CN1380898A - 在流化床催化裂化工艺中选择性生产丙烯的方法 - Google Patents
在流化床催化裂化工艺中选择性生产丙烯的方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G51/026—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only only catalytic cracking steps
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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Abstract
本发明公开了一种由催化裂化或热裂化石脑油物流选择性生产的烯烃并由烯烃生产聚丙烯的方法。在包括温度为500－650℃和烃分压为10－40psia的反应条件下,使石脑油物流与含有10－50wt%的平均孔径小于0.7nm的结晶沸石的催化剂接触。可以用含碳原料使催化剂预结焦。另外,用于使催化剂结焦的含碳原料可以与石脑油原料一起加入。
Description
交叉参照的相关申请
本申请是1998.5.5申请的美国专利申请序列号09/073,085的部分继续申请。
发明领域
本发明涉及一种由催化裂化或热裂化石脑油物流选择性生产的C3烯烃生产聚丙烯的方法。
发明背景
对低排放燃料的需求增加了对烷基化、低聚合、MTBE和ETBE合成工艺中所用的轻烯烃的需求。另外，一直需要低成本供应的轻烯烃特别是丙烯作为生产聚烯烃特别是生产聚丙烯的原料。
为了提高烯烃产量，用于轻烷烃脱氢的固定床工艺最近又引起了人们的兴趣。但是，这些类型的工艺一般需要较大的投资资本和高的运行费用。因此，用需要较小投资资本的工艺来提高烯烃产率是有利的。在催化裂化工艺中提高烯烃产率是特别有利的。
用FCC装置生产烯烃产品的内在问题是该工艺依赖具体催化剂平衡以使轻烯烃产量最大化的同时还能达到650°F+(～340℃+)原料组分的高转化率。另外，即使能够保持具体催化剂平衡以使烯烃的总生产量最大化，但是，由于有不希望的负反应如广度裂化、异构化、芳构化和氢转移反应，所以烯烃的选择性一般较低。不希望的负反应所产生的轻饱和气体会使回收所需的轻烯烃的成本增加。因此，需要在一个能高度控制对C2-C4烯烃的选择性的工艺中使烯烃产量最大化，该C2-C4烯烃被加工和聚合成诸如聚丙烯和聚乙烯产品。
发明概述
本发明的一个实施方案包括一种生产聚丙烯的方法，其包括(a)使催化剂和含碳物质接触以将催化剂预结焦；然后(b)使含有约10-30wt％烷烃和约15-70wt％烯烃的石脑油原料和预结焦催化剂接触形成裂化产物，催化剂包括约10-50wt％的平均孔径小于约0.7nm的结晶沸石，反应条件包括：温度为约500-650℃，烃分压为10-40psia(70-280kPa)，烃停留时间为1-10秒，催化剂与原料的重量比为约4-10，其中，不超过约20wt％的烷烃转化为烯烃，且其中丙烯构成至少90mol％的总C3产品；和(c)将丙烯从裂化产物中分离且将该丙烯聚合成聚丙烯。
在本发明另一个优选实施方案中，催化剂是ZSM-5型催化剂。
在本发明又一个优选实施方案中，原料含有约10-30wt％的烷烃和约20-70wt％的烯烃。
在本发明再一个优选实施方案中，反应区是在温度为约525-600℃下进行操作的。
发明详述
用于生产较高产率的C2、C3和C4烯烃的合适烃类原料是在石脑油沸点范围内且含有约5-35wt％、优选约10-30wt％、更优选约10-25wt％的烷烃，和从约15wt％、优选从约20-70wt％的烯烃的那些物流。原料还可以含有环烷烃和芳香族化合物。石脑油沸点范围的物流一般是沸点范围为约65-430°F(18-225℃)、优选约65-300°F(18-150℃)的那些物流。
石脑油原料可以是由任何合适原料热裂化或催化裂化的石脑油，包括流化催化裂化(FCC)瓦斯油和残油或者延迟焦化或流化焦化的残油。本发明中使用的石脑油物流优选来自于流化催化裂化的瓦斯油和残油，因为产品石脑油一般富含烯烃和/或二烯烃，而含有的烷烃较少。
本发明的方法是在包括反应区、汽提区、催化剂再生区和分馏区的工艺装置中进行的。将石脑油原料加入反应区与热再生催化剂源接触。热催化剂在约500-650℃、优选约525-600℃的温度下蒸发并将原料裂化。裂化反应在催化剂上沉积焦炭，因此使催化剂失活。将裂化产品从结焦催化剂中分离，并送往分馏器。结焦催化剂通过汽提区，在此用蒸汽将挥发分从催化剂颗粒中汽提出来。汽提可在不太严格的条件下进行，以保留较大部分吸收的烃类物质用于热平衡。然后将汽提的催化剂通过再生区，在此于含氧气体优选在空气存在下燃烧催化剂上的焦炭，使催化剂再生。除焦能使催化剂恢复活性，同时将催化剂加热到约650-750℃。然后将热催化剂循环到反应区与新石脑油原料反应。可以将在再生器中燃烧焦炭产生的烟气进行处理以除去颗粒物和转化一氧化碳。从反应区出来的裂化产品送往分馏区，在此回收各种产品，特别是C3馏份和C4馏份。
在本发明的另一个实施方案中，催化剂可以在与石脑油原料接触前进行预结焦。催化剂的预结焦提高了对丙烯的选择性。可以通过从石脑油原料与催化剂接触点的上游注入产生焦炭的含碳原料使催化剂预结焦。另外，预结焦物流可以与石脑油原料一起加入。用于预结焦催化剂的合适的含碳原料包括但不限定为轻催化循环油，重催化循环油，催化浆液残渣或其它沸点大于约180℃、优选约180-540℃、更优选约200-480℃、更优选约315-480℃的重质产生焦炭的原料。另一个益处是增加了δ焦炭，该δ焦炭在再生器中提供了工艺热平衡所需要的附加热。
虽然已尝试过在FCC工艺装置自身中提高轻烯烃产率，但是本发明在实践中使用了其特有的工艺装置，如前所述，其接收来自炼油厂中合适来源的石脑油。反应区的操作条件使C2-C4烯烃、特别是丙烯的选择性最大化，并且具有较高的C5+烯烃转化率。适用于本发明实践的催化剂是包括平均孔径小于约0.7纳米(nm)的结晶沸石的那些催化剂，所说的结晶沸石构成总流化催化剂组合物的约10-50wt％。结晶沸石优选选自中孔(＜0.7nm)结晶硅铝酸盐系列，其也被称为沸石。特别令人关注的是硅铝摩尔比小于约75∶1、优选小于约50∶1、更优选小于约40∶1的中孔沸石，尽管一些实施方案中使用硅铝摩尔比大于40∶1的中孔沸石。所述孔径(也称为有效孔径)是采用标准吸附技术和已知最小动力学直径的烃化合物测定的。参见Breck，Zeolite Molecular Sieves，1974和Anderson等人，J.Catalysis 58，114(1979)，此处引入这两篇文献作为参考。
可用于本发明实践中的中孔沸石描述在“Atlas of Zeolite StructureTypes，”eds.W.H.Meier和D.H.Olson，Butterworth-Heineman，第三版，1992中，此处引入该文献作为参考。中孔沸石的孔径一般是约0.5-0.7nm，其包括如MFI、MFS、MEL、MTW、EUO、MTT、HEU、FER和TON结构型沸石(IUPAC沸石命名委员会)。这样的中孔沸石的非限定性例子包括ZSM-5、ZSM-12、ZSM-22、ZSM-23、ZSM-34、ZSM-35、ZSM-38、ZSM-48、ZSM-50、硅质岩、和硅质岩2。最优选的是描述在美国专利3,702,886和3,770,614中的ZSM-5；描述在美国专利3,709,979中的ZSM-11；描述在美国专利3,832,449中的ZSM-12；描述在美国专利3,948,758中的ZSM-21和ZSM-38；描述在美国专利4,076,842中的ZSM-23；和描述在美国专利4,016,245中的ZSM-35。此处引入的上述专利均作为参考。其它合适的中孔沸石包括硅铝磷酸盐(SAPO)，如描述在美国专利4,440,871中的SAPO-4和SAPO-11；硅铬酸盐；硅酸镓；硅酸铁；磷酸铝(ALPO)，如描述在美国专利4,310,440中的ALPO-11；硅铝酸钛(TASO)，如描述在EP-A 229,295中的TASO-45；描述在美国专利4,254,297中的硅酸硼；铝磷酸钛(TAPO)，如描述在美国专利4,500,651中的TAPO-11；和硅铝酸铁。
中孔沸石可以包括“晶体混合物”，可以认为这是在合成沸石的过程中在结晶或结晶区域产生缺陷的结果。ZSM-5和ZSM-11的晶体混合物的例子公开在美国专利4,229,424中，此处引入该专利作为参考。晶体混合物自身是中孔沸石，不能将其与沸石的物理混合物相混淆，在沸石的物理混合物中，不同结晶沸石的各种晶体物理地存在于同一催化剂组合物或水热反应混合物中。
本发明的催化剂和无机氧化物基质材料组分在一起。该无机氧化物基质组分将催化剂组分粘结在一起，使催化剂产品有足够的硬度。能经受颗粒间及颗粒与反应器壁之间的碰撞。无机氧化物基质可以由无机氧化物溶胶或凝胶制成，这些溶胶或凝胶干燥后将催化剂组分“粘结”在一起。无机氧化物基质优选不具有催化活性，且包含硅和铝的氧化物。优选将单独的氧化铝相加入无机氧化物基质中。可以使用碱式氢氧化铝-γ-氧化铝，勃姆石，水铝石和过渡氧化铝如α-氧化铝、β-氧化铝、γ-氧化铝、δ-氧化铝、ε-氧化铝、κ-氧化铝和p-氧化铝。氧化铝类物质优选是氢氧化铝如三水铝石、三羟铝石、诺三水铝石或doyelite。基质材料还可以含有磷或磷酸铝。
工艺条件包括：温度为约500-650℃，优选约525-600℃，烃分压为约10-40psia(70-280kPa)，优选约20-35psia(140-245kPa)；催化剂与石脑油的重量比是约3-12，优选约4-10，其中催化剂重量是催化剂组合物的总重量。优选将蒸汽和石脑油物流并行加入反应区，且该蒸汽包括高达约50wt％的烃类原料。另外，原料在反应区内的停留时间优选小于约10秒，如约1-10秒。这些条件将使石脑油物流中至少约60wt％的C5+烯烃转化为C4-产品，并且低于约25wt％、优选低于约20wt％的烷烃转化为C4-产品，丙烯构成至少约90mol％、优选高于约95mol％的总C3反应产品，丙烯/总C2-产品的重量比高于约3.5。
乙烯优选构成至少约90mol％的C2产品，丙烯∶乙烯的重量比大于约4，“全范围”C5+石脑油产品在马达法和研究法辛烷值中都相对于石脑油原料得到了提高。将有效量的单环芳香族化合物加到反应区也能提高丙烯对乙烯的选择性，这也在本发明的保护范围内。芳香族化合物可以来自外部如重整工艺装置，或者可由来自本工艺的重石脑油循环产品组成。
下面的实施例仅用于说明本发明，决不是为了限制本发明。
实施例1-13
用下面的实施例说明工艺操作条件对于保持化学级丙烯纯度的重要性，样品为通过ZCAT-40(一种含有ZSM-5的催化剂)裂化产生的催化石脑油样品，该催化剂已在1500°F(815℃)下蒸汽处理16小时以模拟工业平衡。实施例1和2的对比说明提高催化剂/油的比例将提高丙烯产率，但是牺牲了丙烯纯度。实施例3、4、5和6的对比说明降低油分压极大地提高了丙烯纯度，并且不牺牲丙烯产率。实施例7、8、9和10的对比说明提高温度改进了丙烯产率和纯度。实施例11和12的对比说明缩短催化剂的停留时间提高了丙烯产率和纯度，实施例13示出了一个在使用传统FCC反应器/为第二阶段设计的再生器所能达到的反应器温度和催化剂/油比例下，得到高丙烯产率和纯度的例子。
表1
| 实施例 | 原料烯烃，wt％ | 温度，℃ | 催化剂/油 | 油，psia | 油停留时间，秒 | 催化剂停留时间，秒 | C3 ＝，wt％ | C3 -，wt％ | 丙烯纯度，％ |
| 1 | 38.6 | 566 | 4.2 | 36 | 0.5 | 4.3 | 11.4 | 0.5 | 95.8％ |
| 2 | 38.6 | 569 | 8.4 | 32 | 0.6 | 4.7 | 12.8 | 0.8 | 94.1％ |
| 3 | 22.2 | 510 | 8.8 | 18 | 1.2 | 8.6 | 8.2 | 1.1 | 88.2％ |
| 4 | 22.2 | 511 | 9.3 | 38 | 1.2 | 5.6 | 6.3 | 1.9 | 76.8％ |
| 5 | 38.6 | 632 | 16.6 | 20 | 1.7 | 9.8 | 16.7 | 1.0 | 94.4％ |
| 6 | 38.6 | 630 | 16.6 | 13 | 1.3 | 7.5 | 16.8 | 0.6 | 96.6％ |
| 7 | 22.2 | 571 | 5.3 | 27 | 0.4 | 0.3 | 6.0 | 0.2 | 96.8％ |
| 8 | 22.2 | 586 | 5.1 | 27 | 0.3 | 0.3 | 7.3 | 0.2 | 97.3％ |
| 9 | 22.2 | 511 | 9.3 | 38 | 1.2 | 5.6 | 6.3 | 1.9 | 76.8％ |
| 10 | 22.2 | 607 | 9.2 | 37 | 1.2 | 6.0 | 10.4 | 2.2 | 82.5％ |
| 11 | 22.2 | 576 | 18.0 | 32 | 1.0 | 9.0 | 9.6 | 4.0 | 70.6％ |
| 12 | 22.2 | 574 | 18.3 | 32 | 1.0 | 2.4 | 10.1 | 1.9 | 84.2％ |
| 13 | 38.6 | 606 | 8.5 | 22 | 1.0 | 7.4 | 15.0 | 0.7 | 95.5％ |
表1(续)
| 实施例 | C2 ＝，wt％ | C2 -，wt％ | C3 ＝/C2 ＝ | C3 ＝/C2 - | C3 ＝，wt％ |
| 1 | 2.35 | 2.73 | 4.9 | 4.2 | 11.4 |
| 2 | 3.02 | 3.58 | 4.2 | 3.6 | 12.8 |
| 3 | 2.32 | 2.53 | 3.5 | 3.2 | 8.2 |
| 4 | 2.16 | 2.46 | 2.9 | 2.6 | 6.3 |
| 5 | 6.97 | 9.95 | 2.4 | 1.7 | 16.7 |
| 6 | 6.21 | 8.71 | 2.7 | 1.9 | 16.8 |
| 7 | 1.03 | 1.64 | 5.8 | 3.7 | 6.0 |
| 8 | 1.48 | 2.02 | 4.9 | 3.6 | 7.3 |
| 9 | 2.16 | 2.46 | 2.9 | 2.6 | 6.3 |
| 10 | 5.21 | 6.74 | 2.0 | 1.5 | 10.4 |
| 11 | 4.99 | 6.67 | 1.9 | 1.4 | 9.6 |
| 12 | 4.43 | 6.27 | 2.3 | 1.6 | 10.1 |
| 13 | 4.45 | 5.76 | 3.3 | 2.6 | 15.0 |
C2 -＝CH4+C2H4+C2H6
上述实施例(1、2、7和8)示出通过选择合适的反应器条件可以达到C3 ＝/C2 ＝＞4且C3 ＝/C2 -＞3.5。
实施例14-17
包含在石脑油物流(如FCC石脑油、焦化石脑油)中的烯烃和烷烃在小孔或中孔沸石如ZSM-5上的裂化可以生成大量的乙烯和丙烯。乙烯或丙烯的选择性和丙烯对丙烷的选择性是作为催化剂和工艺操作条件的函数而变化。已经发现：将蒸汽和催化石脑油共同加入反应器可以提高丙烯的产率。催化剂可以是ZSM-5或其它小孔或中孔沸石。下表2示出：当5wt％的蒸汽和含有38.8wt％烯烃的FCC石脑油共同加入时，丙烯产率增加。尽管丙烯产率增加了，但是丙烯纯度下降了。因此，需更调节其它操作条件以保持所需的丙烯选择性。
表2
| 实施例 | 共同加入蒸汽 | 温度，℃ | 催化剂/油 | 油，psia | 油停留时间，秒 | 催化剂停留时间，秒 | 丙烯，wt％ | 丙烷，wt％ | 丙烯纯度，％ |
| 14 | 否 | 630 | 8.7 | 18 | 0.8 | 8.0 | 11.7 | 0.3 | 97.5％ |
| 15 | 是 | 631 | 8.8 | 22 | 1.2 | 6.0 | 13.9 | 0.6 | 95.9％ |
| 16 | 否 | 631 | 8.7 | 18 | 0.8 | 7.8 | 13.6 | 0.4 | 97.1％ |
| 17 | 是 | 632 | 8.4 | 22 | 1.1 | 6.1 | 14.6 | 0.8 | 94.8％ |
实施例18-20
在固定床中用Z-CAT40(已在816℃下蒸汽处理15小时)于1100°F(593℃)、12psig和重量时空速度为1.2的条件下裂化轻催化石脑油(沸点低于约140℃)。蒸汽与轻催化石脑油以1∶1的比例—起加入。开始时的催化剂上没有焦炭，当焦炭在催化剂上聚集时，产率是催化剂在物流中时间的函耗粘示出当焦炭在催化剂上积聚时，丙烯对丙烷和乙烯的选挣巨再田3馏分中丙烯的选挣隆都有提高。
表3
| 实施例 | 18 | 19 | 20 |
| 时间(hr) | 0 | 60 | 150 |
| C3 -wt％ | 25 | 23 | 21 |
| C2 -wt％ | 14 | 10 | 6 |
| C3 ＝/C2 ＝ | 1.8 | 2.3 | 3.5 |
| C3馏分中丙烯(Wt％) | 91 | 94.5 | 98 |
可以将优选工艺生成的轻烯烃用作诸如低聚合、聚合、共聚、三聚、及相关工艺的工艺(下面称为“聚合”)中的原料，以形成大分子。根据本领域公知的聚合方法可以将这些轻烯烃单独或与其它物质结合进行聚合。在某些情况下，轻烯烃在聚合之前可能需要将其分离、浓缩、纯化、升级或进行其它加工。丙烯和乙烯是优选的聚合原料二聚丙烯和聚乙烯是优选的由其生成的聚合产品。
Claims (10)
1.一种在反应器中生产丙烯的方法，该反应器包括位于第二区上游的第一区，该方法包括：
(a)在所述第一区内，使沸点大于180℃的含碳原料与包括平均孔径小于0.7nm的结晶沸石的催化剂接触，形成预结焦催化剂；和
(b)在所述第二区内，使含有10-30wt％烷烃和15-70wt％烯烃的石脑油原料和所述预结焦催化剂接触形成裂化产物，反应条件包括：温度为500-650℃，烃分压为10-40psia，烃停留时间为1-10秒，催化剂与原料的重量比为4-10，其中，不超过20wt％的烷烃转化为烯烃，且其中丙烯构成至少90mol％的总C3产物。
2.一种生产丙烯的方法，其包括如下步骤：
使原料和催化剂接触生成裂化产物，所述原料是：
(i)含有10-30wt％烷烃和15-70wt％烯烃的石脑油原料；和
(ii)沸点大于180℃的含碳原料；
所述催化剂包括平均孔径小于0.7nm的结晶沸石；反应条件包括：温度为500-650℃，烃分压为10-40psia，烃停留时间为1-10秒，催化剂与原料的重量比为4-10，其中，不超过20wt％的烷烃转化为烯烃，且其中丙烯构成至少90mol％的总C3产物。
3.根据任一上述权利要求所述的方法，其中结晶沸石选自于ZSM系列。
4.根据任一上述权利要求所述的方法，其中结晶沸石为ZSM-5。
5.根据任一上述权利要求所述的方法，其中丙烯构成至少95mol％的总C3产物。
6.根据任一上述权利要求所述的方法，其中反应温度为500-600℃。
7.根据权利要求4所述的方法，其中原料中至少60wt％的C5+烯烃转化为C4-产物且小于25wt％的烷烃转化为C4-产物。
8.根据权利要求7所述的方法，其中丙烯构成至少90mol％的总C3产物。
9.根据权利要求8所述的方法，其中丙烯与总C2-产物的重量比大于3.5，丙烯与总C2-产物的重量比优选大于4.0。
10.根据任一上述权利要求所述的方法，其还包括将丙烯从裂化产物中分离并将丙烯聚合成聚丙烯的步骤。
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| CN116615516A (zh) * | 2020-04-10 | 2023-08-18 | 加索芬有限公司 | 制备丙烯的方法 |
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-
2001
- 2001-05-19 WO PCT/US2001/016020 patent/WO2001090278A2/en not_active Application Discontinuation
- 2001-05-19 CA CA002380059A patent/CA2380059A1/en not_active Abandoned
- 2001-05-19 CN CN01801297.3A patent/CN1380898A/zh active Pending
- 2001-05-19 EP EP01935659A patent/EP1287092A2/en not_active Withdrawn
- 2001-05-19 AU AU61734/01A patent/AU6173401A/en not_active Abandoned
- 2001-05-19 MX MXPA02000650A patent/MXPA02000650A/es not_active Application Discontinuation
- 2001-05-19 JP JP2001587077A patent/JP2003534444A/ja not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978411B (zh) * | 2005-11-30 | 2010-05-12 | 中国石油化工股份有限公司 | 一种制取小分子烯烃的组合工艺方法 |
| WO2009009965A1 (fr) | 2007-07-19 | 2009-01-22 | China Petroleum & Chemical Corporation | Procédé de traitement d'oléfines |
| US9024100B2 (en) | 2007-07-19 | 2015-05-05 | China Petroleum & Chemical Corporation | Process for producing olefins |
| CN104726131A (zh) * | 2015-03-17 | 2015-06-24 | 东南大学 | 一种催化剂预积碳增加烃类产率的装置和方法 |
| CN104726131B (zh) * | 2015-03-17 | 2016-06-08 | 东南大学 | 一种催化剂预积碳增加烃类产率的装置和方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003534444A (ja) | 2003-11-18 |
| WO2001090278A2 (en) | 2001-11-29 |
| CA2380059A1 (en) | 2001-11-29 |
| US6803494B1 (en) | 2004-10-12 |
| EP1287092A2 (en) | 2003-03-05 |
| MXPA02000650A (es) | 2002-07-02 |
| WO2001090278A3 (en) | 2002-03-28 |
| AU6173401A (en) | 2001-12-03 |
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