌30min,之后加入0.01g硝酸四氨合铂,室温搅拌12h,抽滤后60℃干燥;
4)将步骤3)中所得样品研磨后,与0.04M的硝酸钠溶液混合,80℃水浴搅拌2h,抽滤,干燥。
5)取0.3gZn4Pt0.5@Y催化剂装入石英反应管中,按实施例1中步骤5)的催化剂还原、预处理及反应条件对催化剂进行评价,评价结果见表2。
表2
时间/h | 0.5 | 1 | 1.5 | 2 | 3 | 4 | 5 | 6 |
丙烷转化率/% | 35.5 | 34.3 | 33.8 | 33.4 | 33.1 | 32.7 | 32.4 | 32.1 |
丙烯选择性/% | 97.5 | 97.7 | 97.8 | 98 | 98.2 | 98.3 | 98.5 | 98.5 |
如图3及图5所示分别为Zn4Pt0.5@Y催化剂的TEM表征图和切片样品制备及TEM表征图,从两图中可以看出金属活性组分成功限域在Y分子筛骨架中,结合表2中性能评价结果,该限域结构使得催化剂丙烷转化率高,丙烯选择性高达98%左右,具有良好的催化稳定性。实施例3
本实施例的分子筛限域金属催化剂为Ga2Ir0.4@Beta,Ga负载量为2%,Ir的负载量为0.4%,Beta分子筛脱铝前硅铝摩尔比为60。本实施例中工业分子筛限域金属催化剂的制备方法,包括以下步骤:1)称取工业Beta分子筛5g于250mL圆底烧瓶中,加入150g 6M的浓硝酸进行酸处理脱铝,140℃的油浴锅中搅拌,使Beta分子筛在浓硝酸中回流4h;回流结束后冷却至室温,抽滤、洗涤、干燥,最后焙烧得脱铝Beta分子筛;2)称取1g脱铝Beta分子筛于500mL烧杯中,加入200mL去离子水,室温搅拌30min,之后加入0.153gGa(NO3)2,室温搅拌12h,抽滤后60℃干燥;3)将步骤2)中所得样品研磨后加入200mL去离子水中,室温搅拌30min,之后加入0.01g三氯化铱,室温搅拌12h,抽滤后60℃干燥;4)将步骤3)中所得样品研磨后,与0.03M的硝酸钠溶液混合,80℃水浴搅拌2h,抽滤干燥。
5)取0.3gGa2Ir0.4@Beta催化剂装入石英反应管中,按实施例1中步骤5)的催化剂还原、预处理及反应条件对催化剂进行评价,评价结果见表3。
表3
时间/h | 0.5 | 1 | 1.5 | 2 | 3 | 4 | 5 | 6 |
丙烷转化率/% | 22.8 | 22.2 | 21.7 | 21.2 | 20.5 | 20.1 | 19.7 | 19.2 |
丙烯选择性/% | 95.6 | 95.8 | 96.5 | 97.2 | 97.4 | 97.5 | 97.7 | 97.7 |
如图4所示为Ga2Ir0.4@Beta催化剂的TEM表征图,图中清晰显示了该催化剂的限域结构,金属活性位点在分子筛骨架中分散均匀,保证了催化剂在反应过程中的高活性和稳定性。
Claims (10)
1.一种用于丙烷脱氢制丙烯的工业分子筛限域金属催化剂的制备方法,其特征在于包括以下步骤:
1)分子筛载体改性预处理:将工业分子筛在加热搅拌下进行酸处理改性,过滤、洗涤、干燥、焙烧,得到选择性脱铝分子筛;
2)将步骤1)所得脱铝分子筛与第一金属前驱体溶液混合,搅拌、过滤、干燥;所述第一金属采用Zn、Sn、Ga、Cu、In、Na、K、Cs、Sr中的至少一种;
3)将步骤2)所得样品研磨,加入第二金属前驱体溶液,搅拌、过滤、干燥;所述第二金属采用Pt、Pd、Rh、Ir中的至少一种;
4)将步骤3)所得样品研磨,与碱金属前驱体溶液混合,加热搅拌,过滤、干燥、还原,得到用于丙烷脱氢制丙烯的工业分子筛限域金属催化剂,按质量比计,第一金属的含量为0.2%~10%,第二金属的含量为0.1%~5%,其余为选择性脱铝分子筛。
2.如权利要求1所述的一种用于丙烷脱氢制丙烯的工业分子筛限域金属催化剂的制备方法,其特征在于:步骤1)中,所述工业分子筛采用ZSM-5、Y或Beta工业分子筛;所述ZSM-5分子筛的原始硅铝摩尔比为20~200;所述Y分子筛的原始硅铝摩尔比为5~40;所述Beta分子筛的原始硅铝摩尔比为10~150。
3.如权利要求1所述的一种用于丙烷脱氢制丙烯的工业分子筛限域金属催化剂的制备方法,其特征在于:步骤1)中,所用酸为硝酸、硫酸、盐酸、磷酸中的至少一种,浓度为1~30M;加热温度为40~220℃;酸处理时间为2~16h。
4.如权利要求1所述的一种用于丙烷脱氢制丙烯的工业分子筛限域金属催化剂的制备方法,其特征在于:步骤1)中,所述焙烧的温度为500~700℃,时间为2~10h。
5.如权利要求1所述的一种用于丙烷脱氢制丙烯的工业分子筛限域金属催化剂的制备方法,其特征在于:步骤2)中,所用第一金属前驱体为硝酸盐、盐酸盐、硫酸盐、醋酸盐、氧化物、氢氧化物中的至少一种。
6.如权利要求1所述的一种用于丙烷脱氢制丙烯的工业分子筛限域金属催化剂的制备方法,其特征在于:步骤3)中,所用第二金属前驱体为硝酸盐、盐酸盐、硫酸盐、醋酸盐、氧化物、氢氧化物中的至少一种。
7.如权利要求1所述的一种用于丙烷脱氢制丙烯的工业分子筛限域金属催化剂的制备方法,其特征在于:步骤4)中,所用碱金属前驱体为硝酸盐、盐酸盐、硫酸盐、醋酸盐、氧化物、氢氧化物中的至少一种。
8.如权利要求1所述的一种用于丙烷脱氢制丙烯的工业分子筛限域金属催化剂的制备方法,其特征在于:步骤4)中,加热温度为30~100℃,时间为1~5h;还原温度为400~700℃,时间为4~10h。
9.权利要求1~8任一项制备方法所制备的工业分子筛限域金属催化剂的应用,其特征在于:用于丙烷脱氢制丙烯。
10.如权利要求9所述的应用,其特征在于:在微分固定床反应器中进行,反应前用还原性气体或保护性气体对催化剂进行预处理,预处理温度为400~600℃,处理时间为0.5~4h,然后通入原料气进行丙烷脱氢实验,反应温度为500~650℃,反应压力为0~0.2MPa。
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