CN112934222A - 一种丙烷脱氢催化剂及其制备方法和应用 - Google Patents
一种丙烷脱氢催化剂及其制备方法和应用 Download PDFInfo
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- CN112934222A CN112934222A CN202110109255.1A CN202110109255A CN112934222A CN 112934222 A CN112934222 A CN 112934222A CN 202110109255 A CN202110109255 A CN 202110109255A CN 112934222 A CN112934222 A CN 112934222A
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- metal oxide
- propane
- catalyst
- dehydrogenation catalyst
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 239000001294 propane Substances 0.000 title claims abstract description 48
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 38
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
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- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001038 basic metal oxide Inorganic materials 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 9
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- 229910052593 corundum Inorganic materials 0.000 claims description 19
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- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明公开了一种丙烷脱氢催化剂及其制备方法和应用,以碱性金属氧化物M2进行表面修饰的粉末活性氧化铝制成的微球为载体,该载体上负载有作为活性组分的PtO2‑SnO2‑金属氧化物M1三元金属团簇。本发明工艺过程简单,生产成本低,安全环保及适合工业规模化生产等优点,适用于移动床反应器(可在线连续在线再生),也适用于固定床反应器(可不同反应器交替再生)。
Description
技术领域
本发明属于丙烷脱氢技术领域,具体涉及一种丙烷脱氢催化剂及其制备方法和应用。
背景技术
目前全球丙烯产能超1.4亿吨,需求约1.1亿吨。其中,中国的需求约占全球的30%。丙烯生产传统的工艺路线包括蒸汽裂解、炼厂催化裂化FCC分离、重度催化裂解DCC等,此外还有On-Purpose的工艺,具体包括丙烷脱氢PDH、烯烃歧化和MTP等。目前石脑油裂解乙烯副产仍是丙烯最主要的供应来源,约占45%;其次为炼厂FCC装置,约占30%;丙烷脱氢约占丙烯供应的10%以上。近年来全球丙烯需求增长迅速,丙烷脱氢(PDH)的市场占有率增长最快,在中国已成为一个新兴产业。
PDH是丙烷在500-600℃条件下经催化脱氢得到丙烯,该技术的特点是单一原料生产单一产品(主要是丙烯),流程简短。目前PDH工艺有四种:UOP公司的Oleflex工艺;ABBLummus公司的Catofin工艺;伍德(Krupp Uhdewcng)公司的STAR工艺;Linde-BASF-Statoil共同开发的PDH工艺等。已实现工业化的主要是UOP的Oleflex工艺和ABBLummus的Carofin工艺,UOP和Lummus两种工艺路线大体相同,所不同的只是脱氢和催化剂再生部分,不同丙烷脱氢工艺及催化剂使用情况见表1:
表1不同丙烷脱氢工艺及催化剂
丙烷脱氢工艺是最具前景的丙烯生产新技术,相关技术被美、德等少数国家长期垄断,我国现有的丙烷脱氢制丙烯生产线均从国外高价引进,催化剂也完全依赖进口,而催化剂是该工艺的关键所在。现有技术中可用于丙烷脱氢催化体系的主要有二类催化剂:一类是Cr基催化剂,主要是CrK/Al2O3,具有的特点是价格便宜,初始活性较高,但是其稳定性差,且Cr属于重金属有毒,项目存在环境风险;另一类是Pt基催化剂,主要是PtSnK/Al2O3,尽管Pt基催化剂价格十分昂贵,但相对热稳定性较好,不存在毒性,有更好的应用前景。如何降低成本,减少对环境的污染,提高催化剂稳定性和选择性,抑制生焦反应,是需要深入研究和解决的问题。
自从1990年代初发现PDH以来,工业上PDH工艺一直使用多孔氧化铝负载的PtSn双金属(PtSn/Al2O3)作为反应催化剂。虽然纯Pt金属具有较高的初始催化活性,但是反应过程中焦炭会沉积在Pt表面而导致其迅速失活。同时,焦炭沉积还会使催化剂的选择性大大降低。国内外对于Pt基催化剂进行大量的研究,且已有工业化应用装置。如何得到高稳定性,高活性和高选择性催化剂仍是目前催化领域的重要研究方向。目前国内外对于Pt基催化剂的研究主要在Pt-Sn双组份催化剂基础上进行,包括第三组份,载体改性,制备方法优化及反应条件调变等来提高催化剂的性能。CN108325523A公开了由镁铝尖晶石载体负载金属铂得到催化剂,铂原子以单原子或亚纳米团簇的形式存在,且所述亚纳米团簇的粒径小于1nm,转化率和选择性都取得了显著的提高,并且稳定性好。CN108855197A公开了丙烷脱氢催化剂主要活性组分Pt、金属助剂Sn和金属助剂Na,其中,所述载体为球形三介孔硅藻土复合载体,具有三维立方孔道分布结构。CN106512994A公开了在氧化铝载体上负载铂、锡组分,并引入第二助剂氧化钙,以提高催化剂的稳定性。CN106362791A公开了将Na-ZSM-5分子筛在有机混合碱性溶液中搅拌处理,然后经洗涤、过滤和干燥后与适量的无机酸溶液交换,再经洗涤、过滤、干燥和煅烧后得到含有介孔-微孔复合孔道HZSM-5分子筛。经过分布浸渍和挤条成型得到丙烷脱氢催化剂,催化剂中含有0.01%-0.3%的Pt、0.01%-0.3%的Ru或Ir、0.01%-3%的Sn和0.01%-3%的Zr、Nb、Ta、W中的任意一种。US5143888公开了在铝酸锌中加入10-18%铝酸钙可以提高催化剂活性和寿命,同时提高催化剂机械强度;这种由碱金属或碱土金属促进的铂锡催化剂在反应温度500-700℃和水蒸汽稀释下,烯烃的单程收率在35%左右。
综上所述,尽管目前PtSn/Al2O3催化剂已经应用于低碳烷烃反应中,但催化剂积炭失活的现象仍然经常发生,并且需要频繁且繁琐的再生步骤来恢复其催化活性。为了满足工业化的要求,对催化剂进行优化和改进显得很有必要。因此,开发一种高效高选择性稳定的催化剂和实现丙烷脱氢节能稳定生产具有重要意义。
发明内容
本发明的目的在于克服现有技术缺陷,提供一种丙烷脱氢催化剂。
本发明的另一目的在于提供上述丙烷脱氢催化剂的制备方法。
本发明的再一目的在于提供一种丙烷催化脱氢制备丙烯的方法。
本发明的技术方案如下:
一种丙烷脱氢催化剂,以碱性金属氧化物M2进行表面修饰的粉末活性氧化铝制成的微球为载体,该载体上负载有作为活性组分的PtO2-SnO2-金属氧化物M1三元金属团簇;该金属氧化物M1为In2O3、CeO2、CuO、Cr2O3或La2O3,该碱性金属氧化物M2为K2O、MgO、CaO、BaO、ZrO2或ZnO;
其中,PtO2的含量为0.1-0.5wt%,SnO2的含量为0.2-1.0wt%,金属氧化物M1的含量为1-5wt%,碱性金属氧化物M2的含量为1-5wt%,余量为Al2O3。
在本发明的一个优选实施方案中,所述金属氧化物M1为In2O3、Cr2O3或CuO。
在本发明的一个优选实施方案中,所述碱性金属氧化物M2为K2O或CaO。
在本发明的一个优选实施方案中,所述载体的直径为0.8-1.2mm。
上述丙烷脱氢催化剂的制备方法,包括如下步骤:
(1)将所述碱性金属氧化物M2的可溶性盐溶解在去离子水中,并加入浓度为0.08-0.12mol/L的稀硝酸调节pH值为4-6,配制成盐溶液,再加入铝溶胶搅拌成混合溶胶,制成复合表面修饰胶粘剂;
(2)将步骤(1)制得的复合表面修饰胶粘剂、粉体活性氧化铝和淀粉混捏成塑性料团后,经挤条切粒一体机挤出的颗粒送入滚球机进行整圆致密化;整圆致密化的过程中采用40-50℃热风老化处理0.4-0.6h,制得微球氧化铝载体前驱体;
(3)把步骤(2)制得的微球氧化铝载体前驱体于100-120℃干燥8-12h后,移至马弗炉中,以5-10℃/min升温速率升温至550-650℃,焙烧4-8h,即得到所述载体;
(4)将PtO2、SnO2、金属氧化物M1的可溶性盐、去离子水、柠檬酸和浓度为24-26%的稀氨水混合后,搅拌配制成PtO2-SnO2-M1的络合液;
(5)按二倍浸渍法把步骤(4)制得的络合液浸渍步骤(3)制得的载体,浸渍的时间为4-8h,然后于100-120℃干燥8-12h,接着移至马弗炉中以5-10℃/min升温速率升温至500-600℃,焙烧4-8h,即得所述丙烷脱氢催化剂。
在本发明的一个优选实施方案中,微球氧化铝载体前驱体的直径为0.8-1.2mm,挤条切粒一体机采用的挤出孔径为1.0-1.5mm。
在本发明的一个优选实施方案中,所述碱性金属氧化物M2的可溶性盐为硝酸盐、氯化盐或硫酸盐。
在本发明的一个优选实施方案中,所述金属氧化物M1的可溶性盐为硝酸盐、氯化盐或硫酸盐。
在本发明的一个优选实施方案中,金属氧化物M1的可溶性盐、稀氨水和柠檬酸的比例为1-15g∶10-20mL∶5-10mL。
在本发明的一个优选实施方案中,所述PtO2、SnO2和金属氧化物M1的的可溶性盐的质量比为:1-5∶5-10∶5-20。
一种丙烷催化脱氢制备丙烯的方法,使用上述丙烷脱氢催化剂。
在本发明的一个优选实施方案中,包括如下步骤:
(1)将所述丙烷脱氢催化剂放入反应器中,在常压且氢气气氛下以2-5℃/min的速率升温到590-610℃,恒温反应时间1.5-2.5h;
(2)氢气气氛下,将丙烷按体积空速980-1000h-1通入上述反应器中,于常压且温度为590-610℃的条件下反应。
进一步优选的,所述丙烷与氢气的摩尔比为3-4∶1
本发明的有益效果是:
1、本发明工艺过程简单,生产成本低,安全环保及适合工业规模化生产等优点,适用于移动床反应器(可在线连续在线再生),也适用于固定床反应器(可不同反应器交替再生)。
2、本发明采用碱性氧化物对粉体活性氧化铝进行表面修饰制备的氧化铝微球为载体,既保持了原Al2O3球的物性结构和机械强度,又削弱了载体表面的强酸位,从而抑制积炭的生成速度,提高催化剂的选择性和高温稳定性。
3、本发明采用加入柠檬酸和浓度为24-26%的稀氨水,和PtO2、SnO2和金属氧化物M1的可溶性金属调配成PtO2-SnO2-M1可溶性络合液进行负载;采用弱酸不破坏原Al2O3微球的物性结构和机械强度,带有弱碱性铵根子的络合液有利于形成的Pt-Sn-M1三元金属团族在弱酸性表面的分散,有利于Pt-Sn-M1三元金属协同催作用,从而促进催化活性。
4、本发明通过以氧化铂、氧化锡及金属氧化物M1(In2O3、CeO2、CuO、Cr2O3和La2O3)中的一种组成的三元金属团簇为活性组分,可以调控活性组分密度和几何分散度,同时调控活性组分与氧化铝的作用距离,削弱Pt-Al2O3相互作用,促进Pt纳米颗粒形成或Pt-Sn合金。
附图说明
图1为本发明中实施例1、实施例3、实施例9和实施例10所制得的催化剂的稳定性测试结果图。
具体实施方式
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
实施例1
(1)称取氯化钾(KCl)3.10溶于25g去离子水,加入5ml 0.1mol/l的稀硝酸制成盐溶液调节pH至5,加入10g铝溶胶搅拌成混合溶胶,制成复合表面修饰胶粘剂。
(2)将步骤(1)得到的复合表面修饰胶粘剂与100g粉末活性氧化铝及5g淀粉在混捏机里混捏成塑性料团后,经挤条切粒一体机挤出的颗粒送入滚球机进行整圆致密化,该整圆致密化的过程中采用40-50℃热风老化处理0.5h,制得微球氧化铝载体前驱体。微球的直径为Φ0.8-1.2mm,挤条切粒一体机采用的挤出孔径为Φ1.0-1.5mm。
(3)把制得微球氧化铝载体前驱体在烘箱里以100-120℃干燥8-12h后,移至马弗炉中,以5-10℃/min升温速率升温至550-650℃,焙烧4-8h。即得到以K2O改性的氧化铝微球载体,其中,K2O的含量为2wt%。
(4)称取2.28g氯铂酸水合物(H2PtCl6·6H2O)、2.99g氯化亚锡水合物(SnCl2·2H2O)和9.2g硝酸铟水合物(In(NO3)3·H2O)放入配制桶中,并向其中加入10mL稀氨水(25%)、5g柠檬酸以及适量的去离子水,不断搅拌直到形成络合液,其中,PtO2的负载量为0.5wt%,SnO2的负载量为1wt%,In2O3的负载量为2wt%。
(5)按二倍浸渍法把步骤(4)制得的络合液浸渍步骤(3)制得的氧化铝微球载体,浸渍的时间为8h,然后在120℃的烘箱中干燥12h,接着移至马弗炉中以5℃/min升温速率升温至500,焙烧4h。即得到PtO2SnO2-In2O3/K2O-Al2O3催化剂。
实施例2
催化剂的制备方法与实施例1相似,不同之处在将实施例1中步骤(1)的氯化钾改为氯化镁水合物(MgCl2·6H2O),称取质量10.17g溶于25g去离子水中,其他步骤与条件不变即可制得本实施例的催化剂PtO2SnO2-In2O3/MgO-Al2O3,其中MgO的含量为2wt%。
实施例3
催化剂的制备方法与实施例1相似,不同之处在将实施例1中步骤(1)的氯化钾改为无水氯化钙(CaCl2),称取质量3.96g溶于25g去离子水中,其他步骤与条件不变即可制得本实施例的催化剂PtO2SnO2-In2O3/CaO-Al2O3,其中CaO的含量为2wt%。
实施例4
催化剂的制备方法与实施例1相似,不同之处在将实施例1中步骤(1)的氯化钾改为硝酸钡(Ba(NO3)2),称取质量3.41g溶于25g去离子水中,其他步骤与条件不变即可制得本实施例的催化剂PtO2SnO2-In2O3/BaO-Al2O3,其中BaO的含量为2wt%。
实施例5
催化剂的制备方法与实施例1相似,不同之处在将实施例1中步骤(1)的氯化钾改为硝酸锆(Zr(NO3)4·5H2O),称取质量6.97g溶于25g去离子水中,其他步骤与条件不变即可制得本实施例的催化剂PtO2SnO2-In2O3/ZrO2-Al2O3,其中ZrO2的含量为2wt%。
实施例6
催化剂的制备方法与实施例1相似,不同之处在将实施例1中步骤(1)的氯化钾改为硝酸锌(Zn(NO3)2·6H2O),称取质量7.31g溶于25g去离子水中,其他步骤与条件不变即可制得本实施例的催化剂PtO2SnO2-In2O3/ZnO-Al2O3,其中ZnO的含量为2wt%。
上述实施例1-6均是以碱性金属氧化物(K2O、MgO、CaO、BaO、ZrO2和ZnO中的一种)改性的氧化铝微球为载体、以PtO2、SnO2及In2O3组成的三元金属团簇为活性组分制备的催化剂。
实施例7
催化剂的制备方法与实施例1相似,不同之处在将实施例3中步骤(4)的In(NO3)3·H2O改为La(NO3)3·6H2O,称取的质量为5.32g,其他步骤与条件不变即可制得本实施例的催化剂PtO2SnO2-La2O3/CaO-Al2O3,其中La2O3的负载量为2wt%。
实施例8
催化剂的制备方法与实施例1相似,不同之处在将实施例3中步骤(4)的In(NO3)3·H2O改为Ce(NO3)3·6H2O,称取的质量为5.29g,其他步骤与条件不变即可制得本实施例的催化剂Pt02SnO2-Ce2O3/CaO-Al2O3,其中Ce2O3的负载量为2wt%。
实施例9
催化剂的制备方法与实施例1相似,不同之处在将实施例3中步骤(4)的In(NO3)3·H2O改为Cr(NO3)3·9H2O,称取的质量为10.53g,其他步骤与条件不变即可制得本实施例的催化剂PtO2SnO2-Cr2O3/CaO-Al2O3,其中Cr2O3的负载量为2wt%。
实施例10
催化剂的制备方法与实施例1相似,不同之处在将实施例3中步骤(4)的In(NO3)3·H2O改为Cu(NO3)2·3H2O,称取的质量为6.07g,其他步骤与条件不变即可制得本实施例的催化剂PtO2SnO2-CuO/CaO-Al2O3,其中CuO的负载量为2wt%。
上述实施例6-10均是以CaO改性的氧化铝微球为载体、以PtO2、SnO2及金属氧化物(In2O3、CeO2、CuO、Cr2O3和La2O3中的一种)组成的三元金属团簇为活性组分制备的催化剂。
将上述各实施例制得的催化剂装填于固定化反应器中,在常压下通入氢气,以3℃/min的升温速率升温至600℃,保温3h,接着以980h-1的体积空速通入丙烷进行反应(丙烷和氢气的摩尔比为3.7∶1),以对各实施例的催化剂进行活性评价及热重分析结果,具体结果见下表2和表3:
表2实施例1至5中PtO2SnO2-In2O3/M2-Al2O3催化剂活性评价结果及反应6h积碳量(热重分析结果)
表3实施例6至10中PtO2SnO2-M1/CaO-Al2O3催化剂活性评价结果及反应6h积碳量(热重分析结果)
从表2中可以看出,对催化剂载体改性效果比较好的碱性氧化物是K2O和CaO,对催化剂活性金属改性效果较好的金属氧化物是In2O3、Cr2O3和CuO。
如图1所示,实施例1制得的PtO2SnO2-In2O3/K2O-Al2O3催化剂在120h稳定性试验中,丙烷转化率保持在35%以上,且丙烷选择性保持在98%以上;实施例3制得的PtO2SnO2-In2O3/CaO-Al2O3催化剂在60h稳定性试验中,丙烷的初始转化率从约37%降低到34%,且丙烷选择性保持在97.5%左右;实施例9制得的PtO2SnO2-Cr2O3/CaO-Al2O3催化剂在20h稳定性试验中,丙烷的初始转化率从约35.5%降低到31%,且丙烷选择性由96%上升到97%;实施例10制得的PtO2SnO2-CuO/CaO-Al2O3催化剂在40h稳定性试验中,丙烷的初始转化率从约35.7%降低到33%,且丙烷选择性维持在98%左右。
以上所述,仅为本发明的较佳实施例而已,故不能依此限定本发明实施的范围,即依本发明专利范围及说明书内容所作的等效变化与修饰,皆应仍属本发明涵盖的范围内。
Claims (10)
1.一种丙烷脱氢催化剂,其特征在于:以碱性金属氧化物M2进行表面修饰的粉末活性氧化铝制成的微球为载体,该载体上负载有作为活性组分的PtO2-SnO2-金属氧化物M1三元金属团簇;该金属氧化物M1为In2O3、CeO2、CuO、Cr2O3或La2O3,该碱性金属氧化物M2为K2O、MgO、CaO、BaO、ZrO2或ZnO;
其中,PtO2的含量为0.1-0.5wt%,SnO2的含量为0.2-1.0wt%,金属氧化物M1的含量为1-5wt%,碱性金属氧化物M2的含量为1-5wt%,余量为Al2O3。
2.如权利要求1所述的一种丙烷脱氢催化剂,其特征在于:所述金属氧化物M1为In2O3、Cr2O3或CuO。
3.如权利要求1所述的一种丙烷脱氢催化剂,其特征在于:所述碱性金属氧化物M2为K2O或CaO。
4.权利要求1至3中任一权利要求所述的丙烷脱氢催化剂的制备方法,其特征在于:包括如下步骤:
(1)将所述碱性金属氧化物M2的可溶性盐溶解在去离子水中,并加入浓度为0.08-0.12mol/L的稀硝酸调节pH值为4-6,配制成盐溶液,再加入铝溶胶搅拌成混合溶胶,制成复合表面修饰胶粘剂;
(2)将步骤(1)制得的复合表面修饰胶粘剂、粉体活性氧化铝和淀粉混捏成塑性料团后,经挤条切粒一体机挤出的颗粒送入滚球机进行整圆致密化;整圆致密化的过程中采用40-50℃热风老化处理0.4-0.6h,制得微球氧化铝载体前驱体;
(3)把步骤(2)制得的微球氧化铝载体前驱体于100-120℃干燥8-12h后,移至马弗炉中,以5-10℃/min升温速率升温至550-650℃,焙烧4-8h,即得到所述载体;
(4)将PtO2、SnO2、金属氧化物M1的可溶性盐、去离子水、柠檬酸和浓度为24-26%的稀氨水混合后,搅拌配制成PtO2-SnO2-M1的络合液;
(5)按二倍浸渍法把步骤(4)制得的络合液浸渍步骤(3)制得的载体,浸渍的时间为4-8h,然后于100-120℃干燥8-12h,接着移至马弗炉中以5-10℃/min升温速率升温至500-600℃,焙烧4-8h,即得所述丙烷脱氢催化剂。
5.如权利要求4所述的制备方法,其特征在于:所述碱性金属氧化物M2的可溶性盐为硝酸盐、氯化盐或硫酸盐。
6.如权利要求4所述的制备方法,其特征在于:所述金属氧化物M1的可溶性盐为硝酸盐、氯化盐或硫酸盐。
7.如权利要求4所述的制备方法,其特征在于:金属氧化物M1的可溶性盐、稀氨水和柠檬酸的比例为1-15g∶10-20mL∶5-10mL。
8.一种丙烷催化脱氢制备丙烯的方法,其特征在于:使用权利要求1至3中任一权利要求所述的丙烷脱氢催化剂。
9.如权利要求8所述的方法,其特征在于:包括如下步骤:
(1)将所述丙烷脱氢催化剂放入反应器中,在常压且氢气气氛下以2-5℃/min的速率升温到590-610℃,恒温反应时间1.5-2.5h;
(2)氢气气氛下,将丙烷按体积空速980-1000h-1通入上述反应器中,于常压且温度为590-610℃的条件下反应。
10.如权利要求9所述的方法,其特征在于:所述丙烷与氢气的摩尔比为3-4∶1。
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