CN108863693A - 一种双环烷烃的制备方法及其作为喷气燃料的用途 - Google Patents
一种双环烷烃的制备方法及其作为喷气燃料的用途 Download PDFInfo
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Abstract
本发明公开一种双环烷烃的制备方法,在双功能固体催化剂的存在下,环醇和/或环烯烃中的一种或多种,首先在氮气气氛和一定温度下,自身或相互之间发生C‑C偶联反应,得到双环烷烃母体混合物;然后将氮气更换为氢气并在一定温度下和压强下,将双环烷烃母体混合物进行加氢或加氢脱氧反应,即得到所述的双环烷烃。本发明制备方法所制得的双环烷烃用作喷气燃料的用途。本发明的方法操作流程简单,生产设备简单,生产成本低,得到的双环烷烃具有高密度、高热安定性、低冰点等优点。
Description
技术领域
本发明属于有机燃料应用技术领域,具体涉及一种双环烷烃的制备方法及其作为喷气燃料的用途。
背景技术
高密度碳氢燃料作为液体推进剂的重要组成部分,是决定航天器飞行性能的关键因素之一,其可以是单组分碳氢化合物也可以是多组分碳氢化合物的混合物,可应用于涡喷、冲压、火箭及组合动力等发动机。载人航天、探月工程的发展对高密度燃料提出了更高的要求:一方面要求燃料在油箱体积一定的情况下提供更多的推进动能(即更高的体积热值,密度>0.85g/mL);另一方面要求其还必须具备较好的低温流动性和较好的热安定性等性质。目前使用的高密度碳氢燃料,主要来自于特定石油基化合物及其衍生物(如环戊二烯、茚、萘等)经聚合、加氢等反应制备得到。
双环烷烃(如联环戊烷、联环己烷、十氢萘、烷基取代的十氢萘等)的密度高于0.86g/mL,冰点在-110℃~2.6℃范围内。其中,萘烷烃具有较高的热氧安定(如十氢萘是高密度热安定性喷气燃料JP-900的主要组分)。
目前双环烷烃的合成通常分两步或多步完成,第一步由选定的原料通过C-C偶联反应(如Adol缩合反应、烷基化反应等,有的需要提前脱氢或者还原)合成含有氧的不饱和化合物,经过分离提纯后进行第二步反应,在较苛刻的条件下对含氧化合物进行加氢脱氧反应,通常得到组分单一的化合物,对所用催化剂和反应设备要求比较高;通过两步法得到组分单一的双环化合物,无法结合各组分的性质优势(例如,联环己烷具有较高的密度0.88g/mL,但是冰点2.6℃太高;双甲基取代十氢萘的密度为0.88g/mL,但冰点可以低于-110℃);并且反应条件较苛刻或不适合批量生产。例如双环戊(己)烷的合成(Green Chem.,2015,17,4473–4481),首先以环戊(己)酮为原料,通过Adol缩合反应得到含羰基的不饱和双环化合物,然后在高温高压的条件下(250℃,6MPa的H2,48h)得到饱和联环戊(己)烷。萘烷烃通常由煤基化合物(Fuel Processing Technology,2008,89(4),364–378)如萘经两步高压加氢工艺制备得到,第一步对萘中度加氢,制备出四氢萘,并将原料中绝大部分硫除去;第二步对四氢萘深度加氢制备出十氢萘,这一步加氢比较困难,反应压力根据所用催化剂不同,甚至高达15MPa,反应温度100~220℃不等。Zhang等(ACS SustainableChem.Eng.,2016,4(11),6160–6166)以环戊醇为原料,首先催化其脱水生成环戊烯并分离提纯;再催化环戊烯烷基化反应生成十氢萘并分离提纯,通过高压加氢烷基化产物得到十氢萘(77wt%)和C15烷烃的混合物;混合物的密度为0.90g/mL,但是冰点较高(-10.0℃),制备流程长。
现有的双环烷烃合成方法有以下缺点:1、一般通过两步或多步反应实现,中间过程需要多次分离提纯,操作繁琐;2、得到的是单一组分的化合物,不能结合多种组分的性质优势;3、加氢脱氧反应的条件苛刻,温度高,压力高,对设备要求也较高。
为克服以上缺点,提出本发明。
发明内容
本发明为了解决现有双环烷烃合成方法的步骤复杂、产物组分单一、反应条件苛刻的不足,提供了一种双环烷烃的制备方法及其作为喷气燃料的用途。
本发明的目的通过以下技术方案予以实现:
本发明第一方面公开了一种双环烷烃的制备方法,在双功能固体催化剂的存在下,环醇和/或环烯烃中的一种或多种,首先在氮气气氛和一定温度下,自身或相互之间发生C-C偶联反应,得到双环烷烃母体混合物;然后将氮气更换为氢气并在一定温度下和压力下,将双环烷烃母体混合物进行加氢或加氢脱氧反应,即得到所述的双环烷烃。
优选地,所述环醇选自环戊醇、甲基环戊醇、二甲基环戊醇、乙基环戊醇、丙基环戊醇、环己醇、甲基环己醇、二甲基环己醇、乙基环己醇、丙基环己醇、环庚醇、甲基环庚醇、二甲基环庚醇、乙基环庚醇、丙基环庚醇或5-乙基-3-甲基环庚醇;所述环烯烃选自环戊烯、甲基环戊烯、二甲基环戊烯、乙基环戊烯、丙基环戊烯、环己烯、甲基环己烯、二甲基环己烯、乙基环己烯、丙基环己烯、环庚烯、甲基环庚烯、二甲基环庚烯、乙基环庚烯、丙基环庚烯或5-乙基-3-甲基-环庚烯。
优选地,所述双功能固体催化剂为Ni/Hβ、CuCo/ITQ、Pt/Hβ、Ni/Al-MCM-41、Ir/Al-SBA-15、PtNi/Al-SBA-16、PdFe/SO4 2-/ZrO2、Pd/SAPO、Pt/SiO2-Al2O3、CoMo/Hβ、Au/HY、Ru/Au-MCM-41、CoMo/MMT-K10、CuZn/Hβ、Pd/HY、Ru/H-ZSM-5、Pt/Ti-MCMC-41中的一种或几种;所述双功能固体催化剂的加入量占反应物总质量的1wt%~20wt%
优选地,所述C-C偶联反应的温度范围为100~250℃;所述加氢或加氢脱氧反应的温度范围为100~180℃,氢气的压强2~6MPa。
本发明第二方面公开了所述的制备方法制得的双环烷烃用作喷气燃料的用途。
本发明所述的环醇、环烯烃以及双环烷烃母体混合物的示例性结构示意图如下:
(a):环醇
(b):环烯烃
(c):双环烷烃母体混合物
本发明所制得的双环烷烃的一些示例性结构如下所示:
本发明中,未特别指明的百分含量均为重量百分含量。
本发明的有益效果:
1、针对目前双环烷烃反应的两步或多步法需要分离提纯操作繁琐的问题,本发明的方法以环醇和/或环烯烃为原料,以包含金属位和酸性位的负载型双功能催化剂为催化剂一锅两步法得到产物双环烷烃。首先在氮气气氛保护下实现原料C-C偶联生成双环烷烃母体,再调控反应温度和反应气氛及压力,实现对双环烷烃母体加氢和/或加氢脱氧过程得到产物双环烷烃,从而避免了繁琐的中间产物的转移和分离操作过程。
2、针对目前双环烷烃反应的产物组分单一,无法结合各个组分性质优势的问题,本发明的方法以环醇和/或环烯烃为原料,根据目标产物的性质标准,结合各组分的性质优势,通过调控催化剂的组成和原料的组成,对产物实现单一组分到多组分的调控,在反应过程中通过一锅反应直接调控合成相应组成的燃料混合物,得到综合性能较高的燃料组成混合物。
3、针对目前双环烷烃反应的加氢脱氧条件苛刻的问题,本发明的方法选择了环醇和/或环烯烃化合物为原料,这些原料通过酸性催化剂的作用,在实现C-C偶联后实现了脱氧加氢过程。后续加氢和/或加氢脱氧的过程所需条件温和,对氢气压力要求不高,对设备的要求也较低,生产成本低,可以较容易地实现工业化生产。
4、本发明的一锅两步法制备双环烷烃的方法,原料来源广泛,可以是石油化工中间体、生物质衍生物,通过酸性催化剂的催化作用在氮气保护下将烷基化反应、异构反应和氢转移反应结合起来,得到饱和双环烷烃和不饱和双环烷烃的混合物,然后置换氮气为氢气,通过金属催化剂的的催化作用,得到饱和的双环烷烃混合物。本方法可以通过调控催化剂的组成以及原料组成,调控产物双环烷烃喷气燃料的组成,使得到的双环烷烃具有高密度、高热安定性、低冰点等优点。
附图说明
图1是本发明实施例1中环戊醇在Pt/Hβ催化作用下反应得到的双环烷烃母体及双环烷烃产物的GC-MS图。
具体实施方式
以下实施例旨在说明本发明的内容,而不是对本发明保护范围的进一步限定。
实施例1
将33.25g环戊醇和1.67g的Pt/Hβ同时加入到高压反应釜中,机械搅拌,在氮气保护下保持反应温度150℃反应10h,然后将温度降到120℃,此时将气氛更换为氢气,保持压力4MPa,继续反应5h。
用气相色谱对反应过程中的产物进行分析,在氮气气氛下环戊醇的转化率为100%,双环化合物的收率为90%。在氢气气氛下,不饱和双环化合物完全转化,双环烷烃的收率为95%。由此,整个过程中,环戊醇的转化率为100%,双环烷烃的收率为86%,其中萘烷烃收率为59%。本实施例的双环烷烃母体及双环烷烃母体加氢得到产物双环烷烃的GC-MS图如图1所示。
实施例2-18
同实施例1,以Ni/Hβ、CuCo/ITQ、Ni/Al-MCM-41、Ir/Al-SBA-15、PtNi/Al-SBA-16、PdFe/SO4 2-/ZrO2、Pd/SAPO、Pt/SiO2-Al2O3、CoMo/Hβ、Au/HY、Ru/Al-MCM-41、CoMo/MMT-K10、CuZn/Hβ、Pd/HY、Ru/H-ZSM-5、Pt/Ti-MCMC-41等为催化剂,催化环醇和/或环烯烃的一锅两步反应。反应物及其用量、催化剂及其用量、反应物转化率、反应温度、反应时间以及双环烷烃的收率的结果列于表:
由实施例1~18看出,环醇和/或环烯烃等在Ni/Hβ、CuCo/ITQ、Pt/Hβ、Ni/Al-MCM-41、Ir/Al-SBA-15、PtNi/Al-SBA-16、PdFe/SO4 2-/ZrO2、Pd/SAPO、Pt/SiO2-Al2O3、CoMo/Hβ、Au/HY、Ru/Al-MCM-41、CoMo/MMT-K10、CuZn/Hβ、Pd/HY、Ru/H-ZSM-5、Pt/Ti-MCMC-41催化剂的催化作用下,在氮气气氛,100~250℃的温度范围内发生C-C偶联反应;在2~6MPa氢气气氛下,100~160℃的温度范围内实现偶联产物的加氢和/或加氢脱氧反应。原料转化率都可以达到100%,得到双环烷烃的收率为77~95%,其中萘烷烃收率最高可以达87%,联环烷烃的收率可以达95%。
对所得双环烷烃产物用无水硫酸镁处理后,测其基本的燃料性质。实施例1和实施例3都是以环戊醇为原料,通过选用不同组成的催化剂,得到了不同组成的产物,实施例3主要得到联环戊烷,实施例1得到联环戊烷和萘烷烃的混合物。实施例4以环己烯为单一组分为原料,实施例5在实施例4的基础上添加环戊醇为原料,在双功能催化剂的催化作用下,得到不同组成的产物混合物,其中实施例4主要得到联环己烷,实施例5得到联环己烷、联环戊烷、环戊基环己烷和萘烷烃的混合物。依据国标GB2540-81“石油产品密度测定法”,对实施例1、3、4和5的产物进行密度测定,分别为0.89g·mL-1、0.87g·mL-1、0.88g·mL-1和0.89g·mL-1;依据国标GB2430-81“喷气燃料冰点测定法”,对实施例1、3、4和5的产物进行冰点测定,分别为低于-55℃、低于-36℃、2.6℃、低于-60℃;依据国标GB265-88“石油产品运动粘度测定法和动力粘度计算法”,对实施例1、3、4和5的产物进行动力学粘度测定,分别为2.89mm2/s(20℃)、1.62mm2/s(25℃)、4.00mm2/s(20℃)、2.46mm2/s(20℃);依据国标GB/T 384-81“石油产品热值测定法”,对实施例1、3、4和5的产物进行热值测定,分别为37.0MJ/L、36.8MJ/L、38.1MJ/L、37.0MJ/L。
由以上可知,实施例1的原料为单一的环戊醇,产物为联环戊烷和萘烷烃的混合物,产物的密度较高(0.89g·mL-1)、冰点较低(低于-55℃)、热值较高(37.0MJ/L)且粘度也较低(20℃下为2.89mm2/s)。实施例5的原料为环己烯和环戊醇,产物为联环己烷、联环戊烷、环戊基环己烷和萘烷烃的混合物,产物的密度较高(0.89g·mL-1)、冰点较低(低于-60℃)、热值较高(37.0MJ/L)且粘度也较低(20℃下为2.46mm2/s)。可见通过调控催化剂的组成以及原料组成,可以实现产物的单一组分到多组分的调控,进而调控合成燃料的性质,得到综合性能较高的燃料组成混合物。
Claims (5)
1.一种双环烷烃的制备方法,其特征在于,在双功能固体催化剂的存在下,环醇和/或环烯烃中的一种或多种,首先在氮气气氛和一定温度下,自身或相互之间发生C-C偶联反应,得到双环烷烃母体混合物;然后将氮气更换为氢气并在一定温度下和压强下,将双环烷烃母体混合物进行加氢或加氢脱氧反应,即得到所述的双环烷烃。
2.根据权利要求1所述的制备方法,其特征在于,所述环醇选自环戊醇、甲基环戊醇、二甲基环戊醇、乙基环戊醇、丙基环戊醇、环己醇、甲基环己醇、二甲基环己醇、乙基环己醇、丙基环己醇、环庚醇、甲基环庚醇、二甲基环庚醇、乙基环庚醇、丙基环庚醇或5-乙基-3-甲基环庚醇;所述环烯烃选自环戊烯、甲基环戊烯、二甲基环戊烯、乙基环戊烯、丙基环戊烯、环己烯、甲基环己烯、二甲基环己烯、乙基环己烯、丙基环己烯、环庚烯、甲基环庚烯、二甲基环庚烯、乙基环庚烯、丙基环庚烯或5-乙基-3-甲基-环庚烯。
3.根据权利要求1所述的制备方法,其特征在于,所述双功能固体催化剂为Ni/Hβ、CuCo/ITQ、Pt/Hβ、Ni/Al-MCM-41、Ir/Al-SBA-15、PtNi/Al-SBA-16、PdFe/SO4 2-/ZrO2、Pd/SAPO、Pt/SiO2-Al2O3、CoMo/Hβ、Au/HY、Ru/Al-MCM-41、CoMo/MMT-K10、CuZn/Hβ、Pd/HY、Ru/H-ZSM-5、Pt/Ti-MCMC-41中的一种或几种;所述双功能固体催化剂的加入量占反应物总质量的1wt%~20wt%。
4.根据权利要求1所述的制备方法,其特征在于,所述C-C偶联反应的温度范围为100~250℃;所述加氢或加氢脱氧反应的温度范围为,100~180℃,氢气的压强2~6MPa。
5.根据权利要求1-4任一所述制备方法制得的双环烷烃用作喷气燃料的用途。
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