单萜烯热重排反应过程研究
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摘要
本文对α-蒎烯、p-蒎烯、蒎烷热重排进行了系统深入的研究,探究了它们的热重排反应机理,总结了其热重排工艺,给出了这三种原料在不同反应条件下的热重排反应动力学数据。结合单萜烯热重排反应特点,设计了新型流化床反应器,对其内部流体流态进行了模拟,并进行工业放大设计,得到如下结论：
α-蒎烯热重排并行产物为柠檬烯和罗勒烯,选择性之比54：42(±1),产物罗勒烯迅速重排为别罗勒烯,反应控制步骤为α-蒎烯重排一步,别罗勒烯最高收率达47%；p-蒎烯热重排并行生成月桂烯、柠檬烯、假柠檬烯,月桂烯最高得率达到82.6%；蒎烷热重排主产物二氢月桂烯的最高得率达到67.5%。由于各主产物均可二次重排,为提高其选择性,必须降低原料转化率。
通过对空管、06mm钢珠固定床、03mm钢珠固定床、固定床加流化粒子等几种反应器构型对表观动力学参数的影响规律的研究,表明随着反应器比表面积的增加,表观活化能、表观速率因子、表观活化焓、表观活化熵都随之增大,最终接近其本征反应动力学数值。
在实验研究基础上,提出了新型流化床热重排反应器,小试实验证明,本文提出的新型反应器,在固定床基础上可降低反应温度近20℃,月桂烯最高产率相应提高1-2%,同时具有清除积炭的“自净”功能。
在已有的颗粒床流体力学研究基础上,提出了更详细的流道物理模型,并结合流态化理论,得到了反应器流体力学计算模型,并根据冷态流体力学实验对比,提出了流化粒子驻留率这一概念,并给出了新型反应器的压降关联式：结合反应器内大尺度多孔介质传热方程及本文得到的反应动力学方程,对反应器进行模拟计算,与实验结果一致。
提出了工业化规模反应产物急冷流程及大孔穿流塔板与散堆填料相结合的冷却塔器类型,可以有效降低产物高温下的副反应,解决了现生产所用冷凝换热器结焦(垢)、堵塞的问题；进行了规模为100kg/h的生产流程设计和设备工艺设计。绘制了带控制点的流程图、关键设备的计算说明书和工艺条件图。
The mechanisms of thermal rearrangements of monoterpenoids, namely a-pinene, β-pinene, and pinane are investigated respectively; the processes of thermal rearrangements of the three compounds are summarized and the kinetic data were worked out. A new kind of fluidized bed reactor was designed based on the thermal rearrangement theory, and the dynamical regime of fluid flow was studied. The results are as follows:
The parallel products of thermal rearrangement of a-pinene are limonene and ocimene of which selective ratio is54:42(±1), meanwhile the ocimene are rearranging to allo-ocimene rapidly of which control step is the rearrangement of a-pinene, the highest yield of allo-ocimene was47%. Myrcene, limonene and psi-limonene are the parallel products of β-pinene rearrangement and the highest yield of the myrcene is82.6%.The principal product of the pinane is dihydromyrcene of which highest yield is67.5%. As the possibility of the consecutive reaction of the principal products, the percent conversion must be degraded for promoting the selectivity.
The results of the apparent kinetic parameters by means of thermal rearrangements of above-mentioned monoterpenoids in the flow-type reactors respectively are hollow pipe,06mm steel balls fixed pipe,03mm steel balls fixed pipe and fluidized bed reactors show that by increasing of the area to volume ratio, the apparent active energy, apparent rate factor, apparent active enthalpy and apparent active entropy are all increased and close to their intrinsic reaction kinetics finally. Adding small fluidized particle can also promote the reaction yield.
The new kind of fluidized bed reactor for thermal rearrangement was designed. Preliminary experiments show the novel reactor has the advantages of1-2%higher yield than fixed bed reactor for myrcene, and decreased reaction temperature almost20℃, and has self-clean function.
On the basis of presented theory of particle bed fluidity mechanics, a more detailed flow physical model was proposed and a flow mechanics calculation model was obtained combined with the theory of fluidization in this study. The concept of fluidized particle resident rate was proposed following the cold experiment and brings up the pressing drop correlation in reactor. A simulated calculation of the reactor was completed combined with thermal conduction model for large scale porous media and the reaction kinetic equations.
The commercial-scale quenching process was presented for depressing the side reaction at high temperature combined macroporous draining plate with random packing type of cooling tower to resolve coking, scaling and blocking in condensing heat exchanger. Finally,100kg/h scale industrial process and equipments were designed and the piping&instrument diagram, the calculation specification for key equipment and process conditions were also included.
α-蒎烯热重排并行产物为柠檬烯和罗勒烯,选择性之比54：42(±1),产物罗勒烯迅速重排为别罗勒烯,反应控制步骤为α-蒎烯重排一步,别罗勒烯最高收率达47%；p-蒎烯热重排并行生成月桂烯、柠檬烯、假柠檬烯,月桂烯最高得率达到82.6%；蒎烷热重排主产物二氢月桂烯的最高得率达到67.5%。由于各主产物均可二次重排,为提高其选择性,必须降低原料转化率。
通过对空管、06mm钢珠固定床、03mm钢珠固定床、固定床加流化粒子等几种反应器构型对表观动力学参数的影响规律的研究,表明随着反应器比表面积的增加,表观活化能、表观速率因子、表观活化焓、表观活化熵都随之增大,最终接近其本征反应动力学数值。
在实验研究基础上,提出了新型流化床热重排反应器,小试实验证明,本文提出的新型反应器,在固定床基础上可降低反应温度近20℃,月桂烯最高产率相应提高1-2%,同时具有清除积炭的“自净”功能。
在已有的颗粒床流体力学研究基础上,提出了更详细的流道物理模型,并结合流态化理论,得到了反应器流体力学计算模型,并根据冷态流体力学实验对比,提出了流化粒子驻留率这一概念,并给出了新型反应器的压降关联式：结合反应器内大尺度多孔介质传热方程及本文得到的反应动力学方程,对反应器进行模拟计算,与实验结果一致。
提出了工业化规模反应产物急冷流程及大孔穿流塔板与散堆填料相结合的冷却塔器类型,可以有效降低产物高温下的副反应,解决了现生产所用冷凝换热器结焦(垢)、堵塞的问题；进行了规模为100kg/h的生产流程设计和设备工艺设计。绘制了带控制点的流程图、关键设备的计算说明书和工艺条件图。
The mechanisms of thermal rearrangements of monoterpenoids, namely a-pinene, β-pinene, and pinane are investigated respectively; the processes of thermal rearrangements of the three compounds are summarized and the kinetic data were worked out. A new kind of fluidized bed reactor was designed based on the thermal rearrangement theory, and the dynamical regime of fluid flow was studied. The results are as follows:
The parallel products of thermal rearrangement of a-pinene are limonene and ocimene of which selective ratio is54:42(±1), meanwhile the ocimene are rearranging to allo-ocimene rapidly of which control step is the rearrangement of a-pinene, the highest yield of allo-ocimene was47%. Myrcene, limonene and psi-limonene are the parallel products of β-pinene rearrangement and the highest yield of the myrcene is82.6%.The principal product of the pinane is dihydromyrcene of which highest yield is67.5%. As the possibility of the consecutive reaction of the principal products, the percent conversion must be degraded for promoting the selectivity.
The results of the apparent kinetic parameters by means of thermal rearrangements of above-mentioned monoterpenoids in the flow-type reactors respectively are hollow pipe,06mm steel balls fixed pipe,03mm steel balls fixed pipe and fluidized bed reactors show that by increasing of the area to volume ratio, the apparent active energy, apparent rate factor, apparent active enthalpy and apparent active entropy are all increased and close to their intrinsic reaction kinetics finally. Adding small fluidized particle can also promote the reaction yield.
The new kind of fluidized bed reactor for thermal rearrangement was designed. Preliminary experiments show the novel reactor has the advantages of1-2%higher yield than fixed bed reactor for myrcene, and decreased reaction temperature almost20℃, and has self-clean function.
On the basis of presented theory of particle bed fluidity mechanics, a more detailed flow physical model was proposed and a flow mechanics calculation model was obtained combined with the theory of fluidization in this study. The concept of fluidized particle resident rate was proposed following the cold experiment and brings up the pressing drop correlation in reactor. A simulated calculation of the reactor was completed combined with thermal conduction model for large scale porous media and the reaction kinetic equations.
The commercial-scale quenching process was presented for depressing the side reaction at high temperature combined macroporous draining plate with random packing type of cooling tower to resolve coking, scaling and blocking in condensing heat exchanger. Finally,100kg/h scale industrial process and equipments were designed and the piping&instrument diagram, the calculation specification for key equipment and process conditions were also included.
引文
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