CN1922288B - 在烃的热裂解期间提高液体产率的方法 - Google Patents
在烃的热裂解期间提高液体产率的方法 Download PDFInfo
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Abstract
将金属添加剂引入烃进料流在烃的热裂解期间产生了提高的烃液体产率。合适的添加剂包括金属强碱和金属分散体，合适的金属包括，但不一定限于，镁、钙、铝、锌、硅、钡、铈和锶的强碱以及分散体。焦化器进料特别为可以有利地对其使用本方法的烃进料流，但也可以将该技术用于热裂解的任何烃进料。
Description
发明领域
本发明涉及在烃的热裂解期间提高液体产率的方法和组合物，更特别地，在一个实施方案中涉及通过将添加剂引入烃而在烃的热裂解期间提高液体产率的方法和组合物。
发明背景
许多石油精炼厂采用延迟焦化装置来加工渣油。延迟焦化是一种从重质石油底部级分的另外差的资源中获得有价值的产品的方法。延迟焦化在加热炉或焦化炉中将这些底部级分的温度升高，并且在焦炭塔中将它们的大部分转化成焦炭。焦炭塔中的液体具有长的停留时间以将渣油转化成较低分子量的烃，这些烃从焦炭塔中蒸馏出。来自于焦炭塔的塔顶蒸气通入分馏器，在其中将各种级分分离。其中一种级分是汽油沸程的物流。被普遍称作焦化汽油的该物流通常是相对低辛烷值的物流，其适合于用作提高等级的汽车燃料。得自于该热裂解的液体产品通常比制得的焦炭更有价值。延迟焦化是采用重质底部级分的热裂解以制得有价值的气体和液体级分以及较少价值的焦炭而将有价值的产品从加工过的油中回收的方法的一个例子。
因此，希望的是提供将提高得自于热裂解工艺的液体烃产品的产率的方法和/或组合物。
发明概述
因此，本发明的一个目的是提供一种提高得自于热裂解工艺的液体产率的组合物和方法。可应用本发明的热裂解工艺包括，但不一定限于，延迟焦化、灵活焦化、流化焦化等。
本发明的另一个目的是提供一种使用容易获得的添加剂在延迟焦化、灵活焦化或流化焦化期间提高液体产率的组合物和方法。
在实施本发明的这些和其它目的中，在一个形式中提供了一种在烃的热裂解期间提高液体产率的方法，该方法包括：将金属添加剂引入烃进料流，将烃进料流加热至热裂解温度，和将烃液体产品回收。该金属添加剂可以是金属强碱(overbase)或金属分散体。
在本发明的另一个非限制性实施方案中，提供了一种涉及到焦化操作的精炼方法，该方法包括：将金属添加剂引入焦化器进料流，将焦化器进料流加热至热裂解温度，和将烃液体产品回收。同样，金属添加剂可以是金属强碱或金属分散体或者其结合物。
附图简述
图1是将热裂解用于HTFT烃流的实施例1-5的百分比液体产率结果的图；
图2是将实施例2-4的液体产率增量与图1的空白值(1)(实施例1)作比较的图；
图3是将实施例2-4的液体产率增量与图1的空白值(2)(实施例5)作比较的图；和
图4是将热裂解用于HTFT烃流的实施例6-10的百分比液体产率结果的图。
发明详述
已经发现：在烃的热裂解例如热焦化工艺期间使用强碱添加剂或金属分散体提高了液体产率。在焦炭生产期间提高液体产率的任何方法对于操作者而言都将具有显著的价值。
我们预期，本发明的方法和添加剂将可用于例如在焦化应用中将被热裂解的任何烃进料流，这些进料流包括，但不一定限于，焦化器进料流、常压塔底部级分、减压塔底部级分、得自于FCC装置的浆液、减粘裂化装置流、废油等。如前所述，可应用本发明的热裂解工艺包括，但不一定限于，延迟焦化、灵活焦化和流化焦化等。
用于本发明的合适的金属添加剂包括，但不一定限于，镁强碱、钙强碱、铝强碱、锌强碱、硅强碱、钡强碱、锶强碱、铈强碱和其混合物，以及分散体。这些强碱和分散体可溶于烃，尽管通常与含水体系相比更难以得到分散于烃中的这些添加剂。在本发明的一个非限制性实施方案中，该金属添加剂含有至少约1wt％的镁、钙、铝、锌、硅、钡、铈或锶。在一个选择性实施方案中，该添加剂含有约5wt％的金属，在另一个非限制性实施方案中，金属或碱土金属的量至少为约17wt％，并且在一个不同的选择性实施方案中至少为约40wt％。制备这些金属强碱和分散体材料的方法是公知的。在一个非限制性实施方案中，通过将妥尔油与氢氧化镁加热来制备金属强碱。在另一个实施方案中使用氧化铝制备强碱。在另一个实施方案中使用氧化镁或氧化铝制备分散体。使用其它金属制得的分散体和强碱将类似地制备。在一个非限制性实施方案中，这些分散体和强碱的目标粒度约为10微米或更小，选择性地约为1微米或更小。将理解的是：添加剂中的全部颗粒并非具有该目标粒度，但获得一种“钟形”分布以使得平均粒度分布为10μ或更小，或者选择性地为1μ或更小。
更详细地，可用于本发明的金属分散体或络合物可以现有技术公知的用于制备强碱性盐的任何方式制备，条件是由其得到的强碱络合物处于细碎的形式，并且在一个非限制性实施方案中为在烃进料流中形成稳定分散体的亚微米颗粒。因此，用于制备本发明的添加剂的一种非限制性方法是形成所希望金属的碱(例如，Mg(OH)2)与以和氢氧化物化学计量反应所需的量相比少得多的数量存在的络合剂(例如，脂肪酸如妥尔油脂肪酸)以及非挥发性稀释剂的混合物。将该混合物加热至约250-350℃的温度，由此提供金属氧化物和脂肪酸金属盐的强碱络合物或分散体。
上述制备本发明的强碱络合物的方法特别描述于美国专利No.4,163,728中，其中例如在约280-330℃的温度下在合适的非挥发性稀释剂中将Mg(OH)2和羧酸络合剂的混合物加热。
用于本发明的络合剂包括，但不一定限于，羧酸、酚、有机磷酸和有机硫酸(sulfur acid)。包括目前用于制备强碱性材料(例如，描述于美国专利Nos.3,312,618；2,695,910；和2,616,904中的那些)并且构成本领域公知的酸类型的那些酸。本身为油溶性的羧酸、酚、有机磷酸和有机硫酸，特别是油溶性磺酸尤其可用。这些有机酸性物质的油溶性衍生物，例如它们的金属盐、铵盐和酯(特别是与含有多至6个碳原子的低级脂族醇例如低级链烷醇的酯)可以作为替代使用或者与游离酸组合使用。当提及到酸时，隐含地包括了它的等效衍生物，除非明显仅仅是指酸。可在本文中使用的合适的羧酸络合剂包括：脂族、脂环族和芳族的单-和多元羧酸，例如环烷酸、烷基或烯基取代的环戊酸、烷基或烯基取代的环己酸和烷基或烯基取代的芳族羧酸。脂族酸通常是长链酸并且含有至少8个碳原子，并且在一个非限制性实施方案中为至少12个碳原子。脂环族和脂族羧酸可以是饱和或不饱和的。
可适合用于本发明方法的金属添加剂还包括其中已经进行了碳酸化步骤的真正的强碱化合物。一般而言，如本领域非常公知的那样碳酸化涉及到CO2的加入。
难以提前预计本发明的强碱添加剂将以什么比例处于其所应用的烃进料流中。该比例取决于大量复杂、相关的因素，这些因素包括，但不一定限于，烃流体的性质、焦炭塔或其它加工装置的温度和压力条件、烃流体中沥青质的数量、所使用的特定的本发明组合物等。已经发现：进料中较高程度的沥青质需要较高程度的添加剂，也就是说，添加剂的含量将与进料中沥青质的含量相对应并且与之成正比。然而，为了给出一定意义的合适比例，本发明的强碱添加剂的比例可以基于烃流体约为1ppm-约1000ppm的程度使用。在本发明的另一个非限制性实施方案中，该范围的上限可以约为500ppm，并且选择性地为多至约300ppm。在本发明的一个不同的非限制性实施方案中，强碱添加剂的该比例范围的下限可以约为50ppm，和可选择地，另一个非限制性的范围可以约为75ppm。
尽管可以将强碱添加剂送入焦化器进料或者送入延迟焦化器的侧线，但在本发明的一个非限制性实施方案中，在不影响其它装置的情况下将添加剂在尽可能远离焦化炉的上游引入。在某种程度上，这将确保添加剂与进料流的完全混合，并且提供了使进料流中的油和沥青质稳定的最大时间。
烃进料流的热裂解应该在相对高的温度下进行，在一个非限制性实施方案中在约850℉(454℃)-约1300℉(704℃)的温度下进行。在另一个非限制性实施方案中，本发明的方法在约900℉(482℃)-约950℉(510℃)的热裂解温度下实施。
可以任选地将分散剂与强碱添加剂一起使用以有助于将添加剂分散在整个烃进料中。分散剂的比例可以为基于烃进料的约1-约500ppm。可选择地，在另一个非限制性实施方案中，分散剂的比例可以约为20-约100ppm。合适的分散剂包括，但不一定限于，羧酸酐和α-烯烃，特别是含有2-70个碳原子的α-烯烃的共聚物。合适的羧酸酐包括脂族、环状和芳族的酸酐，并且可以包括，但不一定限于，马来酸酐、琥珀酸酐、戊二酸酐、四丙烯(tetrapropylene)琥珀酸酐、邻苯二甲酸酐、偏苯三酸酐(油溶性、非碱性)、和其混合物。为了制得油溶性产品，典型的共聚物包括这些酸酐与α-烯烃的反应产物。合适的α-烯烃包括，但不一定限于，乙烯、丙烯、丁烯(例如，正丁烯和异丁烯)、C2-C70α-烯烃、聚异丁烯、和其混合物。
为了制得油溶性分散剂，典型的共聚物是马来酸酐与α-烯烃的反应产物。可通过1∶1化学计量加入马来酸酐和聚异丁烯来形成可用的共聚物反应产物。在另一个非限制性实施方案中，所得产物的分子量约为5,000-10,000。
现在将相对于某些更具体的实施例来描述本发明，这些实施例仅仅旨在进一步描述本发明，但不以任何方式限制本发明。
表I-用于实验的材料
| 材料名称 | 说明 |
| 添加剂A | 含有约17wt％镁的镁分散体 |
| 添加剂B添加剂C添加剂D | 羧酸酐/C<sub>20-24</sub>α-烯烃共聚物分散剂金属钝化剂使用磺酸制得的铝强碱 |
实验的高温结垢试验(HTFT)步骤
将加热的焦化器进料样品倒入预先称重的100mL烧杯中。将样品的量称重并且记录。在HTFT运行之前，将装有焦化器进料的预先称重的烧杯加热至约400℉(204℃)。将Parr压力容器的底部预先加热至约250℉(121℃)。对于其中使用添加剂C的样品，用添加剂C将金属取样管预处理。然后将取样管放置在温热的油样品中。如果将加入添加剂B或添加剂A，则当进料被加热并且已经变成液体时这样处理。
将HTFT样品加热至所希望的温度，通常为890℉(477℃)-950℉(510℃)，这取决于其中将焦化器进料加工的炉出口温度。当焦化器样品、高压釜底部和HTFT炉已经全部达到合适的试验温度时，将样品烧杯放入高压釜底部，并且将高压釜顶部相对于底部紧闭。然后将密闭的容器放入加热的炉中。然后在试验运行期间，基于自动化计算机的试验程序每30秒记录试验消耗的时间、样品温度和高压釜压力。当焦化器进料已经达到所希望的试验温度时，在预定的压力水平下将液体烃和蒸气从容器中排出，直到当进行焦化时将所有可获得的液体/气体烃从焦化器进料中除去。在焦化器进料试验样品达到设置的试验温度，即，920℉(493℃)之后，该过程通常在7-10分钟内完成。当冷却时，将冷凝的液体/气体烃测量至最接近0.5mL并且记录液体的重量。记录液体的密度并且计算产率百分比。
结果
测量百分比液体产率的结果示于图1中。该数据表明：当镁强碱添加剂A包含在进料中时，液体产率的水平(实施例2-4)都大于未处理的样品的水平(实施例1和5)。在测量液体产率增量过程中，将加入添加剂时加入样品的液体的量减去，由此使得计算结果守恒。将预期的是加入的任何载体溶剂将与气体级分伴随。
在将含有添加剂A的样品与没有添加剂A的那些作比较时，液体产率增量为1.67-8.63。与空白值(1)(实施例1)和空白值(2)(实施例5)相比的液体产率增量分别示于图2和3中。
另一些结果示于图4中，其使用与实施例1-5相同的加热的焦化器进料。在实施例6的空白值的34.1％产率之上，使用Mg分散体添加剂A的实施例7产生了1.5％的产率％增量，达到35.6％。使用A1强碱添加剂D的实施例8产生了36.7％的产率％，这比空白值高2.6％。使用50/50的添加剂A和添加剂D组合的实施例9产生了36.0％的液体产率％，这在实施例6的空白值之上提高了1.9％。最后，实施例10使用了如同实施例9中的50/50的添加剂A和添加剂D的组合，但处理率为实施例9的一半。实施例10产生了35.6％的液体产率，这在空白实施例6的液体产率％之上1.5％。由此，这些实施例说明使用金属添加剂的组合可以提高液体产率。
精炼厂将观察到本发明的经济价值归因于液体产率水平增加和得到的液体品质的价值。预期的是，使用本发明的强碱添加剂的保守增益将使液体产率提高约2.5％，这在一年的过程期间将是显著的贡献。
在前述的说明书中，已经参照其特定的实施方案描述了本发明，并且已经作为非限制性例子从焦化器进料的热裂解中有效地提高液体产率而阐述了本发明。然而将明显的是：可以对其作出各种改进和变化，只要不偏离描述于附属的权利要求书中的本发明的较宽的精神或范围。因此，本说明书将被看作是说明性的，而不是限制的意义。例如，特定的交联的强碱添加剂，和其与其它分散剂的组合，以及除了特别例举或提及的那些之外的、或者落入所要求的参数内但并未特别地在特定的应用中指出或者尝试以提高液体产率的不同比例的不同含烃液体均处于本发明的范围内。类似地，预期的是将发现本发明的组合物作为用于除了延迟焦化器装置中的流体之外的其它含烃流体的产率提高添加剂的实用性。
Claims (8)
1.一种在烃的热裂解期间提高液体产率的方法，其包括：
将金属添加剂引入烃进料流，其中该金属添加剂选自金属强碱和金属分散体，其中金属添加剂中的金属选自：镁、铝、硅、铈、钡、锶、和其混合物，或者其中金属是钙，钙是唯一的金属；
将烃进料流加热至热裂解温度；和
将烃液体产品回收。
2.权利要求1的方法，其中金属添加剂含有至少1wt％的金属。
3.以上权利要求的任一项的方法，其中将金属添加剂以1-1,000ppm的量加入烃进料流。
4.以上权利要求的任一项的方法，其中热裂解温度为454℃-704℃。
5.以上权利要求的任一项的方法，其中与不存在金属添加剂的相同方法相比，烃液体产品的量增加1.5％、2.6％或1.9％。
6.以上权利要求的任一项的方法，其中烃进料流是焦化器进料流。
7.以上权利要求的任一项的方法，其进一步包括将分散剂引入烃进料流。
8.以上权利要求的任一项的方法，其中该方法是包括焦化操作的精炼方法，和其中烃进料流是焦化器进料流。
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| US5567305A (en) * | 1993-08-06 | 1996-10-22 | Jo; Hong K. | Method for retarding corrosion and coke formation and deposition during pyrolytic hydrocarbon processing |
| TW383911U (en) * | 1997-09-20 | 2000-03-01 | Hon Hai Prec Ind Co Ltd | Module structure for multiple contact points connector |
| US6197075B1 (en) | 1998-04-02 | 2001-03-06 | Crompton Corporation | Overbased magnesium deposit control additive for residual fuel oils |
| AU2003219821A1 (en) | 2002-02-22 | 2003-09-09 | Chevron U.S.A. Inc. | Process for reducing metal catalyzed coke formation in hydrocarbon processing |
| AU2004241454B2 (en) | 2003-05-16 | 2009-04-23 | Exxonmobil Research And Engineering Company | Delayed coking process for producing free-flowing shot coke |
| US7425259B2 (en) | 2004-03-09 | 2008-09-16 | Baker Hughes Incorporated | Method for improving liquid yield during thermal cracking of hydrocarbons |
-
2005
- 2005-03-04 US US11/072,346 patent/US7425259B2/en active Active
- 2005-03-07 CN CN2005800055234A patent/CN1922288B/zh not_active Expired - Fee Related
- 2005-03-07 WO PCT/US2005/007324 patent/WO2005087898A1/en active Application Filing
- 2005-03-07 ES ES05724794.2T patent/ES2481168T3/es active Active
- 2005-03-07 EA EA200601585A patent/EA010011B1/ru not_active IP Right Cessation
- 2005-03-07 BR BRPI0508345-1A patent/BRPI0508345A/pt active Search and Examination
- 2005-03-07 CA CA2559151A patent/CA2559151C/en not_active Expired - Fee Related
- 2005-03-07 PT PT57247942T patent/PT1723216E/pt unknown
- 2005-03-07 KR KR1020067017804A patent/KR101079455B1/ko not_active IP Right Cessation
- 2005-03-07 EP EP05724794.2A patent/EP1723216B1/en not_active Not-in-force
- 2005-07-18 US US11/183,731 patent/US7416654B2/en active Active
-
2006
- 2006-08-07 NO NO20063563A patent/NO20063563L/no not_active Application Discontinuation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4399024A (en) * | 1980-11-27 | 1983-08-16 | Daikyo Oil Company Ltd. | Method for treating petroleum heavy oil |
| US5853565A (en) * | 1996-04-01 | 1998-12-29 | Amoco Corporation | Controlling thermal coking |
| CN1247887A (zh) * | 1999-09-10 | 2000-03-22 | 中国石油化工集团公司北京化工研究院 | 抑制乙烯裂解装置结焦的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| NO20063563L (no) | 2006-10-02 |
| WO2005087898A1 (en) | 2005-09-22 |
| US7416654B2 (en) | 2008-08-26 |
| CA2559151A1 (en) | 2005-09-22 |
| US20050199530A1 (en) | 2005-09-15 |
| EP1723216A1 (en) | 2006-11-22 |
| KR20060126804A (ko) | 2006-12-08 |
| CN1922288A (zh) | 2007-02-28 |
| ES2481168T3 (es) | 2014-07-29 |
| CA2559151C (en) | 2012-12-18 |
| KR101079455B1 (ko) | 2011-11-03 |
| BRPI0508345A (pt) | 2007-07-24 |
| EP1723216B1 (en) | 2014-06-04 |
| US7425259B2 (en) | 2008-09-16 |
| PT1723216E (pt) | 2014-07-14 |
| US20050263439A1 (en) | 2005-12-01 |
| EA010011B1 (ru) | 2008-06-30 |
| EA200601585A1 (ru) | 2007-06-29 |
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