HIGHLY EFFICIENT SEPARATIVE REFINING OF USEFUL COMPOUNDS IN COAL TAR

有用的化合物如多环芳烃（萘、甲基萘、蒽、芘、荧蒽等）和杂环化合物以负载型金属硫酸盐为萃取剂，以正己烷、苯等为萃取溶剂，主要研究结果如下：1）采用10wt%Al^2（SO^4）^3/高比表面积（Al/Si）硅胶吸附分离，正己烷和苯分级萃取的方法，有效地脱除了粗甲基萘油（CMNO）中的氮。2）将上述技术应用于从粗蒽油中选择性分离吖啶，为制备1，2，3，4-四氢-9-氨基吖啶是治疗阿尔采末样老年痴呆的理想药物。3）采用Al/Al 2 O3催化剂对CMNO进行脱氮，Si吸附剂在超临界CO^2萃取条件50 ℃和70 atm下的萃取效果优于常规萃取方法。结果表明，采用高压超临界CO^2和甲醇洗涤的方法可以更有效地回收喹啉和异喹啉中的含氮化合物。4）在100 ℃和70 atm的超临界CO^2条件下，苯并噻吩（BT）在Al/Si催化剂上的二聚反应比在常压正辛烷溶液中的反应更具有选择性。在超临界CO^2条件下，通过选择性脱二聚和萃取，可以从粗萘馏分中分离出BT的二聚体。

Useful compounds such as polyaromatic hydrocarbons (naphthalene, methylnaphthalenes, anthracene, pyrene, fluoranthene and so on) and hetercoyclic compounds (quinoline, isoquinoline, acridine, benzothiophene and so on) were separated from coal tar fractions by combining solvent extraction and adsorption techniques using supported metal sulfates and a series of extraction solvents such as hexane, benzene, methanol and supercritical CO^2.Main research results are as follows ;1) Crude methylnaphthalene oil (CMNO) was effectively denitrogenated by adsorptive separation with 10 wt% Al^2(SO^4)^3 supported on silica gel of high surface area(Al/Si) and fractional extraction wiht hexane and benzene. Nitrogen compounds of quinoline and isoquinoline were concentrated and recovered in the benzene-eluted fraction at the same time.2) The same techniques as described above were applied to the selective separation of acridine from crude anthracene oil, providing an important starting material for preparing 1,2,3,4-tetrahydro-9-aminoacridine of expected remedy for Altzheimer-like senile dementia.3) CMNO was more selectively and effectively denitrogenated by using the Al/Si adsorbent under supercritical CO^2 extraction conditions of 50ﾟC and 70 atm than the conventional extraction methods. Nitrogen compounds of quinoline and isoquinoline were more easily and efficiently recovered by higher pressure supercritical CO^2 and methanol washing.4) Benzothiophene (BT) was more selectively dimerized over tha Al/Si catalyst under supercritical CO^2 conditions of 100ﾟC and 70 atm than its catalytic reaction in atmospheric n-octane solutions. The dimer of BT can be separated from crude naphthalene fraction under the supercritical CO^2 conditions followed by selective dedimerization and etraction.