环己酮氨肟化工艺中HTS分子筛的不可逆失活与再生研究
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- 英文论文题名：Irreversible Deactivation and Regeneration of HTS zeolite from cyclohexanone ammoximation process
- 论文作者：夏长久 ; 彭欣欣 ; 林民 ; 朱斌 ; 舒兴田
- 英文论文作者：Changjiu Xia ; Xinxin Peng ; Min Lin ; Bin Zhu ; Xingtian Shu ; State Key Laboratory of Catalytic Materials and Reaction Engineering ; Research Institute of Petroleum Processing ; SINOPEC
- 年：2016
- 作者机构：石油化工催化材料与反应工程国家重点实验室中国石化石油化工科学研究院;
- 论文关键词：空心钛硅分子筛 ; 环己酮氨肟化 ; 不可逆失活 ; 再生
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第三十二分会： 多孔功能材料
- 语种：中文
- 分类号：O643.36
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第三十二分会 ; 多孔功能材料
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：217k
- 原文格式：D
- 会议级别：全国
摘要
空心钛硅分子筛(HTS)在绿色环己酮氨肟化工艺过程中发挥了重要作用,支撑了中国石化自主己内酰胺成套技术的开发。然而,受到碱性物质腐蚀和高温焙烧的影响,HTS会逐渐失去催化活性,这是由于骨架钛会随着骨架硅溶解而迁移出骨架位置。研究表明,失活剂晶粒外表面附着了大量的酸性无定型TiO_2-SiO_2颗粒,其会在氧化反应中加速双氧水分解,进而降低环己酮转化速率。为了抑制酸性物种的危害,本文采用"溶解-再结晶"手段将富钛颗粒包埋到了HTS分子筛晶体内部,有效隔断了双氧水与酸性副反应中心的接触,如图1所示。所以再生的HTS分子筛在氧化反应中具有与新鲜HTS相同的催化活性。
Cyclohexanone ammoximation catalyzed by hollow titanium Silicalite(HTS) is one of the core reactions for commercial manufacture of s-caprolactam at SINOPEC.However,HTS zeolite loses its catalytic activity under the impact of alkaline corrosion and calcination,owing to the dissolution of framework Si atoms and migration of framework Ti species.Acidic amorphous TiO_2-SiO_2 particles have been confirmed by multiple methods,which significantly accelerate the H_2O_2 decomposition during oxidation processes.Thus,the formation of amorphous Ti-rich particles is considered as the main reason of irreversible deactivation of HTS zeolite.Furthermore,to restrict the effect of acidic sites,these Ti-rich centers have been encapsulated inside zeolite via a "dissolution-recrystallization" post-synthesis treatment,for preventing the accessibility of H_2O_2 to amorphous Ti-rich sites.And the regenerated zeolite is as active as fresh one in catalytic oxidation reactions.
Cyclohexanone ammoximation catalyzed by hollow titanium Silicalite(HTS) is one of the core reactions for commercial manufacture of s-caprolactam at SINOPEC.However,HTS zeolite loses its catalytic activity under the impact of alkaline corrosion and calcination,owing to the dissolution of framework Si atoms and migration of framework Ti species.Acidic amorphous TiO_2-SiO_2 particles have been confirmed by multiple methods,which significantly accelerate the H_2O_2 decomposition during oxidation processes.Thus,the formation of amorphous Ti-rich particles is considered as the main reason of irreversible deactivation of HTS zeolite.Furthermore,to restrict the effect of acidic sites,these Ti-rich centers have been encapsulated inside zeolite via a "dissolution-recrystallization" post-synthesis treatment,for preventing the accessibility of H_2O_2 to amorphous Ti-rich sites.And the regenerated zeolite is as active as fresh one in catalytic oxidation reactions.
引文
[1]Xia,C.;Lin,M.;Zheng,A.,et al.J.Catal.2016,(in press).
[2]夏长久,郑爱国,朱斌,等.石油学报(石油加工),2014,30(4):595-601.
[2]夏长久,郑爱国,朱斌,等.石油学报(石油加工),2014,30(4):595-601.