CN110869122A - 含有氧化促进剂的基于铂-镓的烷烃脱氢催化剂 - Google Patents
含有氧化促进剂的基于铂-镓的烷烃脱氢催化剂 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 31
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 20
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 19
- 230000003647 oxidation Effects 0.000 title claims abstract description 18
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 31
- 230000008929 regeneration Effects 0.000 claims abstract description 27
- 238000011069 regeneration method Methods 0.000 claims abstract description 27
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 38
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
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- 230000000694 effects Effects 0.000 description 24
- 238000000034 method Methods 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000011651 chromium Substances 0.000 description 9
- 239000001294 propane Substances 0.000 description 6
- 230000007420 reactivation Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
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- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- 230000003334 potential effect Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 230000009849 deactivation Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
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- 239000002905 metal composite material Substances 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Abstract
提供了用于烷烃脱氢的基于铂‑镓的催化剂，其具有铈形式的氧化促进剂，所述铈被添加到催化剂组合物中以改善其再生。铈优选以0.001至0.5wt％的量添加到催化剂组合物中。
Description
本发明涉及用于烷烃脱氢，特别是丙烷脱氢(PDH)的基于铂-镓的催化剂的氧化促进剂。更具体地，本发明涉及一种基于铂-镓的烷烃脱氢催化剂，其含有铈形式的氧化促进剂，所述铈被添加到催化剂组合物中以改善其再生。
今天，在商业用途中有四种主要的烷烃脱氢工艺。这些工艺之间的差异主要与反应热的供应有关。重要的Catofin工艺的特点是通过催化剂的预热提供反应热。Catofin工艺在3至8个固定床绝热反应器中进行，使用含有约20wt％氧化铬的氧化铬/氧化铝催化剂。催化剂可以补充有具有高的热容量的惰性材料，或者可替代地，具有选择性地燃烧或与形成的氢反应的材料，即所谓的发热材料(HGM)。可以添加钾等促进剂。
Catofin工艺是成熟的工艺，并且仍然是烷烃脱氢的主要工业工艺。由于反应热是由催化剂提供的，因此使用顺序操作，在此期间催化剂床用于脱氢。然后将气体吹扫出来，使催化剂再生/加热，并用氢气还原Cr(VI)氧化物。最后，在下一次脱氢之前，用蒸汽吹扫床。
常规的催化剂再生方法常常不能将基于铂-镓的烷烃脱氢催化剂的催化活性充分恢复到与此类催化剂在新鲜时相同的水平。因此，进行烷烃脱氢，尤其是PDH的技术人员知道，催化剂活性的降低不可避免地导致烯烃产量的降低，最终导致工艺经济学要求用新鲜催化剂代替失活催化剂的地步。因此，需要更充分地恢复催化剂活性的手段和方法。
为了使用于烷烃脱氢的基于铂-镓的催化剂再生，需要氧化处理。通常，需要高温和长反应时间(长达2小时)才能使催化剂完全再活化。
当前用于Catofin工艺的商业催化剂是基于铬的。这种Cr催化剂需要进行氧化处理以去除积聚的焦炭，但是不需要进行氧化处理以使其自身再活化。通常通过在高温条件下使催化剂与空气或另一种含氧气体接触来完成焦炭去除。
已经证明，再生步骤中延长的反应时间、高温(最高650℃)和高O2分压都有利于基于铂-镓的用于丙烷脱氢的催化剂在随后的丙烷脱氢循环中的性能。这些催化剂与当前市售铬催化剂的比较已表明，Pt/Ga催化剂在第一个循环中的性能优于Cr催化剂，但Cr在后续循环中具有更好的稳态性能。Pt/Ga催化剂从第一个循环到后续循环的性能下降是由于再生/氧化不足。
现已证明，铈(Ce)用作催化氧化步骤的氧化促进剂，从而使铈能够更快地再活化基于铂-镓的催化剂。
将Ce添加到催化剂中改善了催化剂的再活化，从而限制了由不完全再生引起的催化剂的失活。对于商业应用而言，这种改进的再活化行为非常重要，因为工业Catofin工厂中的再生时间通常为少于20分钟。因此，更完全的再生将确保催化活性保持较高，从而导致Catofin工厂的产量随时间推移保持较高。
在许多出版物中描述了将铈与烷烃催化脱氢结合使用。因此，US2004/0029715涉及含有氧化铈的脱氢催化剂的再生，并且在US 9.415.378中描述了一种脱氢催化剂，其中载体含有铈源。
J.Im&M.Choi,ACS Catal.6,2819-2826(2016)公开了一种用于丙烷脱氢为丙烯的基于铂-镓的催化剂，其含有铈形式的氧化促进剂，其以0.5-2wt％的量添加到催化剂组合物中。催化剂在620℃的温度下再生。但是，这种催化剂在Oleflex工艺中表现更好，在该工艺中Pt需要用Cl处理才能重新分散。
WO 2010/133565公开了可以含有铈的各种整料催化剂，其例如可用于脱氢。在WO2004/052535中，公开了一种特别是用于使芳族烃脱氢的煅烧的催化剂。它可包含铈作为选择性改进剂。
在WO 2004/033089中描述了将稀土金属用作氧化脱氢催化剂，并且在US 2015/0202601中公开了可用于烷烃脱氢的催化剂组合物和再活化方法。催化剂包括在催化剂载体(其可以是例如经稀土金属改性的氧化铝)上的IIIA族金属例如Ga、VIII族贵金属例如Pt或Pa、掺杂剂和任选的促进剂金属。
最后，US 2017/0120222公开了用于脱氢的过渡金属/贵金属复合氧化物催化剂。更具体地，该文献描述了使用溶胶-凝胶法制备具有改善性能的催化剂的方法，其中可见添加Ce的明显的积极作用。结果显示在图中，其中使用Ce的溶胶-凝胶的转化率明显高于没有Ce的样品。对于浸渍的样品，对于C3脱氢模糊地看到了相同的效果，而对于C4脱氢几乎观察不到。该催化剂在由掺杂有Ga的氧化铝组成的载体上具有Pt作为活性材料。提出使用Ce来稳定Pt。因此，US 2017/0120222中描述的催化剂在Oleflex工艺中也表现更好，在该工艺中Pt需要用Cl处理才能重新分散。
本发明涉及用于烷烃脱氢的基于铂-镓的催化剂，其中通过将烷烃进料至含有催化剂的脱氢反应器，低级烷烃根据以下反应被脱氢成相应的烯烃：
CnH2n+2<->CnH2n+H2
其中n为2至5的整数，
所述催化剂基于任选地掺杂有硅且被镓和铂浸渍的氧化铝，其中铈作为氧化促进剂与镓和铂一起添加，从而改善催化剂组合物的再生。
添加到催化剂中的铈的量为0.001至0.5wt％。优选的量为0.05至0.1wt％。铈可以盐的形式添加，例如Ce(NO3)2·6H2O。
优选地，铈通过与镓和铂一起浸渍而添加。此外，优选浸渍到催化剂组合物中的铂的量至多为约200ppm。
当使用根据本发明的催化剂进行烷烃脱氢时，观察到的效果不同于根据US 2017/0120222所观察到的效果。更具体地，当添加Ce时，看到对再生效率的明显影响。实际上，通过仅添加0.05wt％的Ce，与未添加Ce的样品相比，观察到催化剂明显更快的再活化。当催化剂被完全再活化时，看不到转化率的任何显著变化。这对于Catofin工艺非常重要，因为再活化非常频繁地进行，并且再活化时间非常短(几分钟)。
该效果也不同于根据US 2015/0202601获得的效果。与其他方面相同的催化剂相比，该文献中使用的催化剂在“空气浸泡”条件下具有缩短的再生时间。更具体地，对于Fe、Cr和V观察到该效果，而对于Ce没有观察到该效果，并且需要至少660℃的温度；而根据本发明，在低于630℃的温度下观察到Ce的有益效果。
已知的是，在长时间的再生步骤中，高温(最高约650℃)和高O2分压有利于基于铂-镓(Pt/Ga)的催化剂在下一个丙烷脱氢循环中的性能。此类Pt/Ga催化剂与当前市售Cr催化剂的实验测试已经表明，尽管Pt/Ga催化剂在第一个循环中的性能优于Cr催化剂，但在后续循环中，Cr催化剂显示出比Pt/Ga催化剂更好的稳态性能。Pt/Ga催化剂从第一个循环到后续循环的性能下降是由于再生/氧化不足。因此，已经研究了铈催化氧化步骤的能力，并且发现其是优异的。
在附图中更详细地说明了本发明，其中
图1显示了铈对再生的影响，以及
图2显示了有和没有铈的催化剂的活性。
通过以下实施例进一步说明本发明。
实施例1
该实施例说明了根据本发明的包括氧化促进剂的催化剂的合成。通过在氧化铝载体上共浸渍约0.1wt％的Ce以及约50ppm的Pt、1wt％的Ga和0.2wt％的K来进行合成。
更具体地，用11g水稀释4g的5％Ga的HNO3溶液、0.2g的0.5wt％的Pt溶液((Pt(NH3)4(HCO3)2))、0.062g的Ce(NO3)2·6H2O和0.05g的KNO3的混合物。所得溶液用于浸渍20g的γ/θAl2O3(球形，1000℃，孔体积为0.75ml/g)。将样品滚动1小时，干燥过夜，并在700℃下煅烧2小时，升温时间为4小时。
在以下实施例2和3中描述了Ce对催化剂再生的影响。
实施例2
铈对再生的影响如图1所示。在导致图1的实验中，第一个PDH循环在630℃再生后完成，而后续循环在555℃再生后完成。在所有情况下，PDH期间的温度都是相同的，更具体地说是555℃。对于Pt/Ga催化剂(图1中的催化剂A)，观察到在较低的再生温度下再循环时活性明显下降。添加0.1％的Ce(图1中的催化剂A-氧化促进剂)在降低再生温度的同时导致活性的略微下降。该发现表明，Ce能够促进催化剂的氧化，从而可以恢复在PDH期间丧失的大部分活性。
实施例3
图2显示了有和没有铈的催化剂的活性。更具体地，图2显示了在单颗粒串反应器中测试0.75g催化剂颗粒的结果。
催化剂B是在1000℃下煅烧的载体上的参考Pt/Ga催化剂。在第一个实验中，催化剂每次在630℃再生2小时。通过这种处理，催化剂达到了其最大潜力。在第二个实验中，相同的催化剂每次在630℃下再生30分钟。可以看出，在这种情况下，活性明显较低。
在随后的实验3至6中，将0.05、0.1、0.2或0.4wt％的量的Ce分别与Pt/Ga共浸渍。在所有情况下，测试均通过在630℃下再生30分钟进行。在相同条件下，具有0.05wt％的Ce的催化剂的性能明显优于催化剂B。实际上，其接近再生2小时后获得的催化剂B的最大潜在活性。看来，尽管铈改善了再生，但它也可能通过阻断活性Ga位点而降低最大潜在活性。这表明对于最终的催化剂，最终必须确定最大潜在活性和再生速度之间的最佳平衡。
在催化剂中没有任何Pt的情况下进行了最后两个实验。倒数第二个催化剂含有0.1wt％的Ce，而最后的催化剂不含Ce。Pt的缺乏导致活性大大降低，而在没有Pt的Ga催化剂中添加Ce并没有改善活性。因此，目前的观点是，Pt主要促进丙烷的脱氢，而Ce促进催化剂的再生，而在PDH步骤中没有任何积极作用。铈的添加对选择性或催化剂上的油或焦炭形成也没有任何影响。
Claims (6)
1.用于烷烃脱氢的催化剂，其中通过将烷烃进料至含有催化剂的脱氢反应器，低级烷烃根据以下反应被脱氢成相应的烯烃：
CnH2n+2<->CnH2n+H2
其中n为2至5的整数，
所述催化剂基于任选地掺杂有硅且被镓和铂浸渍的氧化铝，其中铈作为氧化促进剂与镓和铂一起添加，从而改善催化剂组合物的再生。
2.根据权利要求1所述的催化剂，其中铈以0.001至0.5wt％的量添加到催化剂组合物中。
3.根据权利要求2所述的催化剂，其中添加到催化剂组合物中的铈的量为0.05至0.1wt％。
4.根据权利要求1-3中任一项所述的催化剂，其中铈以盐的形式添加，优选以Ce(NO3)2·6H2O的形式添加。
5.根据权利要求1-4中任一项所述的催化剂，其中铈通过与镓和铂一起浸渍而添加。
6.根据权利要求1所述的催化剂，其中浸渍到催化剂组合物中的铂的量为至多约200ppm。
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| CN115427143A (zh) * | 2020-05-01 | 2022-12-02 | 科莱恩国际有限公司 | 脱氢催化剂系统及其使用方法 |
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| WO2021250567A1 (en) * | 2020-06-10 | 2021-12-16 | Sabic Global Technologies B.V. | A process for reconstructing a spent dehydrogenation catalyst |
| CN115697548A (zh) | 2020-06-10 | 2023-02-03 | Sabic环球技术有限责任公司 | 脱氢催化剂 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104525196A (zh) * | 2014-12-11 | 2015-04-22 | 天津大学 | 负载于双氧化物复合载体的铂镓催化剂及其制备方法和应用 |
| CN105582929A (zh) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | 低碳烷烃脱氢催化剂、制备方法及其用途 |
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-
2018
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105582929A (zh) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | 低碳烷烃脱氢催化剂、制备方法及其用途 |
| CN104525196A (zh) * | 2014-12-11 | 2015-04-22 | 天津大学 | 负载于双氧化物复合载体的铂镓催化剂及其制备方法和应用 |
Non-Patent Citations (2)
| Title |
|---|
| YANHUIWANG等: "Macrodynamic study and catalytic reduction of NO by ammonia under mild conditions over Pt-La-Ce-O/Al2O3 catalysts", 《ENERGY CONVERSION AND MANAGEMENT》 * |
| 陈巧力: "助催化剂Sn、Ga、In和K对丙烷脱氢催化剂Pt/Al2O3性能的影响", 《工业催化》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115427143A (zh) * | 2020-05-01 | 2022-12-02 | 科莱恩国际有限公司 | 脱氢催化剂系统及其使用方法 |
| CN113171801A (zh) * | 2020-11-30 | 2021-07-27 | 谷育英 | 一种低碳烷烃脱氢制烯烃的催化剂及其制备方法和应用 |
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