CN114364455A - 燃料油洗涤以从流化床丙烷脱氢反应器流出物中去除催化剂的用途 - Google Patents
燃料油洗涤以从流化床丙烷脱氢反应器流出物中去除催化剂的用途 Download PDFInfo
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- CN114364455A CN114364455A CN202080064022.8A CN202080064022A CN114364455A CN 114364455 A CN114364455 A CN 114364455A CN 202080064022 A CN202080064022 A CN 202080064022A CN 114364455 A CN114364455 A CN 114364455A
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Abstract
一种方法，其中使用外部燃料油从流化床丙烷脱氢反应器流出物中洗涤夹带的催化剂，其中将燃料油和催化剂混合物返回到反应器中以提供用于催化剂再生所需的净燃料。任选地，使流化床丙烷脱氢反应器流出物和燃料油在进入反应器容器中的闪蒸区之前在直接接触在线设备中接触。
Description
技术领域
本发明涉及一种用于从流出物中去除催化剂的方法，并且更具体地涉及一种用于使用洗涤流体和过滤从丙烷脱氢(PDH)反应器流出物流中去除催化剂的方法。
背景
来自页岩和闲置天然气(stranded gas)的丰富的烷烃和链烷烃(paraffins)推动了生产轻质烯烃的更成本有效的方法的发展，近年来其需求显著增加。蒸汽裂化器单元已经被设计成使用更轻质的页岩冷凝物作为原料以满足对轻质烯烃如乙烯的需求的增加。然而，已发现这些单元由于低的丙烯/乙烯比率和低的丙烯收率而不足以用于丙烯生产。因此，找到用于丙烯的定向生产的路线已经受到相当大的关注。
已经表明，催化脱氢提供对单一烯烃产物的高选择性的可能性。目前用于生产丙烯和其他轻质烯烃的烷烃脱氢方法采用铂基和铬基催化剂。考虑到与铂相关的费用和铬的致癌性性质，需要开发能够在脱氢方法期间具有良好的烯烃选择性和相应的高收率的更便宜、毒性更小的金属氧化物催化剂。
在采用提升管或流化床类型反应器的烷烃或链烷烃脱氢的方法中的潜在缺陷是在离开脱氢反应器的流出物流中包括细粉的催化剂粒子的量。关于反应器流出物流，使用水骤冷塔以冷却反应器流出物并冷凝其中的水，特别是如果使用稀释蒸汽以降低烷烃或链烷烃的分压时。包含在反应器流出物流中的催化剂和细粉不能容易地从骤冷水中分离，导致设备中的过度积垢和随之而来的高维护成本。因此，还需要改善在来自脱氢反应器的流出物流中发现的催化剂细粉的回收。
一些催化剂被从反应器中夹带走并需要在进入下游分离步骤之前去除。反应器流出物含有来自添加在反应器中的稀释蒸汽或汽提/流化蒸汽的蒸汽(水)。在冷却反应器流出物以及冷凝出流出物中的水之后，从水中分离催化剂是有问题的，因为混合物变成泥浆状，其难以过滤或运输。即使过滤催化剂，所得水-催化剂浆液也不适合返回到反应器中用于催化剂回收。
附图简述
图1是本文所描述的用于使用燃料油洗涤以从流化床丙烷脱氢反应器流出物中去除催化剂的方法的非限制性示意图；
图2是本文所描述的用于采用闪蒸区使用燃料油洗涤以从流化床丙烷脱氢反应器流出物中去除催化剂的方法的另一个非限制性实施方案的示意图。
概述
在一个非限制性实施方案中，提供一种用于从流化床丙烷脱氢反应器流出物气体中回收催化剂的方法，其中该方法包括(a)冷却流化床丙烷脱氢反应器流出物气体，(b)使流出物气体与燃料油在洗涤段中接触以洗涤出催化剂，以获得基本上不含催化剂的冷却的流出物气体，(c)从洗涤段提取出油-催化剂浆液并使油-催化剂浆液循环经过过滤器，从而从燃料油中去除催化剂，得到过滤的洗涤油，(d)将过滤的洗涤油作为再循环洗涤油返回到洗涤段；和(e)反冲过滤器，从而回收催化剂。任选地，该方法进一步包括在进入闪蒸区之前使流出物气体与燃料油在直接接触在线设备中接触，随后去除作为浓缩的底部油-催化剂浆液的净量的燃料油和大部分催化剂。
在另一非限制性方案中，进一步提供一种用于从流化床丙烷脱氢反应器流出物气体回收催化剂的系统，其中该系统包括具有用于接收流出物气体的入口的骤冷塔、设置在入口上方用于冷却流出物气体并洗涤出催化剂的蒸气-液体接触元件、在接触元件上方用于排出基本上不含催化剂的冷却的流出物气体的气体出口、以及在入口下方用于从接触元件收集燃料油的液体滞留区、在过滤和反冲模式下可操作的至少一个过滤器、以及用于使来自液体滞留区的燃料油循环经过过滤器并使滤液返回到液体滞留区的过滤回路。任选地，该系统进一步包括直接接触在线设备，其接收和混合流化床丙烷脱氢反应器流出物和燃料油，然后将它们注入闪蒸区。
详述
已经发现，在非限制性实施方案中，在脱氢反应中使一种或多种金属氧化物催化剂与具有2-8个碳原子的链烷烃在反应器中接触约0.05秒至约10分钟的时间段，可以导致对某些烯烃诸如丙烯和丁烯的更好的选择性。还已经发现，由于提升管或流化床类型反应器中的磨损而产生的金属氧化物催化剂粒子和细粉包含在反应器流出物流内。这些催化剂粒子和细粉可以通过以下回收：使反应器的流出物流与洗涤流体，在一个非限制性实施方案中为外部燃料油接触，以形成冷却的催化剂流出物流和基本上不含催化剂的产物流，并且然后用一个或多个过滤器过滤冷却的催化剂流出物流以捕集催化剂细粉用于潜在的再利用。如本文在一个非限制性实施方案中所使用的，“基本上不含催化剂”被定义为不具有有问题量的催化剂粒子或细粉，或者催化剂被去除至实际极限。
在一个实施方案中，有待与(多种)金属氧化物催化剂接触的链烷烃可以包括但不一定限于丙烷、乙烷、正丁烷、异丁烷及其组合。在另一实施方案中，可以在有或没有惰性稀释剂或蒸汽的情况下将链烷烃引入反应器中。
可用于使链烷烃脱氢以产生轻质烯烃产物气体的金属氧化物催化剂可以由以下氧化物中的一种或多种组成：锌、钛、铜、铁、锰、铝、硅、锆、铈、镝、铒、铕、钆、镧、钕、镨、钐、铽、镱、钇或铌。在非限制性实施方案中，所使用的(多种)金属氧化物催化剂基本上不含铂和铬。
在一个非限制性实施方案中，可以通过其中使包含具有2-8个碳的链烷烃的链烷烃原料与一种或多种金属氧化物催化剂在提升管或流化床反应器中在脱氢条件下接触的方法，实现使用以上所描述的种类的金属氧化物催化剂的链烷烃脱氢和反应器流出物流中催化剂细粉的回收。该方法可以在约500℃-800℃的反应温度、约0.1-1h-1的空速和约0.01-0.2MPa的压力下进行。在一个非限制性方案中，反应时间段可以是约0.05秒至约10分钟。在其他非限制性实施方案中，链烷烃与(多种)金属氧化物催化剂之间的脱氢反应也可以在固定床摆动或提升管或流化床反应器中进行，由其形成反应器流出物流。
如图1中示意性地示出的，在一个非限制性方案中，来自流化床丙烷脱氢反应器1的流出物含有少量被夹带的催化剂，其可以理解为催化剂粒子和/或细粉，诸如先前所讨论的金属氧化物催化剂和/或细粉。在逆着反应器进料1冷却流出物1之后，使气体1与骤冷塔A或其他容器中的循环油接触，在非限制性实施方案中，与外部燃料油2接触以洗涤出任何夹带的催化剂，并将其带回到反应器再生器以回收催化剂并提供用于再生的燃料。洗涤步骤在骤冷塔A的油洗涤段B中发生，该油洗涤段B利用接触设备诸如塔板或填料以确保洗涤油2与工艺流出物气体1之间的良好接触，用于有效去除催化剂。将来自外部来源的洗涤油2添加至该洗涤段B的顶部。将油-催化剂浆液3从洗涤段B的底部提取出，并使至少部分流体循环经过过滤系统或过滤器C，其从油-催化剂浆液3中去除催化剂。过滤的洗涤油4在过滤油热交换器D中被冷却(热量用于工艺加热)并返回到洗涤段B的顶部。当反冲(多个)过滤器C时，回收的催化剂5与添加至系统中的净量的洗涤油一起被送至反应器系统再生器，在那里洗涤油提供用于催化剂再生所需的净热量。冷却的流出物气体6被再循环至骤冷水(QW)段。
油洗涤段B可以是单独的塔或者如图1中所示出的，在一个非限制性实施方案中被集成为水骤冷塔A的下部段。
用于催化剂过滤设备C的一个选择将是使用具有固定过滤介质诸如烧结金属型过滤器的多床系统。在过滤床装载有催化剂之后，循环油流3将切换至第二过滤器，而第一过滤器将被再生以清洁过滤器并回收催化剂。
供选择的(多个)过滤设备C将使用连续过滤系统，其中油流过鼓型过滤器，并且催化剂被从过滤器的内表面连续地去除，并且浓缩的催化剂-油浆液被连续地去除并送至反应器再生器。
供选择地，如图2中示意性地示出的，在逆着反应器进料1冷却流化床丙烷脱氢反应器流出物气体1之后，使流出物气体1与燃料油4在进入容器A中的闪蒸区F之前在直接接触在线设备E(诸如骤冷配件)中接触。在闪蒸区F中，净量的油2和大部分夹带的催化剂作为浓缩的底部催化剂-油浆液5去除，该浆液可以被引导至反应器再生系统(未示出)用于催化剂回收并提供净燃料需求。
来自闪蒸区F的气体(其几乎不含催化剂)接着进入洗涤段B，该洗涤段B利用接触设备诸如塔盘或填料以确保洗涤油与工艺气体之间的良好接触，用于有效去除剩余的催化剂，如先前所描述的。来自洗涤段B的油3在油热交换器D中被泵循环并冷却(热量用于工艺加热)，并返回到洗涤段B的顶部。该油4的一部分用于如以上所描述的直接接触在线设备E中。
闪蒸区和油洗涤段可以一起安置在单独的塔中或如图2中示意性地示出的被集成为水骤冷塔的下部段。
使用用于反应器再生的燃料油作为洗涤油2以从反应器流出物1中去除催化剂提供了去除催化剂、回收工艺热和使回收的催化剂返回到反应器系统的有效方式的技术和商业优势。闪蒸区F设计的应用可以消除对催化剂过滤器的需要，或者显著减小过滤器的尺寸，并且还显著减小在油洗涤段B中使用的循环燃料油3中的催化剂含量，这减小了在该回路中积垢的可能性。
在前述说明书中，已经参考本发明的具体实施方案描述了本发明。然而，说明书应被认为是说明性的而不是限制性的。例如，链烷烃、金属氧化物催化剂、脱氢反应条件和设备、燃料油、流化床丙烷脱氢反应器流出物、催化剂细粉回收条件和设备落入要求保护的或公开的参数内，但在具体实施例中未具体确定或尝试，预期在本发明的范围内。
本发明可以在不存在未公开的元件的情况下实施。另外，本发明可以适当地包括所公开的元件、由所公开的元件组成或基本上由所公开的元件组成。例如，可以提供一种用于从流化床丙烷脱氢反应器流出物气体回收催化剂的方法，其中该方法基本上由以下组成或由以下组成：(a)冷却流化床丙烷脱氢反应器流出物气体，(b)使流出物气体与燃料油在洗涤段中接触以洗涤出催化剂，以获得基本上不含催化剂的冷却的流出物气体，(c)从洗涤段提取出油-催化剂浆液并使油-催化剂浆液循环经过过滤器，从而从燃料油中去除催化剂，得到过滤的洗涤油，(d)将过滤的洗涤油作为再循环洗涤油返回到洗涤段；和(e)反冲过滤器，从而回收催化剂。任选地，该方法进一步基本上由以下或由以下组成：使流出物气体与燃料油接触在进入闪蒸区之前在直接接触在线设备中发生，随后去除作为浓缩的底部油-催化剂浆液的净量的燃料油和大部分催化剂。
供选择地，可以在另一非限制性方案中提供一种用于从流化床丙烷脱氢反应器流出物气体回收催化剂的系统，其中该系统基本上由以下或由以下组成：具有用于接收流出物气体的入口的骤冷塔、设置在入口上方用于冷却流出物气体并洗涤出催化剂的蒸气-液体接触元件、在接触元件上方用于排出基本上不含催化剂的冷却的流出物气体的气体出口、以及在入口下方用于从接触元件收集燃料油的液体滞留区、在过滤和反冲模式下可操作的至少一个过滤器、以及用于使来自液体滞留区的燃料油循环经过过滤器并使滤液返回到液体滞留区的过滤回路。任选地，该系统进一步基本上由以下或由以下组成：直接接触在线设备，其接收和混合流化床丙烷脱氢反应器流出物和燃料油，然后将它们注入闪蒸区。
在整个权利要求中使用的词语“包括/包含(comprising)”和“包括/包含(comprises)”应分别理解为“包括但不限于(including but not limited to)”和“包括但不限于(includes but not limited to)”。
如本文所用，词语“基本上”应意指“大部分但不全部是指定的”。
如本文所用，除非上下文另外明确指出，否则单数形式“一个/种(a)”、“一个/种(an)”和“该/所述(the)”也意图包括复数形式。
如本文所用，关于给定参数的术语“约”包括所述值并且具有由上下文规定的含义(例如，其包括与给定参数的测量相关的误差程度)。
如本文所用，术语“和/或”包括一个或多个相关联的所列项目的任何和所有组合。
Claims (18)
1.一种用于从流化床丙烷脱氢反应器流出物气体回收催化剂的方法，所述方法包括：
(a)冷却流化床丙烷脱氢反应器流出物气体；
(b)使冷却的流出物气体与燃料油在洗涤段中接触以洗涤出催化剂，以获得基本上不含催化剂的冷却的流出物气体；
(c)从所述洗涤段提取出油-催化剂浆液并使所述油-催化剂浆液循环经过过滤器，从而从所述燃料油中去除催化剂，得到过滤的洗涤油；
(d)将过滤的洗涤油作为再循环洗涤油返回到所述洗涤段；和
(e)反冲所述过滤器，从而回收催化剂。
2.权利要求1所述的方法，其中，所述接触和返回步骤在骤冷塔中实现，所述骤冷塔包含蒸气-液体接触元件和存留燃料油存量的底部区域。
3.权利要求1所述的方法，其还包括在所述接触步骤之前冷却所述再循环洗涤油。
4.权利要求1所述的方法，其中，使所述油-催化剂浆液循环经过过滤器包括使所述油-催化剂浆液以过滤模式连续经过至少一个第一过滤器以从其中分离所述催化剂，得到滤液，同时与所述第一过滤器并联的至少一个第二过滤器处于反冲模式从而从其中去除分离的催化剂。
5.权利要求4所述的方法，其还包括将滤液从所述第一过滤器返回至所述燃料油存量。
6.权利要求4所述的方法，其中，所述至少一个过滤器的反冲还包括在过滤模式与反冲模式之间周期性地交替所述至少一个第一过滤器和所述至少一个第二过滤器。
7.权利要求4所述的方法，其中，所述反冲包括至少一次使压缩气体脉冲经过所述第二过滤器用于去除催化剂。
8.权利要求2所述的方法，其中，所述燃料油是来自所述燃料油存量的所述燃料油的一部分。
9.权利要求1所述的方法，其中，所述过滤器是包含多个床的多床系统，每个床包含固定的过滤介质，其中在所述方法中使所述油-催化剂浆液循环经过所述多床系统还包括：
(a)使所述油-催化剂浆液循环经过至少第一床，从而用催化剂装载所述第一床，
(b)使所述油-催化剂浆液切换循环经过至少第二床，同时再生所述至少第一床并回收所述催化剂。
10.权利要求9所述的方法，其中，所述固定的过滤介质是烧结金属过滤器。
11.权利要求1所述的方法，其中，所述过滤器是包含具有内表面的鼓式过滤器的连续过滤系统，其中在所述方法中使所述油-催化剂浆液循环经过所述连续过滤系统包括：
(a)从所述内表面连续去除催化剂；和
(b)连续去除浓缩的油-催化剂浆液并将其送至反应器发生器。
12.权利要求1所述的方法，其中，在所述方法中，使所述流出物气体与燃料油接触在进入闪蒸区之前在直接接触在线设备中发生，随后去除作为浓缩的底部油-催化剂浆液的净量的燃料油和大部分催化剂。
13.权利要求1所述的方法，其还包括将来自所述循环步骤的所述浆液的至少一部分引入催化剂再生器中用于燃烧以再生和加热所述催化剂。
14.一种用于从流化床丙烷脱氢反应器流出物气体回收催化剂的系统，所述系统包含：
(a)骤冷塔，其具有用于接收所述流出物气体的入口；蒸气-液体接触元件，其设置在所述入口上方用于冷却所述流出物气体并洗涤出所述催化剂；
(b)气体出口，其在所述接触元件上方用于排出基本上不含催化剂的冷却的流出物气体；和液体滞留区，其在所述入口下方用于从所述接触元件收集所述燃料油；
(c)至少一个过滤器，其在过滤和反冲模式下可操作；和
(d)过滤回路，其用于使来自所述液体滞留区的燃料油循环经过过滤器并使滤液返回到所述液体滞留区。
15.权利要求14所述的系统，其还包括直接接触在线设备，其接收和混合所述流化床丙烷脱氢反应器流出物和所述燃料油，然后将它们注入闪蒸区。
16.权利要求14所述的系统，其中，所述过滤器包括包含多个床的多床系统，每个床包含固定的过滤介质。
17.权利要求14所述的系统，其中，所述固定的过滤介质是烧结金属过滤器。
18.权利要求14所述的系统，其中，所述过滤器是包含具有内表面的鼓式过滤器的连续过滤系统。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US16/570029 | 2019-09-13 | ||
| US16/570,029 US11117108B2 (en) | 2019-09-13 | 2019-09-13 | Use of a fuel oil wash to remove catalyst from a fluidized-bed propane dehydrogenation reactor effluent |
| PCT/US2020/050052 WO2021050631A1 (en) | 2019-09-13 | 2020-09-10 | Use of a fuel oil wash to remove catalyst from a fluidized-bed propane dehydrogenation reactor effluent |
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| EP (1) | EP4028154A4 (zh) |
| JP (1) | JP2022547708A (zh) |
| KR (1) | KR20220087435A (zh) |
| CN (1) | CN114364455A (zh) |
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| US11725153B2 (en) | 2020-04-17 | 2023-08-15 | Uop Llc | Process and apparatus for recovering catalyst from a product stream |
| KR20240072582A (ko) | 2022-11-17 | 2024-05-24 | 한국에너지기술연구원 | 가압 기포유동층 촉매 재생시스템 및 그 운전방법 |
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- 2019-09-13 US US16/570,029 patent/US11117108B2/en active Active
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- 2020-09-10 EP EP20863789.2A patent/EP4028154A4/en active Pending
- 2020-09-10 KR KR1020227010059A patent/KR20220087435A/ko unknown
- 2020-09-10 CN CN202080064022.8A patent/CN114364455A/zh active Pending
- 2020-09-10 JP JP2022516243A patent/JP2022547708A/ja active Pending
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Also Published As
| Publication number | Publication date |
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| JP2022547708A (ja) | 2022-11-15 |
| KR20220087435A (ko) | 2022-06-24 |
| EP4028154A1 (en) | 2022-07-20 |
| EP4028154A4 (en) | 2023-09-20 |
| ZA202202993B (en) | 2022-11-30 |
| US11117108B2 (en) | 2021-09-14 |
| WO2021050631A1 (en) | 2021-03-18 |
| US20210077967A1 (en) | 2021-03-18 |
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