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CN102300836B - 用生物油制备烯烃单体的方法 - Google Patents

用生物油制备烯烃单体的方法 Download PDF

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CN102300836B
CN102300836B CN201080005979.1A CN201080005979A CN102300836B CN 102300836 B CN102300836 B CN 102300836B CN 201080005979 A CN201080005979 A CN 201080005979A CN 102300836 B CN102300836 B CN 102300836B
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阿里·阿尔兰
塔帕尼·彭蒂宁
杰瑞·雷塞宁
奥利·阿尔托宁
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Abstract

用于制备可聚合烯烃单体的方法，所述可聚合烯烃单体尤其用于妥尔油类生物聚合物，如聚烯烃的制备。本方法包括将生物油和氢气进料至催化剂床中，所述生物油具有超过50％的妥尔油脂肪酸含量以及不超过25％的妥尔油树脂酸含量。将妥尔油催化脱氧并且将从所述床排出的流冷却并分离为液相和气相。将含烃液相进行蒸汽裂化以提供含有可聚合烯烃的最终产物。可以在上述床中的脱氧之后在同一床中进行催化裂化或者，用合适的催化剂，可以同时进行所述脱氧和裂化。

Description

用生物油制备烯烃单体的方法
本发明涉及制备用于生物聚合物制备的烯烃单体的方法。
用于聚烯烃如聚乙烯和聚丙烯的制备的传统原料包括原油。含有烷烃并且得自原油的分馏的烃类馏分通过高温水蒸汽裂化为具有较短链的烷烃和烯烃，例如乙烯和丙烯，它们是用于聚乙烯和聚丙烯的制备的源材料。
作为取代化石原料的替代品，已经研究了可再生有机原料源用于聚合物的制备。已经提出过制备例如玉米或糖的聚合物；然而，其缺点是聚合物生产不得不与食品生产争夺相同的原材料，其资源在全球是有限的。原材料的理想来源包括木材，其储量丰富并且它不用于食品生产。
在专利说明书WO2008/039756中描述了将木基原料裂化为石脑油沸点范围内的液体。该方法的起始原料包括废纤维素或木质素，其在起液体载体作用的妥尔油中被淘洗。根据该说明书，该浆液经历催化加氢裂化过程，其催化剂中的金属，如Ni和Mo与沸石或二氧化硅-氧化铝催化剂结合。作为合适的反应器，该说明书提及泥浆床和流化床反应器，然而在一个示例性实施方案中使用了高压釜反应器。根据该说明书，产物以蒸汽形式获得，所述蒸汽被冷凝为液体，并且任意过量的氢可以在该过程中循环。将含有使用过的催化剂的过量液体洗净并循环到进料至该过程的浆液。作为裂化的结果，氧从产物移除并且分子被裂化为更小的分子。该说明书的总体目标包括燃料和化学中间体产品的制造；也提到了用于塑料制造的单体。然而，该说明书中缺少用于这种目的的加氢裂化液体产物的使用的所有更详细的描述。
说明书US-2004/0230085公开了作为生物基柴油生产的一部分的妥尔油脂肪酸催化加氢脱氧。通过催化剂床中的气体氢实现脱氧，所述催化剂床包含金属催化剂，例如NiMO或CoMo，并且载体包括氧化铝和/或二氧化硅。将碳的氧化物和多种杂质从在脱氧步骤产生的气态混合物分离并且将提纯的氢循环返回至该过程。在该过程的第二步骤，使液相经历异构化，所述异构化提供适合用作燃料的产物。因为异构化步骤对于芳烃(aromate)和环烷烃杂质敏感，将在脱氧中可能产生的妥尔油树脂酸从起始原料尽可能有效地移除。在该说明书的实施例1中，脂肪酸中的树脂酸的量为1.9％。
说明书US-2008/0154073公开了用生物可再生原料，如植物油产生柴油的类似方法。提到了除脂肪酸以外还含有树脂酸的妥尔油能够作为原料；然而，根据测试结果，与也被用于测试中的豆油相比，妥尔油产生出相当大部分的比柴油重的烃类馏分。
说明书US-2007/0135669也描述了用生物可再生原料生产柴油并且观察到在最终产物中不饱和烃和芳族烃的有害存在。该说明书描述了作为发明的一种方法，其中首先将从妥尔油蒸馏的脂肪酸异构化，并且其后，在该方法的第二步骤中将其脱氧。
本发明的目的是提供一种工业上可用的方法，所述方法可以被用于将木基原料转化为适合于生产生物聚合物的烯烃单体。从而，聚合物的生产可以基于可再生生物原料来源。根据本发明的方法基本上由以下步骤组成：
-将生物油和氢气进料至催化剂床中，所述生物油具有超过50％的妥尔油脂肪酸含量以及不超过25％的妥尔油树脂酸含量；
-在所述床中用氢将所述油进行催化脱氧；
-将从所述床排出的流冷却并分离为含烃液相和气相；以及
-将含烃液体进行蒸汽裂化以提供含有可聚合烯烃的产物。
起始油原料可以完全是妥尔油类，由至少75％的妥尔油脂肪酸和不超过25％的妥尔油脂肪酸组成。可以将这种酸混合物通过蒸馏从粗制妥尔油分离。可以将作为本发明的方法的最终产物获得的烯烃单体转化为全部基于可再生原料源的生物聚合物。
也可能的是，将起始原料中的妥尔油组分与其它合适的生物油，如植物油，例如，棕榈油混合。
在本发明中妥尔油是指这样的油产品，其不仅可从松树(松属)，而且可以从其它针叶树获得，并且由脂肪酸和树脂酸或它们的酯类组成。
本发明基于以下事实：通过如此已知的方法进行的妥尔油脂肪酸的氢化脱氧产生烃类混合物，所述混合物可以通过蒸汽裂化进一步处理以形成低分子烯烃而没有由相当少部分的芳族烃或不饱和脂族烃或环烃引起的问题。因为蒸汽裂化包括属于普通石油化学的技术，在实践中容易实施根据本发明的方法。
因为根据本发明的方法相比柴油的制造对于所述成分的存在较不敏感，不需要将妥尔油的树脂酸从脂肪酸仔细地分离。然而，因为树脂酸有其它有益的最终用途，值得强调起始原料中妥尔油脂肪酸、油酸和亚油酸的组成。起始原料中树脂酸的量最多约为25％，但是考虑到方法的经济性，它们的份数优选地在2-5％之内。
催化氢化脱氧通过以下方式进行：将氧从脂肪酸释放出来并形成水、一氧化碳和/或二氧化碳。碳链大量破裂为更小的分子尚未发生。在本发明中，可以将对于催化固定床的采用限制在脱氧步骤并且可以通过常规蒸汽裂化有效地进行裂化生成烯烃单体。
本发明的备选应用是这样的应用，其中，在固定床中脱氧之后进行催化裂化以降低分子量，其中脱氧和裂化步骤的催化剂彼此不同。裂化产生不饱和烃并且释放氢，所以优选地将从它们中排出的含氢气体循环返回至脱氧步骤。在这种情况下，甚至可能该过程仅在起始步骤需要外部氢源，并且其后仅仅通过循环氢工作。
可以使用酸性催化剂，如酸性沸石催化剂作为在固定床中进行的裂化的催化剂。与可能的催化裂化无关，可以使用金属催化剂，如NiMo或CoMo作为脱氧步骤的催化剂。以如此已知的方式将后者用氢还原并用硫化氢处理。
采用合适的催化剂，可以在床中同时发生氢化脱氧和相当程度的催化裂化。这样的催化剂包括含镍Y-沸石(NiY-沸石)或含镍蒙脱土(montmorolite)(NiSMM)，它需要反应器中的高氢气压力。NiSMM也裂化树脂酸；因此，它对于妥尔油各组分的有效利用是特别有益的。
在氢化脱氧步骤和可能的催化裂化步骤的合适反应温度在330-450℃之内。在更低的温度下，存在聚合的风险以及在更高的温度下当将脂肪酸进料至反应器中时已经结焦的风险。
从蒸汽裂化获得的最终产物可以包含乙烯和丙烯，它们可以被聚合成聚乙烯或聚丙烯。乙烯也可以用于其它聚合物，如聚对苯二甲酸乙二醇酯的生产。
本发明还包括作为与原油合并的部分流处理生物油的情况，其中最终聚合的产物相应地是部分生物类且部分原油类的混合聚合物。如此可以自由选择在根据本发明的氢化脱氧和裂化过程中生物油和原油的混合比。
首先，参考附图(图1)描述本发明，所述附图示意地显示了打算用于本发明的应用的装置。
根据附图，生物油脂肪酸，如妥尔油脂肪酸的氢化脱氧和裂化过程的主要步骤包括在立式反应器1中发生的催化脱氧和裂化步骤2、3，以及从这些步骤获得的液态烃在独立的装置4中的蒸汽裂化，所述装置4对应于石油化学领域内已知的技术。在反应器1的上端进行妥尔油脂肪酸的进料5，所述妥尔油脂肪酸通过蒸馏分离并且最多可以包含25％树脂酸。此外，可以通过管线6将氢引入反应器1的顶端。将反应器1用石英毛填充，它作为床材料7，以及叠加的独立区2、3，其包含将进料的酸脱氧的NiMo催化剂和裂化碳链的沸石催化剂。在反应器1中液相和气相的流动方向是从上至下。为调节反应温度，反应器1配备有电加热器8。
将通过反应器1的下端排出的热反应产物引入冷却器9，并且液化产物通过管线10移动至分离槽11，所述分离槽11将水相12与油相13分离。主要成分典型地包含饱和脂族烃，并且也可以含有不同量的环烃和芳族烃、不饱和烃和脂肪醇的油相13移动至蒸汽裂化4，其中通过数个中间步骤进行裂化生成低分子烯烃14。烯烃被用作生物聚合物如聚乙烯或聚丙烯生产的起始原料。
未在冷凝器9中凝结并且含有氢、碳的氧化物、可能的低分子烃和其它杂质的气体移动至提纯器15，它将氢与其它气体组分分离。将纯氢通过管线16循环返回至反应器1的上端以构成脱氧气体，并且将碳的氧化物和其它杂质17从该过程移除。
根据本发明的方法的简化实施方案包括以下情况：省略反应器1中的沸石催化剂3以及催化裂化。在该情况中，由于从反应器排出的氢的量较少或没有，也可以省略循环16氢。在其它方面中，装置和工艺流与图中所描绘的相同。
实施例
实施例测试1-6，包括氢化脱氧(HDO)和/或催化裂化(CC)，以分批原理对作为通过反应器的流进行，而不循环气相。分析从反应器获得的液相和气相。在根据本发明的方法中，没有进行后面的有机液相的蒸汽裂化，因为该技术是本领域技术人员所熟知的并且，基于所述的分析，该液体对于蒸汽裂化的适用性是显而易见的。
将1g的沸石裂化催化剂(ZSM-5)装入电炉内部的立式反应器管中并且，在其之上，装入3g的脱硫/脱氧催化剂(带有氧化铝的NiMo)。通过经由填充有催化剂的反应器管在393℃的温度下输送含硫化氢的氢气流5小时将NiMo催化剂预先硫化。
将反应器管的温度调整为360℃并且在31-32巴下从上到下向其中通入氢气。将反应器中的氢气流设定为约0.9g/h。当流和温度变得均匀时，除氢气之外，还开始将妥尔油馏出物泵入反应器管中，所述馏出物除脂肪酸之外还含有少量树脂酸。将妥尔油馏出物从上面进料至反应器管中，在下游进料氢气流。将妥尔油馏出物的进料速度调节为6-9g/h。从而，相对于NiMo催化剂的WHSV(重时空速)为2.0-3.01/h。
将从反应器的下端出来的液体/气体流引入加压收集盘，将所述收集盘用冷水冷却。每隔1小时将收集盘的全部液体成分回收。通过泄压阀将从收集盘排出的气体流引至室外。每隔1小时通过在线分析仪测量气体流的组成并且反应器运行总计10小时。
在反应器完全达到平衡的8h运行时间，回收了占所进料的妥尔油馏出物的量的约83％的液体产物。该液体产物包含有机相和分离的水。该液体产物含有占有机相的量总计61％的烃类。有机相的近似组成包含：6％的芳族烃、42％的饱和烃、总计10％的不饱和脂族烃和脂肪醇以及3％的环烃。饱和烃的70％由十七烷和十八烷组成。从反应器排出的气体流含有占所进料的妥尔油馏出物的量的10％的反应产物。气体流反应产物为：16％的一氧化碳、23％的二氧化碳、总计2％的C1和C2烃类，21％的C3烃类，28％的C4烃类和总计9％的更重烃类。
测试中所测得的质量平衡接近于完全平衡。所测得的流出的质量流总共占向反应器中注入的所有流的92％。
下面的表中显示了测试1-6的结果。测试1-4的进料包含从妥尔油(TOFA)蒸馏的脂肪酸馏分，所述馏分含有2-5％的脂肪酸，测试5的进料包含馏出的妥尔油(DTO)，它含有约25％的树脂酸，并且测试6的进料包含粗制妥尔油(CTO)，它含有更大量的树脂酸。测试1-3和5是根据本发明的测试，测试4和6是参考测试。
分别给出用于氢化脱氧步骤(HDO)和催化裂化步骤(CC)的催化剂。
仅包括CC步骤的测试4中饱和烃的缺乏显示出过度进行的裂化，从而，显示出HDO步骤的重要性。测试5和6显示起始材料的树脂酸增加芳烃的份数；在测试6中，芳烃的份数增加到不适宜的高水平。
Figure BDA0000079695030000071

Claims (16)

1.一种制备用于聚合物生产的烯烃单体的方法，其特征在于以下步骤：
-将生物油和氢气进料至催化剂床（7）中，所述生物油是从粗制妥尔油中分离的馏分，所述馏分由75至98%的妥尔油脂肪酸和2至25%的妥尔油树脂酸组成；
-在所述床（7）中用氢将所述油进行催化脱氧；
-将从所述床（7）中排出的流冷却，并且分离成气相和含烃液相（10）；以及
-将含烃液体（13）进行蒸汽裂化（4）以形成含有可聚合烯烃的产物。
2.根据权利要求1所述的方法，其特征在于，脱氧催化剂是NiMo催化剂或CoMo催化剂。
3.根据权利要求1所述的方法，其特征在于，所述催化剂床是由固定床材料形成的固定床（7）。
4.根据权利要求3所述的方法，其特征在于，在所述固定床（7）中，在所述脱氧（2）之后进行催化裂化（3）以降低分子量，所述脱氧步骤和裂化步骤中的催化剂彼此不同。
5.根据权利要求4所述的方法，其特征在于，所述酸性催化剂是酸性沸石催化剂。
6.根据权利要求4所述的方法，其特征在于，所述脱氧步骤和裂化步骤（2、3）中的催化剂相继被设置在由所述床材料形成的所述固定床（7）中并且间隔开。
7.根据权利要求4-6中任一项所述的方法，其特征在于，所述脱氧和/或裂化步骤中的催化剂是含镍Y-沸石或含镍蒙脱土。
8.根据权利要求4-6中任一项所述的方法，其特征在于，所述脱氧和/或裂化步骤中的催化剂是镍置换的蒙脱土。
9.根据权利要求1-4中任一项所述的方法，其特征在于，所述床（7）中的流从上至下流动。
10.根据权利要求1-4中任一项所述的方法，其特征在于，将与所述液相（10）分离的含氢气相（16）循环返回以构成所述脱氧步骤（2）的进料气体。
11.根据权利要求1-4中任一项所述的方法，其特征在于，在将所述含烃液体（13）进料至所述蒸汽裂化（4）中之前，将水（12）从所述液相（10）中分离。
12.根据权利要求1-4中任一项所述的方法，其特征在于，所述含烃液相（10、13）含有在石脑油沸程内的烃类。
13.根据权利要求1-4中任一项所述的方法，其特征在于，进料至所述床（7）中的所述生物油具有至少75%的油酸和亚油酸含量。
14.根据权利要求1-4中任一项所述的方法，其特征在于，进料至所述床（7）中的所述生物油具有至少95%的油酸和亚油酸含量。
15.根据权利要求1-4中任一项所述的方法，其特征在于，进料至所述床（7）中的所述生物油具有2-5%的妥尔油树脂酸含量。
16.根据权利要求1-4中任一项所述的方法，其特征在于，通过所述蒸汽裂化（4）产生乙烯和/或丙烯。
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