CN111686709A - 一种具有特定孔结构的丙烷脱氢制丙烯负载催化剂及其制备方法 - Google Patents
一种具有特定孔结构的丙烷脱氢制丙烯负载催化剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种具有特定孔结构的高活性和高选择性丙烷脱氢制丙烯催化剂及其制备方法。所述催化剂的载体材料xMaOb·yAl2O3采用沉淀法制备,其中M=Ba、Mg、La、Mn、Zr、K、Na、Ca、Zn、Ce、Bi、Fe、Nb、Sb中的一种或几种,a=1~3,b=1~4,x=0~1,y=1~8。再经500~1000℃焙烧后,加入造孔剂对载体材料进行成型处理,合成出具有特定孔结构的载体。该特定结构载体负载活性组分后的催化剂在烷烃直接脱氢制丙烯反应中表现出优异的催化活性和产物选择性。
Description
技术领域
本发明涉及一种具有特定孔结构的高活性、高选择性丙烷脱氢制丙烯负载催化剂及其制备方法,属于化工领域。
背景技术
丙烯是仅次于乙烯的重要石油化工基本原料,广泛用于生产聚丙烯、丁辛醇、丙烯腈、环氧丙烷、环氧氯丙烷、丙酮、丙烯酸等。近年来,随着聚丙烯等下游产品需求的快速增长,丙烯资源供应逐渐呈现出紧张态势,从而为丙烷脱氢项目提供了商机。特别是,近年来随着世界非常规天然资源如页岩气开发获得突破,获得长期、稳定、相对低廉的丙烷资源成为可能,从而使丙烷脱氢(PDH)制丙烯生产工艺成为备受关注的热点,具有较强的市场竞争力,并由此引发业界巨头纷纷投资。
目前丙烯主要来源于乙烯联产和催化裂化,近年来,我国丙烯的发展速度逐渐超过了乙烯,2017年,我国丙烯当量需求的年均增长率达到7.6%,超过丙烯生产能力的增长速度。从当量需求来看,丙烯供需矛盾日益突出,导致近年来扩大丙烯来源的PDH制丙烯生产工艺前景非常广阔。
发明内容
本发明提供了一种具有特定孔结构的高活性、高选择性丙烷脱氢制丙烯负载催化剂及其制备方法,即通过调变催化剂的孔结构,制备出具有特殊孔结构丙烷脱氢制丙烯Cr系催化剂,该催化剂的丙烷脱氢结果表明:催化剂具有优异的丙烷转化率、丙烯选择性以及高的产物丙烯浓度。
一种具有特定孔结构的载体材料的制备方法,包括如下步骤:
(1)采用沉淀法制备xMaOb·yAl2O3载体粉体材料,其中M=Ba、Mg、La、Mn、Zr、K、Na、Ca、Zn、Ce、Bi、Fe、Nb、Sb中的一种或几种,a=1~3;b=1~4,x=0~1,y=1~8。
(2)将步骤(1)得到的xMaOb·yAl2O3载体材料经500~1000℃焙烧2~10小时后,加入造孔剂对载体材料进行成型处理,合成出具有特定孔结构的载体。其中所述造孔剂用量与载体粉体的质量比为0~30wt%,且不能为0。
基于上述技术方案,优选的,所述造孔剂为柠檬酸、草酸、苯甲酸、聚乙烯醇(PVA)、聚乙烯醇缩丁醛(PVB)、高分子微球(如聚丁二烯微球、聚异戊二烯微球等)、淀粉、硬脂酸、活性炭、石墨、酚醛树脂以及尿素等中的一种或几种。
基于上述技术方案,优选的,所述对载体材料进行成型处理的方法为采用挤条成型方法对载体材料进行成型处理。
本发明另一目的还提供了一种具有特定孔结构的丙烷脱氢制丙烯负载催化剂:所述催化剂由Cr2O3活性组分和载体材料组成,其化学式为:zCr2O3/xMaOb·yAl2O3,其中负载量z=10~30wt%,所述载体材料为上述的具有特殊孔结构的载体材料。
基于上述技术方案,优选的,所述Cr2O3活性组分前驱体材料为硝酸铬、乙酸铬、柠檬酸铬、铬酸酐、乙酰丙酮铬中的一种或几种。
本发明另一目的还提供了一种具有特殊孔结构的丙烷脱氢制丙烯负载催化剂的制备方法,包括如下步骤:
(1)以Cr2O3为活性组分,上述的xMaOb·yAl2O3为载体材料,采用浸渍法制备zCr2O3/xMaOb·yAl2O3负载催化剂;
(2)将步骤(1)制备的zCr2O3/xMaOb·yAl2O3负载催化剂在500~900℃下焙烧2~10小时。
本发明另一目的还提供上述的具有特定孔结构的丙烷脱氢制丙烯负载催化剂在丙烷直接脱氢制丙烯反应中的应用,反应条件为:反应条件为:反应压力40~60kPa,反应温度560~620℃,丙烷反应空速300~400ml·g-1·h-1;优选为,反应压力50kPa,反应温度580℃,丙烷反应空速320ml·g-1·h-1。具体反应条件为:反应为自动顺序控制的4个过程:第一个过程,40~60kPa下的丙烷脱氢反应5~10min;第二个过程,40~60kPa的水蒸气吹扫2~5min;第三个过程,常压下空气再生反应5~10min;第四个过程,10~30kPa下的H2还原处理反应5~10min。优选的,第一个过程,50kPa下的丙烷脱氢反应7min;第二个过程,50kPa的水蒸气吹扫2min;第三个过程,常压下空气再生反应6min;第四个过程,20kPa下的H2还原处理反应6min。
有益效果:
本发明提供的催化剂,用于丙烷直接脱氢制丙烯反应,本发明制备的具有特定孔径结构的负载活性组分后的催化剂在烷烃直接脱氢制丙烯反应中表现出优异的催化活性(丙烯转化率30~48%)和丙烯产物选择性(80~89%)、产物中丙烯浓度(15~27%)。
本发明提供的方法适用性广、简单、成本较低、重复性好。
附图说明
图1为实施例2-9中添加不同造孔剂制备的催化剂的孔径分布图(从下到上依次使用的造孔剂为:柠檬酸、PVA、PVB、活性炭、淀粉、聚丁二烯微球、硬脂酸和酚醛树脂)。
图2为实施例1中具有特定孔结构负载催化剂在580~630℃温度区间丙烷脱氢制丙烯性能(△:丙烯选择性;□:丙烷转化率;○:产物中丙烯浓度)。
具体实施方式
下面的实施例将对本发明予以进一步的说明,但并不因此而限制发明。
实施例1
采用沉淀法制备La2O3·6Al2O3载体,按化学式中La:Al原子比称取硝酸镧和硝酸铝溶于去离子水中,搅拌25min后,逐滴加入过量碳酸氨水溶液,乳白色沉淀生成,继续搅拌120min后,过滤、洗涤,将过滤后固体材料在100℃烘箱中隔夜烘干。将烘干后粉体在马弗炉中1000℃焙烧3小时,得到白色粉体,测其比表面积为120m2/g。
实施例2
实施例1制备的La2O3·6Al2O3载体粉体中加入柠檬酸造孔剂,其与载体的质量比25wt%,挤条机挤出成型后在500℃焙烧2小时用于浸渍法合成负载Cr2O3催化剂,其中Cr2O3的负载量为15wt%。将10ml乙酸铬溶液(3mol/L)逐滴加入到10g成型载体材料中,在50℃烘干后,将负载后催化剂在马弗炉中600℃焙烧6小时,得到淡绿色成型负载催化剂。其孔结构见图1。
实施例3
实施例1制备的La2O3·6Al2O3载体粉体中加入PVA造孔剂,其与载体的质量比25wt%,挤条机挤出成型处理后在500℃焙烧2小时用于浸渍法合成负载Cr2O3催化剂,其中Cr2O3的负载量为15wt%。将10ml乙酸铬溶液(3mol/L)逐滴加入到10g成型载体材料中,在50℃烘干后,将负载后催化剂在马弗炉中600℃焙烧6小时,得到淡绿色成型负载催化剂。其孔结构见图1。
实施例4
实施例1制备的La2O3·6Al2O3载体粉体中加入PVB造孔剂,其与载体的质量比25wt%,挤条机挤出成型处理后在500℃焙烧2小时用于浸渍法合成负载Cr2O3催化剂,其中Cr2O3的负载量为15wt%。将10ml乙酸铬溶液(3mol/L)逐滴加入到10g成型载体材料中,在50℃烘干后,将负载后催化剂在马弗炉中600℃焙烧6小时,得到淡绿色成型负载催化剂。其孔结构见图1。
实施例5
实施例1制备的La2O3·6Al2O3载体粉体中加入活性炭造孔剂,其与载体的质量比25wt%,挤条机挤出成型处理后在500℃焙烧2小时用于浸渍法合成负载Cr2O3催化剂,其中Cr2O3的负载量为15wt%。将10ml乙酸铬溶液(3mol/L)逐滴加入到10g成型载体材料中,在50℃烘干后。将负载后催化剂在马弗炉中600℃焙烧6小时,得到淡绿色成型负载催化剂。其孔结构见图1。
实施例6
实施例1制备的La2O3·6Al2O3载体粉体中加入淀粉造孔剂,其与载体的质量比25wt%,挤条机挤出成型处理后在500℃焙烧2小时用于浸渍法合成负载Cr2O3催化剂,其中Cr2O3的负载量为15wt%。将10ml乙酸铬溶液(3mol/L)逐滴加入到10g成型载体材料中,在50℃烘干后,将负载后催化剂在马弗炉中600℃焙烧6小时,得到淡绿色成型负载催化剂。其孔结构见图1。
实施例7
实施例1制备的La2O3·6Al2O3载体粉体中加入聚丁二烯微球造孔剂,其与载体的质量比25wt%,挤条机挤出成型处理后在500℃焙烧2小时用于浸渍法合成负载Cr2O3催化剂,其中Cr2O3的负载量为15wt%。将10ml乙酸铬溶液(3mol/L)逐滴加入到10g成型载体材料中,在50℃烘干后,将负载后催化剂在马弗炉中600℃焙烧6小时,得到淡绿色成型负载催化剂。其孔结构见图2。
实施例8
实施例1制备的La2O3·6Al2O3载体粉体中加入硬脂酸造孔剂,其与载体的质量比25wt%,挤条机挤出成型处理后在500℃焙烧2小时用于浸渍法合成负载Cr2O3催化剂,其中Cr2O3的负载量为15wt%。将10ml乙酸铬溶液(3mol/L)逐滴加入到10g成型载体材料中,在50℃烘干后,将负载后催化剂在马弗炉中600℃焙烧6小时,得到淡绿色成型负载催化剂。其孔结构见图1。
实施例9
实施例1制备的La2O3·6Al2O3载体粉体中加入酚醛树脂造孔剂,其与载体的质量比25wt%,挤条机挤出成型处理后在500℃焙烧2小时用于浸渍法合成负载Cr2O3催化剂,其中Cr2O3的负载量为15wt%。将10ml乙酸铬溶液(3mol/L)逐滴加入到10g成型载体材料中,在50℃烘干后,将负载后催化剂在马弗炉中600℃焙烧6小时,得到淡绿色成型负载催化剂。其孔结构见图1。
实施例10
实施例2~9中制备的具有不同孔结构的负载催化剂用于丙烷直接脱氢制丙烯反应。称取10g成型催化剂,反应原料气为纯丙烷,反应压力50kPa,反应温度580℃,反应空速320ml·g-1·h-1。反应结果列在表1中。柠檬酸作为造孔剂制备的负载催化剂显示处优异的丙烷转化率和丙烯选择性。
实施例11
实施例2中制备的具有特定孔结构的负载催化剂用于丙烷脱氢制丙烯580~630℃的性能测试,结果见图2。测试过程为:称取10g成型催化剂,反应原料气为纯丙烷,反应压力50kPa,反应温度580~630℃,反应空速320ml·g-1·h-1。很明显,具有特定孔结构催化剂在580~610℃温度区间具有优异的丙烷转化率和丙烯选择性。且随反应温度提高,丙烷转化率提高,但丙烯选择性明显降低。
比较例1
常规负载催化剂Cr2O3/Al2O3的制备:将Al2O3载体用挤条机挤出成型处理后在500℃焙烧2小时,采用浸渍法制备负载Cr基催化剂,含Cr前驱体为三价乙酸铬,活性组分负载量20wt%。将10ml乙酸铬溶液(3mol/L)逐滴加入到10g成型Al2O3载体材料中,在50℃烘干后,将负载催化剂在H2气氛下600℃焙烧4h,得到淡绿色常规负载催化剂。
比较例2
将比较例1中制备的常规负载催化剂Cr2O3/Al2O3用于模拟工业反应条件装置丙烷直接脱氢制丙烯反应。称取10g成型常规催化剂,反应原料气为纯丙烷,反应压力为50kPa,反应温度580℃,反应空速320ml·g-1·h-1。反应结果如表1所示。
表1不同孔结构催化剂的丙烷脱氢性能比较
Claims (9)
1.一种具有孔结构的载体材料的制备方法,其特征在于:包括如下步骤:
(1)采用沉淀法制备金属掺杂的氧化铝盐xMaOb·yAl2O3载体材料,其中M=Ba、Mg、La、Mn、Zr、K、Na、Ca、Zn、Ce、Bi、Fe、Nb、Sb中的一种或几种,a=1~3,b=1~4,x=0~1,y=1~8;
(2)将步骤(1)得到的载体材料经500~1000℃焙烧2~10小时后,加入造孔剂对载体材料进行成型处理;其中所述造孔剂的用量与载体材料的质量分数为0~30wt%,且不能为0。
2.根据权利要求1所述的具有孔结构的载体材料的制备方法,其特征在于:所述造孔剂为柠檬酸、草酸、苯甲酸、聚乙烯醇、聚乙烯醇缩丁醛、高分子微球、淀粉、硬脂酸、活性炭、石墨、酚醛树脂以及尿素中的一种或几种。
3.权利要求1或2所述方法制备的具有孔结构的载体材料。
4.一种具有孔结构的丙烷脱氢制丙烯负载催化剂,其特征在于:所述催化剂由Cr2O3活性组分和载体材料组成,其化学式为:zCr2O3/xMaOb·yAl2O3,其中负载量z=10~30%,所述载体材料为权利要求3所述的载体材料。
5.根据权利要求4所述的具有孔结构的丙烷脱氢制丙烯负载催化剂,其特征在于:所述Cr2O3活性组分前驱体材料为硝酸铬、乙酸铬、柠檬酸铬、铬酸酐、乙酰丙酮铬中的一种或几种。
6.一种权利要求4或5中所述的具有孔结构的丙烷脱氢制丙烯负载催化剂的制备方法,其特征在于:包括如下步骤:
(1)采用浸渍法制备zCr2O3/xMaOb·yAl2O3负载催化剂;
(2)将步骤(1)制备的zCr2O3/xMaOb·yAl2O3负载催化剂在500~900℃下焙烧2~10小时。
7.权利要求4或5所述的具有孔结构的丙烷脱氢制丙烯负载催化剂在丙烷直接脱氢制丙烯反应中的应用。
8.根据权利要求7所述的应用,其特征在于:反应条件为:反应压力40~60kPa,反应温度560~620℃,丙烷反应空速300~400ml·g-1·h-1。
9.根据权利要求8所述的应用,其特征在于:具体反应为4个过程:第一个过程,40~60kPa下的丙烷脱氢反应5~10min;第二个过程,40~60kPa的水蒸气吹扫2~5min;第三个过程,常压下空气再生反应5~10min;第四个过程,10~30kPa下的H2还原处理反应5~10min。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112812751A (zh) * | 2020-10-14 | 2021-05-18 | 中国科学院大连化学物理研究所 | 一种丙烷脱氢制丙烯工艺用储热材料及其制备方法 |
CN113441129A (zh) * | 2021-08-06 | 2021-09-28 | 西南化工研究设计院有限公司 | 一种复合金属氧化物型烷烃脱氢催化剂及其制备方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB823626A (en) * | 1957-09-27 | 1959-11-18 | Houdry Process Corp | Improvements in or relating to dehydrogenation of hydrocarbons |
WO2000072967A1 (en) * | 1999-05-28 | 2000-12-07 | Den Norske Stats Oljeselskap A.S | PRETREATMENT OF A Pt/Sn-BASED CATALYST |
CN1647857A (zh) * | 2004-01-19 | 2005-08-03 | 中国石油化工股份有限公司 | 一种大孔氧化铝载体及其制备方法 |
CN101450327A (zh) * | 2007-11-29 | 2009-06-10 | 南化集团研究院 | 一种氧化铝载体的制备方法 |
CN102989517A (zh) * | 2011-09-09 | 2013-03-27 | 中国石油天然气股份有限公司 | 双峰孔径分布的氧化铝载体及其制备方法 |
CN103418377A (zh) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | 用于低碳烷烃脱氢制备低碳烯烃的薄壳型催化剂 |
CN107537534A (zh) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | 正丁烷脱氢制丁烯/丁二烯催化剂及用途 |
CN110152650A (zh) * | 2018-02-11 | 2019-08-23 | 中国科学院大连化学物理研究所 | 一种丙烷脱氢制丙烯负载催化剂及其制备方法 |
-
2020
- 2020-01-23 CN CN202010076239.2A patent/CN111686709B/zh active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB823626A (en) * | 1957-09-27 | 1959-11-18 | Houdry Process Corp | Improvements in or relating to dehydrogenation of hydrocarbons |
WO2000072967A1 (en) * | 1999-05-28 | 2000-12-07 | Den Norske Stats Oljeselskap A.S | PRETREATMENT OF A Pt/Sn-BASED CATALYST |
CN1647857A (zh) * | 2004-01-19 | 2005-08-03 | 中国石油化工股份有限公司 | 一种大孔氧化铝载体及其制备方法 |
CN101450327A (zh) * | 2007-11-29 | 2009-06-10 | 南化集团研究院 | 一种氧化铝载体的制备方法 |
CN102989517A (zh) * | 2011-09-09 | 2013-03-27 | 中国石油天然气股份有限公司 | 双峰孔径分布的氧化铝载体及其制备方法 |
CN103418377A (zh) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | 用于低碳烷烃脱氢制备低碳烯烃的薄壳型催化剂 |
CN107537534A (zh) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | 正丁烷脱氢制丁烯/丁二烯催化剂及用途 |
CN110152650A (zh) * | 2018-02-11 | 2019-08-23 | 中国科学院大连化学物理研究所 | 一种丙烷脱氢制丙烯负载催化剂及其制备方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112812751A (zh) * | 2020-10-14 | 2021-05-18 | 中国科学院大连化学物理研究所 | 一种丙烷脱氢制丙烯工艺用储热材料及其制备方法 |
CN113441129A (zh) * | 2021-08-06 | 2021-09-28 | 西南化工研究设计院有限公司 | 一种复合金属氧化物型烷烃脱氢催化剂及其制备方法 |
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