在MFI型高硅沸石上用一乙醇胺选择性合成三乙烯二胺  

Selective synthesis of triethylenediamine from monoethanolamine over MFI-type silicious zeolite

作　　者：赵凌雁[1] 郭洪臣[1] 陈黎行[1] 王祥生[1] 曾高峰 

机构地区：[1]大连理工大学化工学院催化化学与工程系及精细化工国家重点实验室,辽宁大连116012

出　　处：《现代化工》2003年第z1期193-197,共5页Modern Chemical Industry

摘　　要：在常压和无载气条件下,使一乙醇胺(MEOA)与18％质量分数的NH_3及50％质量分数的H_2O共进料反应,用小型固定床反应器评价了一种MFI型高硅沸石催化剂 TEDA^(MAX)-01催化一乙醇胺合成三乙烯二胺(TEDA)的性能。研究表明当反应温度在 330～380℃内变化时,TEDA^(MAX)-01的活性和选择性随反应温度的提高而增加。当混合料液的质量空速(V_(WHS))在 1～4 h^(-1)区间内变化时,TEDA^(MAX)-01的活性和选择性保持不变。在 370℃和 V_(WHS)为 2 h^(-1)的条件下,TEDA^(MAX)-01催化剂能使一乙醇胺转化率接近99％,三乙烯二胺选择性达到97％以上。按此条件连续运转 266 h,一乙醇胺转化率保持不降,三乙烯二胺选择性在前100 h 缓慢下降,之后维持在 90％左右。对将分离母液循环作为进料氨源和水源的反应,以及催化剂经过反复 4次高温焙烧再生之后的反应进行了评价,该催化剂都表现出同样高的活性、选择性和稳定性。The performance of TEDA^(MAX)-01, a kind of catalyst with the topological structure of high silicious zeolite MFI, in catalyzing the reaction of monoethanoamine (MEOA) to triethylenediamine (TEDA) has been evaluated by a small fixed-bed reactor under the ambient pressure and carrier gas free conditions. In order to avoid forming morpholinium compounds as well as pipe-blocking by TEDA, MEOA was co-fed by 18% (wt) of ammonia and 50% (wt) of water. Results show that the activity and the selectivity of TEDA^(MAX)-01 increase notably at reaction temperature in the range of 330-380℃, meanwhile keep stable with weight-hourly-space-velocity (WHSV) of reactant mixture in the range of 1-4h^(-1). Under conditions of 370℃ and WHSV = 2h^(-1), TEDAMAX-01 can give aPProximately 99% conversion under MEOA and more than 97% selectivity to TEDA. During a period of 266 h of continuous operation under these conditions, the conversion of MEOA does not decrease, the selectivity of TEDA decreases slowly before 100 hrs but keeps around 90% thereafter. The recycling of separative mother liquor as the source of feeding ammonia and feeding water, and repetitious regeneration of coked catalyst by the high-temperature calcination for four times seem to have no obvious influence on the activity,selectivity and durability of TEDAMAX-01 catalyst. It is therefore rea- sonable to expect a promising foreground of commercialization for TEDA^(MAX)-01 catalyst.

关 键 词：三乙烯二胺 高硅沸石 一乙醇胺 选择性合成 

分 类 号：TQ203.2[化学工程—有机化工]