甲缩醛和甲醛催化合成柴油添加剂聚甲氧基二甲醚.pdf

石油化
888
PETROCHEMICAL TECHNOLOGY
2015年第44卷第7期
甲缩醛和甲醛催化合成柴油添加剂
聚甲氧基二甲醚
刘显科,夏成良,张建强,刘殿华
(华东理工大学化学工程联合国家重点实验室,上海200237)
[摘要]以甲缩醛(PODE1)和甲醛为原料,在固定床反应器中利用对甲苯磺酸改性的大孔阳离子树脂为催化剂,通过连续进
料的方式制备了柴油添加剂聚甲氧基二甲醚(PODE,)(x为聚合度),利用化学滴定和GC法考察了反应温度、反应压力、重
时空速、原料配比及不同原料对反应的影响。实验结果表明,适宜的反应条件为:反应温度70℃、反应压力1.SMPa、重时
空速3h、原料配比n(甲醛):n(PODE1)=4:1。在此条件下,PODE1的转化率为60.54%,PODE3s的选择性和收率分别为
3392%和20.54%。加入PODE2可提高目标产物PODE3s的选择性和收率。
关键词]甲缩醛;甲醛;聚甲氧碁二甲醚;柴油添加剂
文章编号]1000-8144(2015)07-0888-05
[中图分类号]TE624.8
文献标志码]A
Synthesis of Polyoxymethylene Dimethyl Ethers as Diesel Fuel Additives from
Methylal and Formaldehyde
Liu Xianke, Xia Chengliang, Zhang ianqian, Liu Dianhua
(State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China)
Abstract J Polyoxymethylene dimethyl ethers( PODE, x: degree of polymerization) which
could be used as diesel fuel additives were synthesized from formaldehyde and methylal in a fixed bed
reactor using para-toluenesulfonic acid modified macroporous cation exchange resin as the catalyst
The effects of temperature, pressure, WHSV and molar ratio of the raw materials on the reaction
were investigated by means of chemical titration and GC. The results indicated that under the optimum
reaction conditions of reaction temperature 70 C, reaction pressure 1. 5 Mpa, WHSV 3 h"and
n(formaldehyde): n(methylal)4: 1, the conversion of PODE, selectivity to PODE s and yield
of PODE .s were 60.54%0, 33.92%o and 20.54%0, respectively. And the selectivity and yield could b
increased significantly by adding PODE
Keywords J methylal; formaldehyde; polyoxymethylene dimethyl ethers; diesel fuel additive
近年来,随着环境问题的日益严峻,开发清柴油添加剂的组分?。有研究?发现,将PODE3s
洁的柴油添加剂迫在眉睫。目前主要的柴油添加剂掺入柴油中后,柴油机尾气中含碳颗粒物排放下降
有甲醇、二甲醚和甲缩醛。其中,甲醇的主要问题明显,因此PODE35是一种清洁型的柴油添加剂。
是不易溶于柴油,且会降低柴油的闪点和十六烷
合成PODE3的原料主要包括以下3类:1)甲
值;二甲醚1和甲缩醛(PODE1)的缺陷在于沸醛和甲醇7-9,以甲醛和甲醇为原料合成PODE35
点低、爆炸范围宽、蒸气压高。而聚甲氧基二甲瞇的工艺流程简单,原料廉价易得。2)三聚甲醛和
(PODE)(x为聚合度)是一种可克服上述缺点的化PODE1(或甲醇)014,该方法由于三聚甲醛价格
合物,其物性与柴油相似,被认为是最适合作为高昂,经济效益较差。3)多聚甲醛和PODE1"12,
收稿日期]2015-01-13;[修改稿日期]2015-04-24。
L作者简介]刘显科(1991~),男,安徴省六安市人,硕土生。联系人:刘殿华,电话021-64252151,电邮 dhliu(@eust.edu.en
[基金项目]中央高校基本科研业务费专项资金资助项目(WA0914014)。