CN1279661A - 异丁烯的低聚方法 - Google Patents

异丁烯的低聚方法 Download PDF

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CN1279661A
CN1279661A CN98811247A CN98811247A CN1279661A CN 1279661 A CN1279661 A CN 1279661A CN 98811247 A CN98811247 A CN 98811247A CN 98811247 A CN98811247 A CN 98811247A CN 1279661 A CN1279661 A CN 1279661A
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trimethyl carbinol
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T·I·埃范斯
L·J·卡拉斯
R·拉梅斯瓦兰
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Lyondell Chemical Technology LP
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00Aliphatic unsaturated hydrocarbons
    • C07C11/02Alkenes
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04Preparation 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
    • C07C2/06Preparation 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00Aliphatic saturated hydrocarbons
    • C07C9/14Aliphatic saturated hydrocarbons with five to fifteen carbon atoms
    • C07C9/16Branched-chain hydrocarbons
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/06Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • C07C2531/08Ion-exchange resins
    • C07C2531/10Ion-exchange resins sulfonated

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  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

本发明涉及生产富异辛烷的汽油混合馏份的方法,该方法在采用叔丁基醇改性剂和异烷烃稀释剂条件下二聚异丁烯;来自叔丁基醇的脱水的异丁烯是有利的,在二聚反应中作为稀释剂的异烷烃是由低聚产品的氢化形成的产物。

Description

异丁烯的低聚方法
                      发明背景
发明领域
本发明涉及异丁烯选择性二聚合的一种一体化方法,特别涉及应用二异丁烯氢化生成的异丁烷作二聚合溶剂。具体的优点包括采用来自环氧烷类的环氧丙烷/叔丁醇过程的叔丁醇作原料和采用叔丁醇作二聚合过程的选择性增强改性剂。
现有技术描述
如异丁烯的烯烃类的低聚,采用酸性催化剂来进行是一种已知的反应。
如美国专利3,760,026所述,已知一系列催化剂可用于这种反应,包括冷硫酸,附着于硅藻土上的磷酸,硅石/矾土(有时用Ni、Co、Fe、Pt或Pd促进);活化的天然粘土加上活化物质诸如ZnO金属磷酸盐,诸如铁(Ⅲ)和铈的磷酸盐,还可附着于载体上如活性炭,铝土矿,单独的活性碳和含金属卤化剂的活性炭,卤化剂诸如TiCl2杂多元酸,如附着于硅胶上的硅钨酸和磷钼酸;BF3H3PO4和BF3HPO3;二羟基氟硼酸HF和氟化物或沸点在300℃以下的S、Se、N、P、Mo、Te、W、V和Si的氧氟化物;BF3二甲基醚络合物;BF3烃络合物;BF3SO2;和带共催化剂如二甲基醚、HCl、和硝基甲烷的AlCl3。这些催化剂和二聚过程,包括操作条件在专业领域内皆是已知的。
一种特别优选的催化剂是一种磺酸型离子交换树脂,诸如Amberlyst A-15。美国专利4,447,688叙述利用A-15,以甲基t-丁基醚作溶剂的异丁烯二聚合。
与异丁烯二聚合相关的因素包括去除大量反应加以及保持对二聚合产物高选择性的要求。本发明提出了一种达到这些目的的方法。
                      发明简述
本发明提出了一种在有选择性增强量的叔丁醇存在下和异烷烃稀释剂存在下的异丁烯二聚合的方法。在一个具体的优选实例中,叔丁醇如从环氧烷类的环氧丙烷/叔丁醇过程得到的叔丁醇被用作原料,而异辛烷则是最终产品。
                      附图简述
附图是本发明一个特别优选实例的流程。
                      发明详述
参照附图及其中所示之方法,由环氧烷类过程得到的叔丁醇产品组成过程的原料。叔丁醇经管线1送入脱水区2,其中叔丁醇根据已知方法脱水生成异丁烯,水经管线3从区2排出。
部分叔丁醇经管线4送去作异丁烯二聚合的选择性增强改性剂,该过程在区5进行并将在下面叙述。
异丁烯产物从区2经管线6排出并送入二聚合区5,其中异丁烯以高选择性二聚合为二异丁烯。为了在区5中达到高选择性的二聚合,选择性增强量的叔丁醇经管线4和10和作二聚合稀释剂的异辛烷经管线7送入,对于过程的进行皆是很重要的。
对区5的进料组成进行调节,以提供选择性增强量的叔丁醇,一般为1-30%(重量),及提供异烷烃稀释剂的量以有效去除热量,并将异丁烯的浓度减少到能取得最佳选择性如97%的水平,一般异烷烃为区5总进料的30-80%(重量)。
用作二聚合的异烷烃稀释剂至少含有50%(重量)的异辛烷,通常至少是90%(重量)异辛烷少量如1-10%(重量)异十二烷(2,2,4,4,6五甲基庚烷)。
区5中含异丁烯的进料与固体二聚合催化剂,优选磺酸树脂催化剂,如Rohm&Haas公司的Amberlyst A-15接触,二聚合反应条件是对二聚物有特别高的反应选择性。通常在区5内亦生成少量三聚物,例如小于被转化的异丁烯的10%。
区5流出的反应混合物含有叔丁基醇、异烷烃、未反应的异丁烯以及异丁烯二聚物和三聚物,该混合物经管线8送入分离区9,其中用常规方法将含有未反应的异丁烯和叔丁基醇和少量C8的物流分离出并经管线10循环到二聚合区5。该循环物流的少量去除是必须的,以保持叔丁基醇的水平,去除量由管线15排出。该去除物可循环到区2以便利用叔丁基醇和异丁烯等有用成份。含异烷烃和异丁烯二聚物和三聚物的高沸点物流经管线11送入氢化区12,其中异丁烯聚合产物经氢化成聚合物汽油组分。氢经管线13引入。
来自区12的产品物流主要含异辛烷及一些异十二烷,该物流经管线14排出,其一部分经管线7循环到区5作二聚合过程的稀释剂和除热剂,而其余部分为产品,该产品适于作高辛烷值汽油池的混合组分。
采用环氧烷类过程生产叔丁基醇是众所周知的,并有工业规模的实践经验,可参见如美国专利3,351,635。
与此类似,叔丁醇脱水生成异丁烯亦是熟知的,可参见如美国专利5,625,109、3,510,538、4,165,343以及4,155,945。
本发明的异丁烯二聚合包括各种新特点。首先,采用叔丁醇作选择性增强改性剂,其结果对二聚合物的反应选择性较无改性剂的操作有实质性的改进。
其次,采用主要含异辛烷的异烷烃作稀释剂,在减小异丁烯进料浓度的条件下进一步提高了反应选择性,并有助于去除反应的放热。
当然,一体化系统是本发明的优选实例,该系统中采用叔丁醇作总进料,并将来自异丁烯二聚物和三聚物产物氢化的异烷烃循环到二聚合反应。但是,上述特点是新颖的,并可申请专利。
总的说来,已知的低聚催化剂和条件可用于低聚步骤。适应的条件包括较宽的温度范围0-200℃,优选10-100℃,所用压力足以维持液相,例如高于50psig,即50-500psig。
可采用的已知二聚合催化剂包括现有技术如美国专利3,760,026所述的催化剂。特别优选磺酸型离子交换树脂,诸如Amberlyst A-15,Dowex 50等等。
本发明之特点在于采用叔丁醇作烯烃二聚合的选择性增强改性剂。
所用改性剂的量至少为反应混合物中烯烃的重量加改性剂和稀释剂重量的1%(重量),优选5-15%(重量)。
采用叔丁基醇和异烷烃进行低聚时,反应选择性可将至少90%的转化异丁烯变为二异丁烯,其余的反应产物主要是三聚物,很少生成或不生成高聚物。
反应混合物从低聚区5送入区9,该区相当于蒸馏区。留在混合物中的未反应的异丁烯及叔丁基醇改性剂被分离并经管线10循环到区5。应该指出,在区5中叔丁基醇可能有一些脱水,区9中叔丁基醇可能有损失,这要求经管线4向系统补充叔丁基醇。
根据叔丁基醇和异丁烯和水的平衡,区5中叔丁基醇或者消耗,或者产生。宜在接近平衡的条件下进料操作,这样净叔丁基醇的变化接近零。
异烷烃和异丁烯聚合产物经管线11送入氢化区12,其中不饱和聚合物根据已知方法氢化为饱和产物,主要是异辛烷,氢经管线13引入。
区12的产品经管线14排出,并可直接送至汽油混合池,因为该物流基本上由掺合高辛烷汽油的烃类组成。部分经管线7循环到区5以便提供低聚过程所必需的稀释剂。
下面的实施例说明本发明。
参照附图,从环氧烷类的丙烯氧化物/叔丁醇过程来的叔丁醇组成系统的进料。该进料含约94%(重量)叔丁醇,其余主要是水和丙酮。
大约150,000磅/时的叔丁醇经管线1送入脱水区2,在区2内于约371℃和200psig条件下用矾土脱水催化剂脱水。脱水生成的水和随进料引入的水经管线3以60,000磅/时的速率排出。异丁烯产品物流含96.5%(重量)的异丁烯、1%叔丁醇、0.02%水、1.3%丙酮和1.18%其它物质,该物流从脱水区2经管线6以190,000磅/时的速率送入二聚合区5。部分环氧烷类过程的叔丁醇亦经管线4以20磅/时的速率送入区5,(该物流按需间歇供料),含78%(重量)异丁烯、15%叔丁基醇和7%C8和C12异烷烃的再循环异丁烯和叔丁基醇物流从区9以221,000磅/时的速率经管线10送入区5,以及组成为95%(重量)异辛烷和5%较高烷烃(主要是异十二烷)的异辛烷物流从区12以327,000磅/时的速率经管线7送入区5。
送入区5的组合进料物流的组成为48%(重量)的异丁烯、4.5%的叔丁醇、44%的异辛烷,0.3%水、2%较高烷烃和1.2%其它物质。区5是充填有A-15磺酸树脂催化剂的反应器,液体进料的小时空间速度为6hr-1,在190℃和300psig下与催化剂接触。
反应混合物从区5经管线8排出,并送入分离区9,其中轻物质在60℃和50psig下以塔顶馏出物蒸馏出并按上述方式经管线10送入区5。去除物流以1800磅/时的量从管线15引出。
异丁烯二聚物混合物塔底流含34%(重量)的二异丁烯、2%的较高异丁烯低聚物、63%异烷烃稀释剂和1%其它物质,该物流以510,000磅/时的速率经管线11送入氢化区12,其中异丁烯聚合物氢化为异烷烃。氢经管线13以11,500磅/时的速率引入,采用附着在碳上的Pd作氢化催化剂,氢化条件采用150℃,200psig,重量小时空间速度为5hr-1
氢化可按照已知的方法采用不同的催化剂和反应条件进行。为了载出氢化反应的放热,建议按循环∶进料为3∶1(重量)的比例进行冷循环。
异烷烃反应产物混合物从区12排出,部分混合物按上述经管线7循环至区5,净产品以186,000磅/时的速率经管线14回收。
基于转化的叔丁醇计,整个系统对异辛烷的总选择性约为94%。与此相比,在不采用叔丁醇改性剂和也不采用异辛烷稀释剂的情况下,总选择性仅约30%。

Claims (4)

1.一种用于异丁烯的低聚方法的改进,该改进包括在有叔丁醇存在下低聚异丁烯,叔丁醇的用量是足以提高二聚物的低聚选择性。
2.一种用于异丁烯的低聚方法的改进,该改进包括在异烷烃稀释剂存在下低聚异丁烯,稀释剂主要含异辛烷,其用量是足以提高二聚物低聚选择性和吸收反应放热。
3.一种生产主要含异辛烷高辛烷值汽油掺合混合物的方法,该方法包括将异丁烯低聚为二聚物,其选择性至少为90%,低聚在具有磺酸树脂催化剂、叔丁基醇选择性增强改性剂和异烷烃稀释剂下进行,将低聚产物氢化以生成主要是异辛烷,其一部分作为过程产品,一部分循环返回低聚反应。
4.权利要求1的方法,其中异丁烯由叔丁醇脱水生成。
CNB988112477A 1997-11-21 1998-09-29 异丁烯的低聚方法 Expired - Fee Related CN1140486C (zh)

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