CN1227191C - 烯烃的选择性低聚反应 - Google Patents

烯烃的选择性低聚反应 Download PDF

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CN1227191C
CN1227191C CNB018035639A CN01803563A CN1227191C CN 1227191 C CN1227191 C CN 1227191C CN B018035639 A CNB018035639 A CN B018035639A CN 01803563 A CN01803563 A CN 01803563A CN 1227191 C CN1227191 C CN 1227191C
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T·I·埃文斯
L·J·卡拉斯
R·拉梅斯瓦兰
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Lyondell Chemical Technology LP
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    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
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    • C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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Abstract

在反应器(5)中通过使用叔丁醇改性剂和较低级烷烃稀释剂的异丁烯的二聚制备一种富含异辛烷的汽油调和馏分。可有利地通过在脱水区(2)将叔丁醇脱水来制备所述异丁烯。

Description

烯烃的选择性低聚反应
发明领域
本发明涉及一种选择性二异丁烯的方法，具体是涉及在叔丁醇作为二聚时的选择性增强改性剂的条件下，C3和/或C4烷烃作为二聚溶剂的用途。
先有技术的说明
使用酸催化剂的烯烃(如异丁烯)的低聚是人们熟悉的反应。
正如美国专利3,760,026中所述，用于该反应的各种催化剂为人们所熟悉，包括在硅藻土、硅石/铝土上的冷硫酸、磷酸(有时用Ni、Co、Fe、Pt或Pd助催化)；活化的天然粘土加上活化物质如ZnO金属磷酸盐，如铁(III)和铯的磷酸盐，任选装载于载体上，如活性炭、铝土矿、单独的活性炭以及连同金属卤化物(如TiCl2)的活性炭；杂多酸，如在硅胶上的硅钨酸和磷钼酸；BF3H3PO4和BF3HPO3；二羟基氟硼酸HF和沸点低于300℃的S、Se、N、P、Mo、Te、W、V和Si的氟化物或氟氧化物；BF3二甲基醚络合物；BF3烃络合物；BF3SO2；和具助催化剂如二甲醚、HCl和硝基甲烷的AlCl3。这些催化剂和二聚方法，包括操作条件均为本领域所熟悉。
一种特别优选的催化剂是磺酸型离子交换树脂如Amberlyst A-15。美国专利4,447,668描述了使用A-15与甲基叔丁基醚为溶剂的的异丁烯的二聚。
我们的美国专利5,877,372描述了使用磺酸树脂催化剂、叔丁醇选择性增强改性剂和异辛烷稀释剂的异丁烯的选择性二聚。
美国专利4,100,220描述了使用磺酸树脂催化剂和叔丁醇选择性增强改性剂的异丁烯二聚。少量的丁烷出现在二聚原料中。
在异丁烯二聚中需要考虑的包括去除大量的反应热以及要求保持对二聚产物的高选择性。本发明提供了一种可实现这些目的的方法。
发明概述
按照本发明，提供了一种在选择性增强量的叔丁醇和作为稀释剂的C3和/或C4(优选C4)烷烃两者的存在下异丁烯二聚的方法。在一个特别优选的实践中，叔丁醇，如源于由异丁烷制异丁烯法中的环氧丙烷/叔丁醇的叔丁醇被用作原料，通过二聚物的氢化形成的异辛烷为最终产物。
附图的简要说明
附图是本发明的一个特别优选实施方案的示意图。
详细说明
参照附图和其所示的方法，源于由异丁烷制异丁烯法的叔丁醇产物作为本发明方法的原料。叔丁醇经管线1送入到脱水区2，并在那里叔丁醇按照已知方法脱水成为异丁烯，水经管线3从区2去除。
如将在以下描述，一部分叔丁醇经管线4导入，以用作在区5进行的异丁烯二聚的选择性增强改性剂。
产物异丁烯经管线6从区2移出并送入二聚区5，其中所述异丁烯被高选择性二聚成二异丁烯。为了在区5获得高的二聚选择性，经管线4和10以选择性增强的量提供叔丁醇和经管线10提供作为二聚稀释剂的丁烷，在进行本发明方法中均是重要的。
调节进入5区的进料组成以提供选择性增强量的叔丁醇(一般为1-30％重量)和有效去除热和降低异丁烯浓度的量的烷烃稀释剂，其中异丁烯浓度被降低到可获得最佳选择性如97％的水平，通常烷烃为进入区5进料总量的30-80％重量。
用于所述二聚的烷烃稀释剂优选为异丁烷或正丁烷或它们任何比例的混合物，并且需要时可经管线7加入。也可使用丙烷。
在区5中，含异丁烯的进料与固体二聚催化剂(优选为磺酸树脂催化剂，如Rohm&Haas的Amberlyst A-15)在二聚反应条件下接触，从而获得对所述二聚物有非常高的反应选择性。通常在区5也形成少量(如占转化的异丁烯10％以下)的三聚物。
包括叔丁醇、烷烃稀释剂、未反应的异丁烯以及异丁烯二聚物和三聚物的来自区5的反应混合物经管线8进入分离区9，在分离区9通过常规方法将包括未反应的异丁烯、烷烃稀释剂和叔丁醇及少量C8的流分离，并经管线10循环到二聚区5。这种循环流的少量吹扫可能对维持叔丁醇水平是需要的，并且经管线15提供。这种吹扫流可循环到区2以回收叔丁醇、烷烃和异丁烯等有用成分。包括烷烃连同异丁烯二聚物和三聚物的高沸流经管线11送到氢化区12，在氢化区12异丁烯聚合物产物被氢化形成聚合汽油组分。氢气经管线13导入。
主要包括异丁烷连同一些异十二烷的来自区12的产物流作为适合作为高辛烷值汽油池调合组分的产品经管线14排出。
通过由异丁烷制异丁烯法进行的叔丁醇的生产是众所周知的，并以工业规模广泛使用。参见例如美国专利3,351,635。
同样，叔丁醇的脱水形成异丁烯也是众所周知的。参见例如美国专利5,625,109、3,510,538、4,165,343和4,155,945。
按照本发明的异丁烯的二聚包含各种新特征。首先，使用叔丁醇作为选择性增强改性剂，结果是对二聚物反应的选择性与没有这种改性剂的操作相比具有实质性的改善。
其次，使用C3-C4烷烃(优选丁烷)作为稀释剂，在降低异丁烯进料浓度的条件下进一步提高反应选择性，并有助于去除反应放热。
通常，在所述低聚步骤中可使用已知的低聚催化剂和条件。适合的条件包括0-200℃，优选10-100℃的宽范围温度和使用足以保持液相的压力，如高于50psig，例如50-500psig。
可使用已知的二聚催化剂，包括描述于先有技术如美国专利3,760,026中的二聚催化剂。特别优选使用磺酸型离子交换树脂，如Amberlyst A-15，Dowex 50等。
本发明的一个特征是使用叔丁醇作为烯烃二聚的选择性增强改性剂。
基于反应混合物中烯烃加上改性剂加上稀释剂的重量计算，所用的改性剂的量为至少1％重量，优选5-15％重量。
通过使用叔丁醇和较低级烷烃两者来进行低聚，反应选择性可将至少90％转化的异丁烯变为对二异丁烯。其余的反应产物基本上是三聚物，几乎没有或没有形成更高级聚合物。
从低聚区5出来后，反应混合物被送到相当于蒸馏区的区9。所述混合物中剩余的未反应异丁烯、烷烃稀释剂和这种叔丁醇改性剂被分离并经管线10循环到区5。应该指出在区5中可能会发生一些叔丁醇的脱水和在区9可能存在叔丁醇的损失，这样要求经管线4将叔丁醇提供到***中。
根据叔丁醇与异丁烯和水的平衡，其在区5中或是被消耗或产生。以***衡条件进料操作是有利的，这样使叔丁醇净变化接近零。
异丁烯聚合产物经管线11送到氢化区12，在那里将不饱和聚合物按照已知方法氢化成主要为异辛烷的饱和产物。氢气经管线13导入。
来自区12的产物经管线14排出，并可直接送入到汽油调合池，因为这种产物流主要包括高辛烷值汽油调合烃。
下面的实施例用于举例说明本发明。
参见附图，来自由异丁烷制异丁烯法的环氧丙烷/叔丁醇的叔丁醇构成了***的原料。这种原料包括约94％重量的叔丁醇与主要为水和丙酮的剩余物质。
将约250,000磅/小时的叔丁醇经管线1送到脱水区2，在那里使用铝土脱水催化剂在约371℃和200psig下脱水。通过脱水形成的水和与进料一起导入的水经管线3以60,000磅/小时的速率排出。包括96.5％重量异丁烯、1.0％重量叔丁醇、0.02％水、1.3％丙酮和1.18％其它物质的产物异丁烯流从脱水区2经管线6以190,000磅/小时的速率送到二聚区5。一部分由异丁烷制异丁烯法的叔丁醇也经管线4以20磅/小时的速率送入区5，(该流体按需要间歇供料)，包括31.8％异丁烯、52.3％丁烷、5.6％叔丁醇和2.7％C8和C12异烷烃的来自区9的循环异丁烯、丁烷和叔丁醇流以576,400磅/小时的速率经管线10送到区5。所述丁烷组分为10％异丁烷和90％正丁烷。
送到区5的混合进料流具有48％重量异丁烯、4.5％重量叔丁醇、44％重量丁烷、0.3％重量水、2％重量较高级烷烃和1.2％重量其它物质的组成。区5是填充A-15磺酸树脂催化剂的反应器，液体进料的液体时空速度为6小时-1，在190℃和300psig下与催化剂接触。
反应混合物经管线8从5区排出并送到分离区9，在分离区9较轻的物质在60℃和50psig下从塔顶蒸馏出来并经管线10送到如上所述的区5中。吹扫流以6650磅/小时的量经管线15排出。
包括95％重量二异丁烯、5％重量更高级异丁烯低聚物和痕量其它物质的底流异丁烯二聚物混合物以183350磅/小时的速率经管线11送到氢化区12，在那里将异丁烯聚合物氢化成异烷烃。氢气以11,500磅/小时的速率经管线13导入，使用载于碳上的Pd氢化催化剂和使用150℃、200psig的氢化条件和5小时-1的重量时空速度。
所述氢化可按照已知方法使用各种催化剂和反应条件进行。虽然上面显示了Pd催化剂，但是也可使用各种其它已知的氢化催化剂。为了调节氢化反应的放热，建议以约3∶1(重量)的循环∶进料比进行冷却循环。
将氢化反应产物混合物以185,819磅/小时的速率经管线14从区12排出并回收。过量的氢气循环到区12中。
基于转化的叔丁醇计，上述整个***对异辛烷的总选择性为约95％。比较起来，在没有使用叔丁醇改性剂也没有使用丁烷稀释剂的情况下，总体选择性只有约30％。

Claims (2)

1.一种在固体二聚反应催化剂的存在下，将异丁烯选择性低聚成二聚物的方法，其中所述异丁烯是通过叔丁醇的脱水形成，所述方法的改进之处包括：在C3-C4烷烃稀释剂和叔丁醇的存在下低聚所述异丁烯，其中
该C3-C4烷烃稀释剂的量足以提高对二聚物的低聚选择性和吸收反应放热的量，即C3-C4烷烃稀释剂的量，占异丁烯、C3-C4烷烃稀释剂和叔丁醇总重量的30-80重量％范围之间，及
该叔丁醇的量足以提高对二聚物的低聚选择性，即叔丁醇的量，占异丁烯、C3-C4烷烃稀释剂和叔丁醇总重量的至少1重量％。
2.一种制备主要包含异辛烷的高辛烷值汽油调合混合物的方法，所述方法包括以至少90％的选择性将异丁烯低聚成二聚物，所述低聚用磺酸树脂催化剂、叔丁醇选择性增强改性剂和C4烷烃稀释剂实施，并且在氢化反应催化剂存在下，将低聚产物氢化形成主要为异辛烷的产物，其中
该叔丁醇选择性增强改性剂的量，占异丁烯、C4烷烃稀释剂和叔丁醇选择性增强改性剂总重量的至少1重量％。
该C4烷烃稀释剂的量，占异丁烯、C4烷烃稀释剂和叔丁醇选择性增强改性剂总重量的30-80重量％范围之间。
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