Liu Hongjie, Su Yunrui, Liu Cheng, Zhou Andi, Chu Xiaomeng, Liu Shaojie, Xing Xuteng, Tang Erjun
College of Chemical & Pharmaceutical Engineering, Hebei University of Science & Technology, Shijiazhuang 050018, P. R. China.
ACS Omega. 2021 Feb 15;6(8):5451-5462. doi: 10.1021/acsomega.0c05637. eCollection 2021 Mar 2.
Decolorization plays an important part in the industrial production of acetaminophen (APAP) drugs. The impurities generated from the APAP pharmaceutical industry decolorization refining process were primarily separated and purified, and their structures were determined by MS and H NMR technology. Then the catalytic effects of three samples of modified powdered activated carbon (PAC) on APAP in heterogeneous solution systems and the adsorption catalysis system were systematically investigated, which indicated that PAC catalyzed the APAP oxidative coupling side reaction and thus increased the impurities in the APAP product. The M-T-RAC (thermal regeneration PAC modified by ammonium sulfate) possessing more acidic surface groups can effectively inhibit this side reaction. Furthermore, according to the different catalytic results of O-T-RAC (thermal regeneration PAC modified by hydrogen peroxide) in solid-liquid catalytic and adsorption catalytic systems, we speculated that the multimer impurities were generated by the oxidative coupling reaction of APAP being oxidized to rated -acetyl--benzoquinone (NAPQI) during decolorization, while free radical polymerization of APAP mainly occurred in the pores of the spent PAC. The pore textural structure and chemical properties of M-T-RAC were further characterized to ensure its feasibility of industrial application. The process of simulating industrial decolorization substantiated the excellent ability of M-T-RAC to inhibit side reactions. This study contributes to the development of green materials for sustainable recycling of activated carbon to reduce pollution and costs, and provides an effective advice for the pharmaceutical process.
脱色在对乙酰氨基酚(APAP)药物的工业生产中起着重要作用。对APAP制药工业脱色精制过程中产生的杂质进行了初步分离和纯化,并通过质谱(MS)和核磁共振氢谱(H NMR)技术确定了其结构。然后系统研究了三种改性粉末活性炭(PAC)样品在非均相溶液体系和吸附催化体系中对APAP的催化作用,结果表明PAC催化了APAP的氧化偶合副反应,从而增加了APAP产品中的杂质。具有更多酸性表面基团的硫酸铵热再生PAC(M-T-RAC)能有效抑制该副反应。此外,根据过氧化氢热再生PAC(O-T-RAC)在固液催化和吸附催化体系中的不同催化结果,推测多聚体杂质是在脱色过程中APAP被氧化为对乙酰亚胺醌(NAPQI)后发生氧化偶合反应生成的,而APAP的自由基聚合主要发生在废PAC的孔隙中。进一步对M-T-RAC的孔结构和化学性质进行了表征,以确保其工业应用的可行性。模拟工业脱色过程证实了M-T-RAC抑制副反应的优异能力。本研究有助于开发用于活性炭可持续循环利用的绿色材料,以减少污染和成本,并为制药工艺提供了有效的建议。