石油学报（石油加工）
石油學報（石油加工）
석유학보（석유가공）
ACTA PETROLEI SINICA(PETROLEUM PROCESSING SECTION)
2010年
1期
46-51
,共6页
喻惠利%罗文国%俞芳%温朗友
喻惠利%囉文國%俞芳%溫朗友
유혜리%라문국%유방%온랑우
异辛烯%加氢%异辛烷%Ziegler-Natta催化剂%反应动力学
異辛烯%加氫%異辛烷%Ziegler-Natta催化劑%反應動力學
이신희%가경%이신완%Ziegler-Natta최화제%반응동역학
isooctene%hydrogenation%isooctane%Ziegler-Natta catalyst%reaction kinetics
采用Ziegler-Natta型镍基均相加氢催化剂和半连续操作的管式反应器,研究了异辛烯(2,4,4-三甲基戊烯-1(TMP-1)和2,4,4-三甲基戊烯-2(TMP-2))液相加氢制异辛烷的反应动力学.结果表明,反应开始阶段,因存在反应诱导期和TMP-1与TMP-2的异构化反应,致使加氢反应动力学十分复杂而难于用简单的数学方程式来描述;在反应诱导期结束后,异辛烯加氢反应可以采用幂函数型动力学模型描述.通过对动力学数据的线性回归,得到TMP-1加氢反应的级次对烯烃为1级、对氢分压为1.5级,反应活化能为25.6 kJ/mol;TMP-2加氢反应的级次对烯烃为1.2级、对氢分压为1.6级,反应活化能为46.5 kJ/mol.经检验,TMP-1、TMP-2加氢反应模型的计算值与实验结果的平均偏差分别为6.5%、7.6%,具有较高的可信度,可用于反应过程模拟和反应器设计.
採用Ziegler-Natta型鎳基均相加氫催化劑和半連續操作的管式反應器,研究瞭異辛烯(2,4,4-三甲基戊烯-1(TMP-1)和2,4,4-三甲基戊烯-2(TMP-2))液相加氫製異辛烷的反應動力學.結果錶明,反應開始階段,因存在反應誘導期和TMP-1與TMP-2的異構化反應,緻使加氫反應動力學十分複雜而難于用簡單的數學方程式來描述;在反應誘導期結束後,異辛烯加氫反應可以採用冪函數型動力學模型描述.通過對動力學數據的線性迴歸,得到TMP-1加氫反應的級次對烯烴為1級、對氫分壓為1.5級,反應活化能為25.6 kJ/mol;TMP-2加氫反應的級次對烯烴為1.2級、對氫分壓為1.6級,反應活化能為46.5 kJ/mol.經檢驗,TMP-1、TMP-2加氫反應模型的計算值與實驗結果的平均偏差分彆為6.5%、7.6%,具有較高的可信度,可用于反應過程模擬和反應器設計.
채용Ziegler-Natta형얼기균상가경최화제화반련속조작적관식반응기,연구료이신희(2,4,4-삼갑기무희-1(TMP-1)화2,4,4-삼갑기무희-2(TMP-2))액상가경제이신완적반응동역학.결과표명,반응개시계단,인존재반응유도기화TMP-1여TMP-2적이구화반응,치사가경반응동역학십분복잡이난우용간단적수학방정식래묘술;재반응유도기결속후,이신희가경반응가이채용멱함수형동역학모형묘술.통과대동역학수거적선성회귀,득도TMP-1가경반응적급차대희경위1급、대경분압위1.5급,반응활화능위25.6 kJ/mol;TMP-2가경반응적급차대희경위1.2급、대경분압위1.6급,반응활화능위46.5 kJ/mol.경검험,TMP-1、TMP-2가경반응모형적계산치여실험결과적평균편차분별위6.5%、7.6%,구유교고적가신도,가용우반응과정모의화반응기설계.
The kinetics for liquid-phase hydrogenation of isooctenes (2, 4, 4-trimethylpentene-1(TMP-1) and 2,4,4-trimethylpentene-2 (TMP-2)) to isooctane were studied with Ziegler-Natta type Ni-based homogeneous complex as catalyst in a semi-batch reactor. Experimental results revealed that the hydrogenation reaction was too complicated to describe with simple mathematics equations due to the formation of "reaction induce period" and the isomerization between TMP-1 and TMP-2 at the beginning of the reaction. After the " reaction induce period", the empirical power-law model could be used to describe the kinetics o{ the hydrogenation reaction. The model parameters were estimated by linear regression of the kinetic experimental data,from which it was known that TMP-1 hydrogenation was first order reaction to TMP-1 and 1.5 order reaction to hydrogen partial pressure, the apparent activation energy was 25.6 kJ/mol; while TMP-2 hydrogenation was 1.2 order reaction to TMP-2 and 1.6 order reaction to hydrogen partial pressure, the apparent activation energy was 46.5 kJ/mol. The analysis of verification of variance and the average deviation showed that the kinetic equations were acceptable with a high credibility, therefore, could be used in process simulation and reactor design.
