CN112979404B - 一种使用外表面钝化的催化剂制备2,5-降冰片二烯的方法 - Google Patents
一种使用外表面钝化的催化剂制备2,5-降冰片二烯的方法 Download PDFInfo
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Abstract
本发明公开了一种使用外表面钝化的催化剂制备2,5‑降冰片二烯的方法,包括以下步骤:①将双环戊二烯与丙酮加入混合罐中,氮气吹扫置换后,低温下通入乙炔;②用恒流泵以固定流速将步骤①的液体输送至装有外表面钝化的酸性微孔沸石催化剂的高温连续管道反应器中进行反应;③反应结束后收集产物精馏提纯即得到2,5‑降冰片二烯。本发明采用外表面钝化的酸性微孔沸石为催化剂,显著抑制了副反应,从而显著提高了2,5‑降冰片二烯的选择性和收率,降低了生产成本。
Description
技术领域
本发明属于有机合成领域,具体涉及一种使用外表面钝化的催化剂制备2,5-降冰片二烯的方法。
背景技术
2,5-降冰片二烯(2,5-norbornadiene,NBD)为易燃液体,能溶于石油醚,不溶于水,相对密度为0.909(20℃),沸点89℃。NBD本身及其二聚物经全加氢后可用作赛车、导弹和火箭的高能燃料或高能燃料主组分。NBD的光异构化产物为四环庚烷(QC),是一种可自燃的高能燃料。并且,NBD和QC的可逆光异构反应,可用于吸收和释放太阳能。NBD还可以作为保鲜剂对鲜花、果蔬等起到很好的保鲜作用。
2,5-降冰片二烯通常是由乙炔与环戊二烯进行Diels-Alder加成而得到。由于环戊二烯在室温下极易聚合生成双环戊二烯,因此环戊二烯通常是通过双环戊二烯高温分解而得到。2,5-降冰片二烯的现有技术的制备方法如下:
专利1:美国专利US2875256公布的2,5-降冰片二烯的制备方法,采用连续的管式反应器,乙炔与环戊二烯的摩尔比为(1-10):1,反应温度为150-400℃、反应压力为1.76MPa左右,物料在反应区停留时间为1-15分钟。
专利2:中国专利CN03142244.6公布的2,5-降冰片二烯的制备方法,采用混合罐,并且引入丙酮作为溶剂,乙炔与双环戊二烯的摩尔比为(1.0-3.0):1,丙酮与双环戊二烯的重量比为(1.0-2.5):1,反应温度为170-230℃、反应时间为3-7小时。
专利3:中国专利CN200610117484.3公布的2,5-降冰片二烯的制备方法,采用连续的管式反应器,并且用丙酮作为溶剂溶解双环戊二烯,乙炔与双环戊二烯的摩尔比为(4.0-6.0):1,丙酮与双环戊二烯的重量比为(1.5-3.0):1,反应温度为180-200℃、物料在管式反应器中的停留时间为10-30分钟。
上述的专利都存在目标产物收率较低的缺点,其中专利1的目标产物收率≤25.0%,专利2≤45%,专利3≤58.5%。它们的2,5-降冰片二烯的收率较低主要是因为乙炔与环戊二烯的Diels-Alder加成反应较慢,并且在反应过程中有较多副反应发生,包括双环戊二烯与环戊二烯加成反应、双环戊二烯与乙炔加成反应和2,5-降冰片二烯的聚合反应等。
为解决上述问题提出本发明。
发明内容
为解决现有技术都存在目标产物2,5-降冰片二烯收率较低的缺点,本发明采用外表面钝化的酸性沸石分子筛为催化剂来抑制部分副反应的发生。本发明选择外表面钝化的酸性沸石分子筛催化剂,在反应过程中催化剂外表面及孔口的副反应被抑制,从而提高目标产物2,5-降冰片二烯的产率和选择性。
本发明的技术方案如下:
本发明公开了一种使用外表面钝化的催化剂制备2,5-降冰片二烯的方法,包括以下步骤:
①将双环戊二烯与丙酮加入混合罐中,氮气吹扫置换后,低温下通入乙炔;
②用恒流泵以固定流速将步骤①的液体输送至装有外表面钝化的酸性微孔沸石催化剂的连续管道反应器中进行反应;
③反应结束后收集产物精馏提纯即得到2,5-降冰片二烯。
优选地,所述酸性微孔沸石为ZSM-5、ZSM-35、HY、Hβ、ZSM-22、MOR中的一种。
优选地,所述催化剂的外表面钝化的方法为化学气相/液相沉积、酸处理、碱金属/碱土金属改性、硅烷化、硼烷化、硼改性、磷改性中的一种。
优选地,步骤①的环戊二烯与丙酮的质量比为1:(3-5)。
优选地,步骤①的乙炔与双环戊二烯的摩尔比为(3-5):1。
优选地,步骤②的反应温度为160-240℃。
本发明的有益效果
在2,5-降冰片二烯的制备过程中,首先是双环戊二烯热分解生成环戊二烯,环戊二烯再与乙炔进行Diels-Alder加成反应生成2,5-降冰片二烯。反应过程中容易发生双环戊二烯与环戊二烯加成、双环戊二烯与乙炔加成和2,5-降冰片二烯聚合的副反应。这些副产物的分子动力学直径均大于2,5-降冰片二烯(0.54×0.46nm),因此选择具有适宜孔道尺寸的催化剂可以抑制部分副反应的发生。沸石分子筛的酸性催化环戊二烯与乙炔的Diels-Alder加成反应,可以利用孔道的择形性限制较大尺寸副产物的生成,但是部分副反应仍然可以在催化剂的外表面或孔口发生。本发明选择使用外表面钝化的催化剂制备2,5-降冰片二烯,外表面钝化可以对催化剂外表面和孔口的酸性位点进行钝化,进一步提高2,5-降冰片二烯的选择性和收率。本发明的制备方法能够很好地避免部分副反应的发生,从而提高目标产物的产率和选择性。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。实施例中未注明具体技术或条件者,按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者,均为可以通过购买获得的常规产品。
实施例1
步骤一:将双环戊二烯与丙酮按质量比为1:4的比例溶解后,加入混合罐中,氮气吹扫置换后,低温下通入乙炔;
步骤二:用高压恒流泵以固定流速将步骤一的液体输送至装有外表面钝化的ZSM-5分子筛(Si/Al=50,)的高温连续管道反应器中反应,乙炔与双环戊二烯的摩尔比为4:1,反应温度为160-240℃,反应结束后收集产物精馏提纯得到2,5-降冰片二烯。
催化剂外表面钝化的方法可以根据文献(勾明雷,王俊锴,宋文生.介孔ZSM-5沸石外表面酸性位选择性钝化及其催化性能[J].硅酸盐学报,2020,48(12):1960-1965.)的方法进行。
实施例2-10
各实施例异构反应过程同实施例1,不同之处为:催化剂、反应器中的反应温度等。结果见下表。
由上述的结果可知,本发明使用外表面钝化的催化剂制备2,5-降冰片二烯,收率都在70%以上,最高可以接近90%。实施例2使用了外表面未钝化的ZSM-5催化剂,2,5-降冰片二烯的收率为72.6%,也较高,但明显低于使用外表面钝化的催化剂的收率(实施例1)。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (1)
1.一种使用外表面钝化的催化剂制备2,5-降冰片二烯的方法,其特征在于,包括以下步骤:
①将双环戊二烯与丙酮加入混合罐中,氮气吹扫置换后,低温下通入乙炔;双环戊二烯与丙酮的质量比为1:(3-5);乙炔与双环戊二烯的摩尔比为(3-5):1;
②用恒流泵以固定流速将步骤①的液体输送至装有外表面钝化的酸性微孔沸石催化剂的连续管道反应器中进行反应;所述酸性微孔沸石为ZSM-5、ZSM-35、HY、Hβ、ZSM-22、MOR中的一种;所述催化剂的外表面钝化的方法为磷改性;反应温度为160-240℃;
③反应结束后收集产物精馏提纯即得到2,5-降冰片二烯。
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