CN104302736A - 妥尔油脱氧的方法和由其制备可聚合单体的方法 - Google Patents

妥尔油脱氧的方法和由其制备可聚合单体的方法 Download PDF

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CN104302736A
CN104302736A CN201380019582.1A CN201380019582A CN104302736A CN 104302736 A CN104302736 A CN 104302736A CN 201380019582 A CN201380019582 A CN 201380019582A CN 104302736 A CN104302736 A CN 104302736A
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阿里·阿尔兰
奥利·阿尔托宁
安德鲁·莱塔宁
杰瑞·雷塞宁
欧蒂·屈利埃宁
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Abstract

本发明涉及一种妥尔油脱氧的方法，以及一种用于由妥尔油制备脂族烃和可聚合单体的方法。将含硫粗妥尔油(5)与氢气(6)一起进料至包含催化剂床(2，3)的反应器(1)中。通过使用硫化金属催化剂，例如NiMoS催化剂，将所述油在所述床中进行通过氢的催化脱氧。将离开所述反应器的流冷却并且将含烃的液相(10)从气相(18)分离，之后对所述液相进行蒸馏(14)用于移除无用的芳族烃，并且之后进行蒸汽裂化(4)以形成含有烯烃如乙烯或丙烯的所得物。通过将脱氧温度调节为至少270℃但小于360℃，产品富含可用于在蒸汽裂化中转化为烯烃的直链和环状脂族物，同时石脑油的形成减少。

Description

妥尔油脱氧的方法和由其制备可聚合单体的方法
本发明关于妥尔油脱氧的方法和用于由妥尔油制备脂族烃和可聚合单体，如乙烯和丙烯的方法。
聚合物传统上由化石来源的粗油制造。近年来，由可再生原材料制成的生物聚合物日益作为替代物而被研究。一种这样的原材料是作为来自纤维浆熬煮法的副产物获得的妥尔油。
妥尔油含有脂肪酸和树脂酸，可以对其进行催化加氢脱氧(HDO)和裂化，产生含烃的液体产物以及气体和水。液体烃转变为生物燃料，但是还存在将它们转化为单体化合物的文献，所述单体化合物可以作为用于制备聚合物的原材料。
WO 2011/151528描述了多种妥尔油材料，如粗妥尔油(CDO)，蒸馏妥尔油(DTO)或妥尔油脂肪酸(TOFA)的催化加氢脱氧，之后将合适的芳族烃如对二甲苯或邻二甲苯从液体产物分离，并且将它们氧化为可用于制备生物起源的聚对苯二甲酸乙二醇酯(生物-PET)的对苯二甲酸。
WO 2010/086507教导了一种用于由至少75％的妥尔油脂肪酸和不大于25％的妥尔油树脂酸的蒸馏混合物制备可聚合乙烯和丙烯的方法，之后用氢对其进行催化脱氧，之后对所产生的液体烃进行蒸汽裂化，其产生所述单体。
为了通过更简单的方法并且以提高的收率制备生物基烯烃单体如乙烯或丙烯，所希望的是使用粗妥尔油作为原材料，代替通过蒸馏提纯的酸。提纯酸的原因是杂质有使催化剂中毒的倾向。甚至粗妥尔油中存在的树脂酸已经被认为是较不理想的，产生了不可以通过氢化裂化转化为可聚合烯烃的芳族烃。
通过本发明所要解决的问题是获得一种改进的方法，其允许使用粗妥尔油作为用于催化加氢脱氧的原材料，以及随后的用于获得可聚合烯烃的蒸汽裂化，而不需要蒸馏或以其他方式提纯妥尔油，不存在催化剂的劣化，并且来自脱氧步骤的脂族和非芳族的环烃的收率被提高，以及来自蒸汽裂化步骤的烯烃单体的收率被提高。
作为本发明的第一方面，以上问题通过粗妥尔油脱氧的方法解决，所述方法包括以下步骤：
(i)将含硫粗妥尔油和氢气进料至催化剂床中，以及
(ii)通过使用硫化的金属催化剂，使所述油在床中用氢在至少270℃但低于360℃的温度进行催化脱氧。
根据本发明的第二方面，提供一种用于由妥尔油制备脂族烃的方法，所述方法包括以下步骤：
(i)将含硫粗妥尔油和氢气进料至催化剂床中；
(ii)通过使用硫化的金属催化剂，使所述油在床中在至少270℃但低于360℃的温度进行通过氢的催化脱氧；
(iii)将含烃的液体从脱氧的所得物(yield)回收；以及
(iv)将富集脂族烃的馏分通过蒸馏分离。
根据本发明的第三方面，提供一种由妥尔油制备可聚合烯烃单体的方法，所述方法包括以下步骤：
(i)将含硫粗妥尔油和氢气进料至催化剂床中；
(ii)通过使用硫化金属催化剂，使所述油在床中在至少270℃但低于360℃的温度进行通过氢的催化脱氧；
（iii)将已经离开床的流冷却，并且将含烃的液相从气相分离；以及
(iv)将含烃的液体进行蒸汽裂化以形成含有可聚合烯烃的产物。
通过本发明获得的益处是在脱氧阶段的所得物中多芳烃所占比例的减少。为获得该改进，发现在低于360℃的温度工作是重要的。多芳烃不能通过蒸汽裂化转化为可聚合单体，并且因此在生物聚合物的制备方面是废物，生物聚合物是本发明的主要目标。
催化剂中的硫对于脂肪和树脂酸的有效加氢脱氧是重要的，但是因为它具有在该过程中逃逸的倾向，结果造成催化剂失去其效果。然而，通过使用根据本发明的含硫粗妥尔油，存在可用于代替任何硫损失的硫，并且从而保持在该过程中存在硫化的催化剂。
形成用于本发明的方法的原材料的含硫粗妥尔油可以具有30至70重量％的含量的脂肪酸和20至50重量％的含量的树脂酸。由使用硫酸而由黑液妥尔油皂释放脂肪酸和树脂酸得到的含硫粗妥尔油中的硫的含量可以在0.05至0.5重量％的范围内。
脱氧催化剂可以是硫化的NiMo或CoMo催化剂，优选包含NiMoS的催化剂。这种硫化的催化剂可以通过使用H2S和H2硫化相应的金属催化剂(NiMo，CoMo)获得。
根据本发明的一个优选的实施方案，脱氧温度在280至350℃，优选280至320℃的范围内。
根据本发明的另一个实施方案，脱氧步骤中的氢压力为30至100巴。
根据本发明的另外的实施方案，催化剂床是由固定床材料形成的固定床。催化剂床中的流优选从顶部运行至底部。
在脱氧阶段之后与含烃的液相分离的气相可以有益地用二乙胺处理，以分离其中所含的气态C1-C4-烃。这些烃可以被用于传递至蒸汽裂化，同时将富集氢气的残留物循环返回至作为含有氢的进料气体以用于脱氧阶段。
除了在脱氧步骤形成含有有机烃的液相水之外，并且优选地，在将后者进料至蒸汽裂化中之前将该水相从含烃的液体中分离。
除了脂族烃和环烃之外，由脱氧步骤获得的含烃的液体含有石脑油的沸点范围内的烃。优选地，在蒸汽裂化步骤之前将任意芳族烃从含烃的液相移除。
通过将含烃的液体蒸汽裂化制备的优选的产物是乙烯和丙烯，其分别可用于制备聚乙烯和聚丙烯。
首先，参考附图(图1)描述本发明，该附图示意性地显示预期用于本发明的应用的装置。
根据附图，该方法一般包括含硫粗妥尔油5在依次具有催化脱氧区和裂化区2、3的垂直反应器1中的处理。将来自反应器1的输出物分离为不同馏分，并且将所获得的直链的和环状脂族物(aliphates)特别地在如由石油化学领域已知的并且以本领域技术人员已知的方式操作的蒸汽裂化装置4中进一步裂化。蒸汽裂化的产物是烯烃，如乙烯或丙烯，其可用作用于制备生物聚合物的单体。
将含有30-70重量％的脂肪酸和20-50重量％的树脂酸，以及约5重量％的甾醇和/或固醇，0.05-0.5重量％的硫等作为次要组分的粗妥尔油的进料5输送到反应器1的上端。此外，将氢通过管线6进料至反应器1的上端。反应器1填充有石英棉，其充当床材料7，以及层状的分离的区域2、3，这些区域包含NiMoS催化剂以将所进料的酸脱氧，以及沸石催化剂，以使碳链断裂。反应器1中的液相和气相的流动方向是从顶部至底部。为调节反应温度，反应器1设置有电加热器8。
将通过反应器1的下端离开的热反应产物传送至冷却器9，并且液化的产物通过管线10移动至分离槽11，该分离槽将水相12与油相13分离。油相13前进至蒸馏器14，该蒸馏器将饱和脂族烃以及环烃作为流出物15与芳族烃和酯的残留物16分离，所述残留物是要从该工艺抛弃。残留物16将不会在蒸汽裂化中产生有用的单体，并且通过蒸馏移除芳族物防止它们垢化并且最终阻塞水蒸汽裂化器4。流出物15之后前进至蒸汽裂化4，其中至所需的最终产物低分子烯烃17的裂化通过数个中间阶段发生。使用烯烃作为制备生物聚合物如聚乙烯或聚丙烯的原材料。
未在冷却器9中冷凝并且含有氢、碳的氧化物、可能的低分子烃和其他杂质的气体18移动至洗涤器19，用二乙胺处理气流。将纯氢20循环返回至反应器1的上端以构成脱氧气体的一部分，将低级烷烃和水蒸气的流21传送至水蒸汽裂化器4，并且将碳的氧化物和其他气态杂质22从该工艺移除。
在根据本发明的方法的更简单实施中，可以省略反应器1中的沸石催化剂3以及，与之一起的催化裂化。在这种情况下，归因于较小量的氢或没有氢离开反应器，所以循环20氢也可以省略。在其他方面，装置和工艺流程如附图中所示。
实施例
通过使用粗妥尔油(CTO)的样品进行一系列十一个实验(1-11)。实验1-5是比较例并且实验6-11是根据本发明的。
含硫CTO得自硫酸盐熬煮法。在将CTO进料至脱氧之前不向其中加入水。反应器对应于图1中所示的那个反应器。使用氢作为脱氧气体。脱氧催化剂为用H2S和H2在320℃或从20逐渐升高至400℃的温度预硫化的NiMo。测试中的脱氧温度在300-406℃的范围内，并且气体压力在50-56巴的范围内。分析得自催化脱氧的液体和气体产物。结果在表1中给出。
来自结果的最重要的发现是脱氧的液体产物中芳烃的比例随着脱氧温度从大约400℃降低至300-350℃而显著地降低。该变化伴随着有用的链烷烃(脂族)和石脑油(环状)烃的比例的增加。当将所得物通过蒸汽裂化转化为可聚合烯烃时，烯烃的最终收率将因此增加。

Claims (15)

1.一种妥尔油脱氧的方法，所述方法包括以下步骤：
-将含硫粗妥尔油和氢气进料至催化剂床中；以及
-通过使用硫化的金属催化剂，使所述油在所述床中在至少270℃但低于360℃的温度进行通过氢的催化脱氧。
2.一种用于由妥尔油制备脂族烃的方法，所述方法包括以下步骤：
-将含硫粗妥尔油和氢气进料至催化剂床中；
-通过使用硫化的金属催化剂，使所述油在所述床中在至少270℃但低于360℃的温度进行通过氢的催化脱氧；
-从脱氧的所得物中回收含烃的液体；以及
-将富含脂族烃的馏分通过蒸馏分离。
3.一种用于由妥尔油制备可聚合单体的方法，所述方法包括以下步骤：
-将含硫粗妥尔油和氢气进料至催化剂床中；
-通过使用硫化的金属催化剂，使所述油在所述床中在至少270℃但低于360℃的温度进行通过氢的催化脱氧；
-将已经离开所述床的流冷却，并且将含烃的液相从气相分离；以及
-将所述含烃的液体进行蒸汽裂化以形成含有可聚合烯烃的产物。
4.权利要求3所述的方法，其特征在于，在将所述液体进料至蒸汽裂化之前将水从所述含烃的液相分离。
5.权利要求3或4所述的方法，其特征在于，在所述蒸汽裂化步骤之前将芳族烃从所述含烃的液相移除。
6.权利要求3至5中任一项所述的方法，其特征在于，乙烯和/或丙烯通过所述蒸汽裂化制备。
7.权利要求3至6中任一项所述的方法，其特征在于，将气相从所述含烃的液相分离并且用二乙胺处理以分离C1-C4-烃，将所述C1-C4-烃送至蒸汽裂化，同时将氢气循环返回，以作为用于所述脱氧阶段的含有氢的进料气体使用。
8.在前权利要求中任一项所述的方法，其特征在于，所述含硫粗妥尔油具有含量为30至70重量％的脂肪酸和含量为20至50重量％的树脂酸。
9.在前权利要求中任一项所述的方法，其特征在于，所述含硫粗妥尔油含有0.05至0.5重量％的硫。
10.在前权利要求中任一项所述的方法，其特征在于，所述脱氧催化剂是硫化的NiMo或CoMo催化剂，优选包含NiMoS的催化剂。
11.权利要求10所述的方法，其特征在于，将所述脱氧催化剂用H2S和H2预硫化。
12.在前权利要求中任一项所述的方法，其特征在于，所述脱氧温度在280至350℃的范围内，优选在280至320℃的范围内。
13.在前权利要求中任一项所述的方法，其特征在于，在所述脱氧步骤中的氢压力为30至100巴。
14.在前权利要求中任一项所述的方法，其特征在于，所述催化剂床是由固定床材料形成的固定床。
15.在前权利要求中任一项所述的方法，其特征在于，所述催化剂床中的流从顶部运行至底部。
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