跨临界CO2强化石油树脂催化加氢-脱硫耦合反应机理及其热力学安全特性

Based on the self-invented technology, which modified petroleum resin was prepared by catalytic hydrogenation coupled with desulfurization in a transcritical CO2 system, the mechanism and thermodynamics safety characteristics of transcritical reaction process will be conducted. The by-product, H2S formed by the hydrogenation-desulfurization will be constantly taken out of the hydrogenation reactor by transcritical CO2 expansion to eliminate the feedback inhibition caused by the products accumulation, and the mechanism of catalytic hydrogenation coupled with desulfurization of petroleum resin will be discussed. The fluid mechanics and the transfer process will be studied using the on-line detecting system formed by laser holographic interferometry monitoring combined with particle imaging velocimetry based on non-invasive method, then the transfer mechanism of hydrogenation coupled with desulfurization in transcritical CO2 will also be discussed. The super cavitation behavior will be investigated by ventilated cavitation experiment and visual-high pressure reactor method, and the formation of supercavity and the drag reduction mechanism will also be investigated. Using bentonite with sulfur resistance as carrier, the Ni eggshell catalyst of high holding sulfur capacity will be prepared, then the structure-property relationship of catalyst performance can be explored further. Joule-Thomson (J-T) throttling coefficient model of mixed gas with CO2 and H2 under the hydrogenation of petroleum resin will be established based on the EOS and mixing rule, and the throttling thermal effect of reaction process will also be quantitatively described. Finally, the assessment method (by DOW Chemical Co.) of fire and explosion risk indexes, and hazard and operability analysis (HAZOP) will be used to evaluate the safety of the hydrogenation process. These will provide a theoretical foundation for preparing effectively hydrogenated petroleum resin by transcritical CO2 in the reaction of hydrogenation coupled with desulfurization and process safety.

以自主发明的"跨临界CO2反应系统催化加氢-脱硫耦合制备改性石油树脂"技术为来源开展跨临界反应机理及其热力学安全特性研究。采用跨临界膨胀方法使加氢-脱硫生成的H2S不断移出反应器，消除产物积累引起的反馈抑制作用，探讨石油树脂加氢-脱硫的耦合机制；采用激光全息干涉-粒子成像测速非侵入式技术在线跟踪研究流体力学与传递过程，探讨CO2跨临界强化加氢-脱硫反应过程的传递机理；采用高压可视-通气空化实验装置研究反应器内的超空泡行为，探讨超空泡的形成与减阻机制；以膨润土为载体负载Ni制备高容硫加氢蛋壳型催化剂，表征催化性能的构-效关系；采用EOS+混合规则建立石油树脂加氢反应条件下CO2与H2混合气体的J-T节流系数模型，定量描述反应过程的节流热效应；采用DOW火灾爆炸危险指数法结合HAZOP分析法对加氢过程进行安全性评价，为跨临界CO2强化加氢-脱硫制备氢化石油树脂的反应与安全过程夯实理论基础。

石油树脂是以乙烯工业副产物为原料制备的最大宗合成类增粘树脂，氢化石油树脂是其最重要的改性产品。针对大分子石油树脂催化加氢体系由于传质困难而导致需要苛刻反应条件的瓶颈问题，以及加氢过程缺乏安全性研究的现状，进行跨临界反应系统催化加氢-脱硫耦合制备改性石油树脂反应机理及其热力学安全特性研究。利用自主研发的的跨临界反应系统减小反应体系传递阻力、消除副产物积累而引起的反馈抑制作用打破化学平衡限制，建立“强化石油树脂聚合物内扩散传质”新策略，解决负载型加氢催化剂面临的大分子尺寸反应底物引起严重内扩散限制的难题，成功构筑MOFs衍生和碳纳米管负载型系列非贵金属高效加氢催化剂；结合材料的系统制备与表征技术，基于实验与数学模拟法深入研究催化加氢动力学与机理，采用DFT理论计算揭示强化石油树脂催化加氢性能的作用机制，在150℃的较温和条件下合成水白色氢化石油树脂，温度比已报道的Ni和Pd基催化剂分别低100℃和60℃。建立非侵入式图像法考察石油树脂溶液中的气泡行为，测定CO2的平衡溶解度和体积传质系数，提出新的预测传质阻力系数模型和气泡形状关联式，为打破石油树脂加氢反应系统制备过程的传递限制提供理论依据。定量确定H2及其H2-CO2体系的焦耳-汤姆逊节流热效应，预测节流转化曲线，提出“利用CO2的节流制冷效应提高加氢系统安全性”的策略，为石油树脂催化加氢过程节流致热效应可能导致的爆炸风险与安全措施建议提供重要的理论依据和基础数据。采用TG-FTIR/MS联用技术和DFT理论计算相结合系统研究石油树脂/氢化石油树脂热分解特性及其燃烧行为与机理，建立热分解与燃烧动力学模型，不仅为避免潜在的热危害提供基础数据，还为石油基树脂及其废物的能源应用提供理论依据。建立基于道化学指数法的石油树脂加氢单元安全评价方法，定性定量分析与评价石油树脂加氢过程爆炸危险性，确定加氢单元的初始火灾爆炸指数危险等级，并提出相应的安全补偿措施，为指导石油树脂加氢生产安全运行提供科学依据。