CN101360556B - 双环流反应器中的动态压力控制 - Google Patents
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Abstract
本发明公开了一种包括至少两个串联连接的环流反应器且其中连接两个环流的管线经受动态压差的淤浆环流反应器。
Description
技术领域
本发明涉及在双环流反应器中的烯烃聚合领域。
背景技术
高密度聚乙烯(HDPE)最先是通过在为所得聚合物的溶剂的液体中进行加聚反应生产的。该方法迅速被依照齐格勒或菲利普的淤浆条件下的聚合所替代。更具体而言，淤浆聚合在管式环流反应器中连续地进行。形成聚合流出物，其为悬浮在液体介质，常为反应稀释剂和未反应单体中的颗粒聚合物固体物的淤浆(参见US-A-2,285,721)。需要将聚合物与包括惰性稀释剂和未反应单体的液体介质分离而不暴露液体介质形成污染，以便该液体介质在最少或无纯化下再循环至聚合区域。如US-A-3,152,872中所述，聚合物与液体介质的淤浆收集在淤浆环流反应器的一个或者多个沉降腿中，所述淤浆周期性地从所述沉降腿排放到闪蒸室中由此以间隙方式操作。闪蒸混合物以从聚合物中除去液体介质。然后必需再压缩气化的聚合反应稀释剂以浓缩其至液态，若需要纯化后，然后将其作为液体稀释剂再循环至聚合区域。
沉降腿典型用于提高从反应器抽提出的淤浆中的聚合物浓度；但是由于连续工艺上施加了间隙工艺因而沉降腿有很多问题。
EP-A-0,891,990和US-A-6,204,344公开了两种用于减少反应器不连续行为从而提高固体物浓度的方法。一种方法在于用富集淤浆的连续补偿代替沉降腿的不连续操作。另一种方法在于使用更强劲的循环泵。
新近，EP-A-1410843公开了一种淤浆环流反应器，该反应器包括在环流之一上通过与主路线具有不同输送时间的替换路线来连接同一环流两点的支路管线，用于提高循环淤浆均一性。
双环流体系由于通过在各反应器中提供不同的聚合条件而提供了制备高度定制聚烯烃的可能性而十分令人满意。然而，由于在当前的结构下，双环流反应器需要彼此靠近以确保从一环流到另一环流的生长聚合物足够地输送，因而找到合适空间建造这些双环流反应器经常是困难的。在输送管线中循环的物料的平均速度小于1米/秒，因而这些输送管线必须非常短以避免残留单体聚合导致的沉降和堵塞。因此需要提供手段以连接两彼此距离很远的现有反应器，或者如可用空间要求这样则建造两个不需要彼此靠近的新反应器。
发明内容
本发明一个目的在于提供用于连接两个或者多个环流反应器的控制手段。
本发明一个目的还在于降低连接反应器的管线中材料的滞留时间。
本发明另一目的在于提高环流反应器中的流体均一性。
本发明进一步目的在于提高第一反应器中的烯烃浓度。
本发明另一目的为增加固体物含量。
因此，本发明公开了一种包括至少两个串联连接的环流反应器且其中连接两环流的管线经受动态压力差的淤浆环流反应器。
由于控制用于间隙排放与连续操作的混合，因而难以维持两环流反应器间的恒定压差。本发明因而公开了一种体系，其中第二反应器中压力实时受控于第一反应器中的压力变化以维持预定的压力差。
本发明提供了一种包括下列步骤的烯烃淤浆聚合方法：
-提供至少两个串联连接的环流反应器；
-提供连接两个环流反应器的管线，其中连接两个环流的所述管线经受动态压力差；
该方法特征在于第二反应器中的压力实时受控于第一反应器中的压力变化以维持预定的压力差。
典型的压力差最多为5巴，优选0.5～2巴，更优选1.5～2巴。必须指出两环流之间在各排空处(排空(dump))末端的压差可大于或等于差示设定值。
在根据本发明的第一个实施方案中，两个环流反应器通过连接第一反应器的沉降腿与第二反应器的传统管线连接。
在根据本发明的另一优选实施方案中，两个环流反应器通过支路管线(11)连接，如图1所示，该支路管线(11)通过与主路线有不同输送时间的替换路线来连接同一反应器的两点(12)和(13)，该支路管线(11)还在出口点(14)收集排出第一环流反应器(1)的生长聚合物并将所述生长聚合物输送到第二反应器(2)的入口点(13)。
附图说明
图1所示为双环流反应器结构，其中两反应器通过支路管线连接。
图2所示为第一第二反应器中作为时间函数的典型压力图，压力用巴表示，时间用时:分:秒表示。
图3所示为包括表示为LPn的低压指示和可激活以控制反应器操作的阀系统的双环流反应器结构。
所有实施方案中，通过设定值与腿排空之间的相互作用对压力进行典型控制。每次达到设定值，对一个腿进行排空，随后压力降至低于设定值的值，这对维持压力控制是必要的。若压力下降不充分，有方案恢复控制。这类控制对于为间隙过程的腿清空与环流反应器中连续过程的聚合是必需的。
现有技术中，操作双环流反应器的传统方法是用静态设定值和静态差压工作。
本发明直接关联第二反应器的设定值与第一反应器的过程值。5采用能关联两反应器中间隙清空过程与连续聚合过程的动态控制系统。
本发明因而一直能维持需要的压力差。
因而，相比第一反应器，第二反应器的清空动态需更受约束以应付第一与第二两反应器的所有扰乱。第一与第二反应器的典型压力图如图2所示。
清空第一反应器的一个腿时，第一反应器的压力下降，第二反应器的压力直接升高，同时维持压差。第二反应器达到设定值，其为第一反应器的实际过程值时，此时压力低于初始压力，降低差压，第二反应器的一腿被清空。
循环然后重新开始，第一反应器的压力再次升高。
可通过连续放料或者沉降腿技术收集排出第一反应器的生长聚合物。优选使用沉降腿。
在整个说明书中，构成淤浆环流反应器的环流串联方式连接，且各环流可以折叠。
任选地，管线可以加上夹套。
使用支路管线时，连接环流反应器的管线中循环材料的速度必须足以避免沉降和可能的堵塞，必须至少为3米/秒。
本发明可与所有类型催化剂体系一起使用。可用于烯烃优选乙烯和丙烯的均聚或共聚。已证明对用茂金属催化剂体系制备双峰聚合物特别有用。
实施例
差压控制
通常操作中，采用差压测量通过第一反应器B的压力对第二反应器A的压力级联控制。该控制有固定、在0～5巴变化的可手动调整的设定值。
也可手动打开/关闭级联控制，用双模调节组件进行个别和独立控制以允许起动。
通常结构如附图3所示。
偏离状况下，考虑和研究多种可能性。
1.第二反应器A的压力过高。
设置“两清空间最小等待时间”为1秒防止第二反应器中的压力升高。然而，如该压力已升高且如果没有实现此后所述的额外标准，则反应器被毁。这些额外标准与差压相关。典型地，差压(DP)设定值在0.5～5巴间调整。反应器操作过程中激活压差控制时，若差压连续30秒下降到设定值一半以下，则两反应器都被毁。这通过一级差压互锁进行级联处理。
2.第二反应器A压力过低。
该偏离状况下无需对差压互锁采取动作：该状况包括在如图3所示的LP6低压指示器中。若LP6低于35巴(barg)，则自动关闭阀12，13，14和15，若降到30巴(barg)，则自动锁定阀10和11。
3.第一反应器B压力过低。
这种形势在例如产品取出阀(PTO)在开启位置被阻塞时发生。第一反应器B的压力降低，第二反应器A也如此。发生了压差保持太高无法激活一级差压互锁。若由于反馈错误导致的阻塞，且如同时第二反应器A的压力小于37巴(barg)超过5秒，则阻塞的PTO上方的Borsig阀关闭。这种情形通过差压互锁2，3和4进行级联处理。
在根据本发明的另一实施例中，第一反应器B中低温导致该反应器低压。反应器中的大量氢减缓了反应从而降低了温度。若差压控制不能补偿第一反应器B的这种压力降，则反应器毁坏。
4.第一反应器B压力过高。
这种形势并不危急，无需执行特定动作。
Claims (6)
1.一种在连接有关腿清空的间隙过程和有关聚合的连续过程的体系中进行烯烃的淤浆聚合方法，包括下列步骤：
-提供至少两个串联连接的环流反应器；
-提供连接两个环流反应器的管线(11)，该管线(11)在出口点(14)收集
排出第一环流反应器(1)的生长聚合物并将所述生长聚合物输送到第二反
应器(2)的入口点(13)，其中该连接两个环流的管线经受动态压差；
该方法特征在于第二反应器中的压力实时受控于第一反应器中的压力变化以维持预定的压力差。
2.权利要求1的方法，其中压力差至多5巴。
3.权利要求2的方法，其中压力差为0.5～2巴。
4.前述权利要求中任一项的方法，其中所述两个环流反应器通过支路管线(11)连接，所述支路管线(11)通过与主路线具有不同输送时间的替换路线来连接同一环流反应器的两点(12)和(13)，所述支路管线(11)还在出口点(14)处收集排出所述第一环流反应器(1)的生长聚合物并将该生长聚合物送至所述第二反应器(2)的入口点(13)。
5.权利要求4的方法，其中在连接所述两个环流反应器的所述支路管线中的速度大于3米/秒。
6.权利要求1-3中任一项的方法，其中所述烯烃为乙烯或者丙烯。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP05028726A EP1803498A1 (en) | 2005-12-30 | 2005-12-30 | Dynamic pressure control in double loop reactor |
| EP05028726.7 | 2005-12-30 | ||
| PCT/EP2006/012534 WO2007076996A1 (en) | 2005-12-30 | 2006-12-27 | Dynamic pressure control in double loop reactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101360556A CN101360556A (zh) | 2009-02-04 |
| CN101360556B true CN101360556B (zh) | 2012-09-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800498631A Expired - Fee Related CN101360556B (zh) | 2005-12-30 | 2006-12-27 | 双环流反应器中的动态压力控制 |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US8455595B2 (zh) |
| EP (2) | EP1803498A1 (zh) |
| JP (1) | JP5203966B2 (zh) |
| KR (2) | KR20120123151A (zh) |
| CN (1) | CN101360556B (zh) |
| EA (1) | EA013387B1 (zh) |
| WO (1) | WO2007076996A1 (zh) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2148892B2 (en) † | 2007-05-18 | 2014-06-18 | INEOS Manufacturing Belgium NV | Slurry phase polymerisation |
| ATE509035T1 (de) * | 2007-08-27 | 2011-05-15 | Basell Poliolefine Srl | Verfahren zur polymerisierung von olefinen mithilfe mehrerer schlaufenreaktoren |
| EP2055725A1 (en) * | 2007-11-05 | 2009-05-06 | Total Petrochemicals Research Feluy | Reduced blockage when transferring polymer product from one reactor to another |
| US9556283B2 (en) * | 2010-05-21 | 2017-01-31 | Chevron Phillips Chemical Company, Lp | Polyethylene production with multiple polymerization reactors |
| US20140171601A1 (en) * | 2012-12-13 | 2014-06-19 | Chevron Phillips Chemical Company, Lp | Polyethylene production with multiple polymerization reactors |
| US8344078B2 (en) | 2010-05-21 | 2013-01-01 | Chevron Phillips Chemical Company Lp | Continuous take off technique and pressure control of polymerization reactors |
| ES2462166T3 (es) | 2011-12-19 | 2014-05-22 | Borealis Ag | Reactor de bucle que proporciona un avanzado control de la división de la producción |
| US9765165B2 (en) * | 2013-01-22 | 2017-09-19 | Total Research & Technology Feluy | Olefin polymerization process with continuous discharging |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1681582A (zh) * | 2002-09-23 | 2005-10-12 | 托塔尔石油化学产品研究弗吕公司 | 淤浆环管聚烯烃反应器 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1503642A (fr) * | 1966-09-22 | 1967-12-01 | S I C E R Soc Ind & Commercial | Réacteur continu pour fluides liquides et éventuellement gazeux |
| GB9312225D0 (en) * | 1993-06-14 | 1993-07-28 | Exxon Chemical Patents Inc | Process and apparatus |
| US20050272891A1 (en) * | 2004-02-13 | 2005-12-08 | Atofina Research S.A. | Double loop technology |
| EP1564224A1 (en) * | 2004-02-13 | 2005-08-17 | Total Petrochemicals Research Feluy | Slurry loop reactors |
| EP1564223A1 (en) * | 2004-02-13 | 2005-08-17 | Total Petrochemicals Research Feluy | Interconnected loop reactors |
| EA200601490A1 (ru) * | 2004-02-13 | 2007-02-27 | Тотал Петрокемикалс Рисерч Фелюй | Многоконтурный реактор для полимеризации олефинов |
| EP1611948A1 (en) * | 2004-07-01 | 2006-01-04 | Total Petrochemicals Research Feluy | Polymerization reactors with a by-pass line |
-
2005
- 2005-12-30 EP EP05028726A patent/EP1803498A1/en not_active Withdrawn
-
2006
- 2006-12-27 EP EP06829873A patent/EP1965904A1/en not_active Withdrawn
- 2006-12-27 KR KR1020127024938A patent/KR20120123151A/ko not_active Application Discontinuation
- 2006-12-27 WO PCT/EP2006/012534 patent/WO2007076996A1/en active Application Filing
- 2006-12-27 JP JP2008547894A patent/JP5203966B2/ja not_active Expired - Fee Related
- 2006-12-27 EA EA200801169A patent/EA013387B1/ru not_active IP Right Cessation
- 2006-12-27 KR KR1020087014548A patent/KR101226054B1/ko not_active IP Right Cessation
- 2006-12-27 US US12/159,302 patent/US8455595B2/en not_active Expired - Fee Related
- 2006-12-27 CN CN2006800498631A patent/CN101360556B/zh not_active Expired - Fee Related
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2013
- 2013-04-24 US US13/869,272 patent/US20130231446A1/en not_active Abandoned
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1681582A (zh) * | 2002-09-23 | 2005-10-12 | 托塔尔石油化学产品研究弗吕公司 | 淤浆环管聚烯烃反应器 |
Also Published As
| Publication number | Publication date |
|---|---|
| EA200801169A1 (ru) | 2009-12-30 |
| JP5203966B2 (ja) | 2013-06-05 |
| EP1965904A1 (en) | 2008-09-10 |
| KR20120123151A (ko) | 2012-11-07 |
| US20130231446A1 (en) | 2013-09-05 |
| CN101360556A (zh) | 2009-02-04 |
| US8455595B2 (en) | 2013-06-04 |
| KR20080080120A (ko) | 2008-09-02 |
| WO2007076996A8 (en) | 2008-07-10 |
| KR101226054B1 (ko) | 2013-01-24 |
| WO2007076996A1 (en) | 2007-07-12 |
| US20110105701A1 (en) | 2011-05-05 |
| EA013387B1 (ru) | 2010-04-30 |
| JP2009522384A (ja) | 2009-06-11 |
| EP1803498A1 (en) | 2007-07-04 |
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