CN116199567A - 一种苯酚羟基化制备苯二酚产生的焦油的绿色处理方法 - Google Patents
一种苯酚羟基化制备苯二酚产生的焦油的绿色处理方法 Download PDFInfo
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- C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
- C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
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- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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Abstract
本发明涉及一种苯二酚焦油的处理方法,提供一种含酚类焦油的回收、再利用的方法。将酚类焦油经臭氧氧化、裂解后,然后再加氢可得到另一种高附加值的苯三酚,及解决了酚类焦油的难处理问题,又实现了高附加值利用,变废为宝。本发明利用臭氧的Criegee臭氧化反应,引入新的苯并噻唑配体催化剂,具有反应条件温和,副产物无污染等优点,是一条绿色的工艺路线。
Description
技术领域
本发明涉及一种焦油再利用的方法,尤其适用于苯酚羟基化反应制备苯二酚的酚类的焦油。
背景技术
邻苯二酚和对苯二酚是重要的精细化工产品,其中邻苯二酚又称儿茶酚,是制备洋茉莉醛、香兰素等香料的中间体,对苯二酚为高效阻聚剂,常用于合成橡胶防老剂和医药的原料。苯酚和双氧水在催化剂的作用下发生羟基化反应,是一条绿色、高效的制备苯二酚的生产工艺。具有工艺流程简单,反应条件温和、氧化副反应无污染等突出优点,符合绿色化工的目的,近些年来得到较大的发展。
目前国内外以苯酚、双氧水为原料生产苯二酚主要有以下四种路线:Rhone-Poulenc法、UBE法、Brichima法和Enichem法。由于二元酚为热敏感物质,容易与过氧化物继续反应,因此无论哪种工艺都不可避免发生氧化缩合反应,生成缩聚焦油,焦油生成量与催化体系、反应工艺条件甚至产物的分离过程有关。值得注意的是,反应体系的溶剂也会对焦油的组成产生较大的影响。常规的苯酚羟基化工艺多采用水和丙酮等极性溶剂作为反应溶剂,生成的焦油大部分为两分子的酚类的醚类耦联化合物,如2,2’—二羟基二苯醚等。
由于含酚焦油中含有大量有毒的挥发性物质,直接在空气中焚烧处理会导致严重的空气污染,因此难以用做燃料进行热量回收。
关于含酚焦油的处理,专利CN101565182A通过将含酚焦油加入到碳化炉中,一边升温一边进行气体吹扫,可以将含酚焦油转化成活性炭。但此工艺能耗较高,焦油虽然能够生成活性炭进行再次利用,但活性炭经济价值不高,得不偿失。专利CN108569753A采用聚合反应的技术,将羟基化反应液萃取后的水相与分散剂配成溶液,在催化剂的作用下,水相中的焦油进一步聚合形成微球沉淀,经过滤脱除,实现了焦油的无害化处理,但因参与聚合反应的化合物较少,无法将体系内含酚焦油脱除干净。
然而,当苯酚羟基化反应不采用极性溶剂,而是采用正己烷作为反应溶剂时,产生的焦油和极性溶剂的焦油组成差别较大,生成的焦油多为两分子的双键类耦联化合物。经过对焦油进行精馏分离,确定焦油的组成,其中结构式为C12H12O4占比约80%,2,2’-二羟基二苯醚和4,4’-二羟基二苯醚共占比约20%。经过质谱分析,结构式C12H12O4推测结构为二酚类物质的缩合产物,如下所示:
目前,未见到关于上述焦油的研究及处理方式的报道。
发明内容
为了更好的实现双键类耦联化合物二酚焦油的有效利用,本发明提供一种酚焦油的再利用的方法:在臭氧的作用下,将焦油裂解,再加氢可得到另一种高附加值的产物苯三酚,实现了焦油的高附加值利用,变废为宝。合成方程式如下:
式中羟基位于苯环上1-6位,可以生成联苯三酚、间苯三酚或偏苯三酚。
为了实现上述技术目的,本发明采用的技术路线如下;
(1)将焦油用溶剂溶解后加入少量催化剂A,缓慢通入臭氧发生裂解氧化反应;
(2)将步骤1)得到的产物在催化剂B作用下发生加氢反应,得到苯三酚。
本发明所述步骤(1)中采用的催化剂A为锰配体催化剂,合成方法例如硫酸锰和苯并噻唑在一定温度,例如100℃下反应一段时间,例如3h即可得到该催化剂A,催化剂A结构式如下所示:
本发明所述步骤(1)中催化剂A和焦油的质量之比为1:(100-500),优选质量比为1:(200-300)。
本发明所述步骤(1)中选用的溶剂为丙酮、DMF、DMAC、四氢呋喃中的至少一种,优选为DMF。
本发明所述步骤(1)中,焦油与溶剂的重量比为1:(5~15),优选1:(8~12)。
本发明所述步骤(1)中,反应温度为-5~10℃,优选反应温度为0~5℃。
本发明所述步骤(1)中,反应压力为常压。
本发明所述步骤(1)中,臭氧的流量为10-100ml/min,优选流量为40-80ml/min。臭氧来源为臭氧发生器,型号例如为国林CF-G。臭氧是以气体鼓泡形式参与反应的。
本发明所述步骤(1)中,反应时间为20-80min,优选为40-60min。
本发明所述步骤(1)反应完毕无需提纯,直接进行加氢反应。
本发明所述步骤(2)中,加氢选用的催化剂B为雷尼镍、钯碳等,钯碳催化剂中Pd的含量可以是10%-30%。
本发明所述步骤(2)中,焦油与催化剂B质量比为(100-500):1,优选质量比为(200-300):1。
本发明所述步骤(2)中,反应温度为60-200℃,优选温度为100-150℃。
本发明所述步骤(2)中,反应压力为0.1-5MPa,优选压力为1-3MPa。
本发明所述步骤(2)中,反应时间为20-80min,优选反应时间为40-60min。
本发明具有如下有益效果:
采用本发明方法,酚类缩聚物焦油经臭氧氧化裂解、加氢反应得到苯三酚及其衍生物(羟基处于不同位置的苯三酚),实现了酚类焦油转化再利用,既解决了酚类焦油难处理的问题,同时也能得到高附加值的苯三酚衍生物,实现了废物再利用。本发明利用臭氧的Criegee臭氧化反应,并引入新的催化体系,将大分子量、难处理的物质裂解成小分子化合物,反应条件温和,副产物无污染,是一条绿色的合成路线,为以后含有多酚类重组分焦油的处理提供一定的借鉴意义。
具体实施方式
下面的实施例将对本发明所提供的方法予以进一步的说明,但本发明不限于所列出的实施例,还应包括在本发明所要求的权利范围内其它任何公知的改变。
锰配体催化剂A的制备:
将10g硫酸锰和40g苯并噻唑溶解于200gDMF中,升温至100℃,反应3h,分离提纯可得到苯并噻唑的锰配体催化剂。对催化剂进行元素分析,C含量56.08%、H含量4.03%、Mn含量9.16%、N含量9.34%、S含量21.39%。
实施例1
取100g二酚反应的焦油用500g丙酮溶解后,和0.5g锰配体催化剂一起加入到鼓泡塔反应器中,在-5℃条件下,以40ml/min速度向反应器中通入臭氧,反应时间为60min。将臭氧氧化后的反应液无需提纯,和1g雷尼镍一起加入到加氢反应釜中,通入氢气至压力为1MPa,升温至60℃,在此条件下反应80min,经分离提纯后得到苯三酚及其衍生物,整体收率为82.56%。
实施例2
取100g二酚反应的焦油用1000g四氢呋喃溶解后,和0.25g锰配体催化剂一起加入到鼓泡塔反应器中,在0℃条件下,以70ml/min速度向反应器中通入臭氧,反应时间为30min。将臭氧氧化后的反应液无需提纯,和0.3g雷尼镍一起加入到加氢反应釜中,通入氢气至压力为4.5MPa,升温至150℃,在此条件下反应30min,经分离提纯后得到苯三酚及其衍生物,整体收率为85.78%。
实施例3
取100g二酚反应的焦油用800gDMF溶解后,和1g锰配体催化剂一起加入到鼓泡塔反应器中,在3℃条件下,以50ml/min速度向反应器中通入臭氧,反应时间为50min。将臭氧氧化后的反应液无需提纯,和0.6g钯碳催化剂(20%Pd含量)一起加入到加氢反应釜中,通入氢气至压力为2MPa,升温至75℃,在此条件下反应25min,经分离提纯后得到苯三酚及其衍生物,整体收率为81.89%。
Claims (9)
1.一种苯二酚焦油的处理方法,包括:
(1)将焦油用溶剂溶解后加入少量催化剂A,缓慢通入臭氧发生裂解氧化反应;
(2)将步骤(1)得到的产物在催化剂B作用下发生加氢反应,得到苯三酚。
2.根据权利要求1所述的方法,其特征在于,步骤(1)溶剂为丙酮、DMF、DMAC、四氢呋喃中的至少一种,焦油与溶剂的重量比优选为1:(5~15)。
4.根据权利要求1或3所述的方法,其特征在于,催化剂A和焦油的质量之比为1:(100-500)。
5.根据权利要求1-4任一项所述的方法,其特征在于,步骤(1)中,臭氧的流量为10-100ml/min。
6.根据权利要求1-5任一项所述的方法,其特征在于,步骤(1)中,反应温度为-5~10℃,反应时间为20-80min。
7.根据权利要求1-6任一项所述的方法,其特征在于,步骤(2)中,催化剂B选自雷尼镍、钯碳。
8.根据权利要求1-7任一项所述的方法,其特征在于,步骤(2)中,焦油与催化剂B质量比为(100-500):1。
9.根据权利要求1-8任一项所述的方法,其特征在于,步骤(2)中,反应温度为60-200℃,反应压力为0.1-5MPa,反应时间为20-80min。
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