乙烯/乙烷络合分离吸附剂的制备及表征
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摘要
分离过程的高选择性、高分离能力及高传质速率是其追求的目标，对于难以用物理法分离或物理法分离能耗甚高的体系，则着眼于研究高分离能力的化学方法，这已成为改进传统分离技术的一个重要发展方向。
传统的低温精馏法分离乙烯／乙烷，能耗巨大。络合吸附分离是将π络合反应与吸附过程相结合的分离方法，用于乙烯／乙烷的分离具有潜在的节能优势，其关键是络合分离吸附剂的开发。本文在综述了络合吸附分离研究进展及工业应用现状的基础上，探讨络合吸附机理，制备高选择性、高分离能力的乙烯络合吸附剂，并研究新型络合分离吸附剂的吸附平衡及固定床动态吸附行为，为低能耗的乙烯／乙烷分离新过程的工业应用奠定基础。
CO与C_2H_4都能与某些过渡金属离子如Cu~+，Ag~+发生可逆络合反应，CO络合分离已经有许多工业应用实例，而乙烯络合分离的工业应用至今尚未见报道。本文从CO络合与乙烯络合分离的差别出发，采用量子化学计算工具，结合分子轨道理论，研究络合物分子的构型、络合物分子中各原子间的电荷分布和电子转移以及络合键能，比较CO、C_2H_4和C_3H_6分别与CuCl、AgCl的相互作用，揭示CO、C_2H_4和C_3H_6与CuCl、AgCl发生络合反应的实质，结果表明：CO、C_2H_4和C_3~-H_6均能与CuCl、AgCl发生络合反应，其络合能力大小为：CO＞C_2H_4＞C_3H_6；对同一配体，CuCl的络合能力大于AgCl。从空间结构看，CO与CuCl的络合物为直线结构，而乙烯与CuCl的络合物则为平面三元环结构。这些研究结果的取得不仅可以给出CO和C_2H_4络合能力差异的合理解释，也为新型乙烯络合分离吸附剂的制备提供了理论指导。
通过比较CO和C_2H_4络合吸附及其分离体系的不同特点，在络合吸附剂制备过程中，本文提出以表面氧化改性活性炭为载体的设想，并考察了活性炭氧化改性前后负载CuCl的微观特征，研究了CuCl在活性炭表面的单层分散，用现代固体表征方法如BET、XRD以及TEM进行了表征。探讨了活性炭负载CuCl吸附剂的制备工艺，得到新型络合分离吸附剂。与文献报道的乙烯络合吸附剂相比，本文制备的吸附剂具有较大的乙烯选择性、较低的吸附热和稳定的变压再生特性，因此具有更好的工业应用前景。
对所研制的络合吸附剂，测定了乙烯、乙烷纯组分及其二元混合气吸附平衡数据，依据络合吸附剂的吸附机理，建立了分别考虑物理吸附和化学吸附的吸附平衡模型，模型不仅可以很好地关联乙烯、乙烷纯组分在络合吸附剂上的吸附平衡数据，参数物理意义明确，而且可以实现从单组分模型参数预测二元
南京工业大学博士学位论文 摘要
混合组分在络合吸附剂上的吸附平衡，为络合吸附剂工业应用提供了必要的基
础数据和设计依据。
研究了乙烯／乙烷及其二元混合体系在络合吸附剂上的吸附动态性能，比较
了浓度、温度、压力和流量对穿透曲线的影响，并实验测定了在惰性气吹扫的
条件下络合吸附剂的再生流出曲线，结果对乙烯乙烷混合气体循环吸附分离过
程的设计提供了重要的数据。在实验的基础上建立了孔扩散模型，模型不仅可
以比较好地拟合乙烯、乙烷在络会吸附剂上的吸附透过曲线，而且可以预测其
再生透过曲线，为络合吸附剂的工业应用提供了设计优化工具。
在上述研究工作基础上，本文从络合吸附剂的工业应用可行性角度，考察
了络合吸附剂对工业实际排放气的适应性，研究了络合吸附剂对N卜CH八CO。、
O。等气体的吸附选择性以及变温、变压循环吸附特性，并提出采用真空变压吸
附（VPSA）工艺回收环氧乙烷尾气中乙烯的方法。结果表明，由于本文研制的
络合吸附剂具有常温真空再生的稳定性和可行性，装置规模不大，操作方便，
运行成本低，经济效益显著。进一步表明本文开发的络合吸附剂具有良好业应
用前景。
Some separation processes based chemical action could bring higher selectivity, separation efficiency and transfer rate. Because of these characteristics, this method was becoming the one of important ways to improve the traditional separation techniques with high energy consumed.
The separation process of ethylene and ethane by traditional rectification at low temperature consumed a great deal of energy. Adsorption separation via complexation was a method which combined both -complexation reaction and the process of adsorption. This method could be used on the process of ethylene and ethane's separation because of the potential superiority of economizes on energy, and this would focus on development of complexation adsorbent. In this paper, current situation of adsorption separation via complexation in industry application and complexation adsorbent research were summarized. At the same time, adsorption mechanism and preparation of new adsorbents with high adsorption selectivity of ethylene were studied respectively, so did both adsorption equilibrium of the prepared sorbent and behavior of adsorption on fixed bed. All of these studies established a solid foundation of application in industry scale that the new process of ethylene and ethane's separation had lower economizes on energ
y.
Both carbon monoxide and ethylene could form complexation with some transition metal cations such as Cu+ and Ag+. Separation via complexation of CO had already been used in industry scale, but there had no report about that of ethylene as yet. On the basis of the differences between carbon monoxide and ethylene in their adsorption behaviors, the molecular configurations of the complex compounds were studied by using calculation tool of quantum chemistry combined with the theory of molecular orbit. In addition, carbon monoxide, ethylene and propylene could react with copper chloride and silver chloride respectively, and from study of these reactions, it could be concluded that the order of complexation abilities was: CO>C2H4>C3H6, and to the same ligand, CuCl > AgCl. Moreover, the structure of the complex of CO and CuCl was linear, and that of alkenes and AgCl was planar three-member ring. These results could offer theoretical guidance to preparation of complexation adsorbent.
Through comparing the different characteristics of adsorption via complexation and the separation systems of carbon monoxide and ethylene, it had been put forward that surface qualities of active carbon carrier could be modified by oxidation during the course of preparation. At the same time the microcosmic characteristics of active carbon modified by load of CuCl had also been studied. Besides of that, monolayer
dissipation of CuCl on the surface of active carbon was characterized by BET, XRD and TEM. Preparation techniques of CuCl-loaded active carbon adsorbent were also discussed and new complexation adsorbent for ethylene/ethane separation was obtained. Compared to the ethylene complexation adsorbent, which reported on other documents, CuCl-loaded active carbon adsorbent had higher ethylene selectivity, smaller adsorption heat and more stable regenesis of pressure swing. Therefore, it had better industry application foreground.
Adsorption equilibrium data of ethylene, ethane and their mixture had been determined after the preparation of complexation adsorbent. An adsorption equilibrium model with physical adsorption and chemical adsorption was established respectively, which according the mechanism of complexation adsorption. Physical meanings of the model parameters were authentic. The adsorption equilibrium of binary mixture on complexation adsorbent could be predicted from the mono component pattern. Thus, necessary data of industry application and design-foundation of the complex adsorbent had been obtained.
The adsorption dynamic performance of ethylene, ethane and their binary mixture on complexation adsorbent had been studied. The effects of concentration, temperature, pressure and flow rate on breakthrough curve were compared. T
传统的低温精馏法分离乙烯／乙烷，能耗巨大。络合吸附分离是将π络合反应与吸附过程相结合的分离方法，用于乙烯／乙烷的分离具有潜在的节能优势，其关键是络合分离吸附剂的开发。本文在综述了络合吸附分离研究进展及工业应用现状的基础上，探讨络合吸附机理，制备高选择性、高分离能力的乙烯络合吸附剂，并研究新型络合分离吸附剂的吸附平衡及固定床动态吸附行为，为低能耗的乙烯／乙烷分离新过程的工业应用奠定基础。
CO与C_2H_4都能与某些过渡金属离子如Cu~+，Ag~+发生可逆络合反应，CO络合分离已经有许多工业应用实例，而乙烯络合分离的工业应用至今尚未见报道。本文从CO络合与乙烯络合分离的差别出发，采用量子化学计算工具，结合分子轨道理论，研究络合物分子的构型、络合物分子中各原子间的电荷分布和电子转移以及络合键能，比较CO、C_2H_4和C_3H_6分别与CuCl、AgCl的相互作用，揭示CO、C_2H_4和C_3H_6与CuCl、AgCl发生络合反应的实质，结果表明：CO、C_2H_4和C_3~-H_6均能与CuCl、AgCl发生络合反应，其络合能力大小为：CO＞C_2H_4＞C_3H_6；对同一配体，CuCl的络合能力大于AgCl。从空间结构看，CO与CuCl的络合物为直线结构，而乙烯与CuCl的络合物则为平面三元环结构。这些研究结果的取得不仅可以给出CO和C_2H_4络合能力差异的合理解释，也为新型乙烯络合分离吸附剂的制备提供了理论指导。
通过比较CO和C_2H_4络合吸附及其分离体系的不同特点，在络合吸附剂制备过程中，本文提出以表面氧化改性活性炭为载体的设想，并考察了活性炭氧化改性前后负载CuCl的微观特征，研究了CuCl在活性炭表面的单层分散，用现代固体表征方法如BET、XRD以及TEM进行了表征。探讨了活性炭负载CuCl吸附剂的制备工艺，得到新型络合分离吸附剂。与文献报道的乙烯络合吸附剂相比，本文制备的吸附剂具有较大的乙烯选择性、较低的吸附热和稳定的变压再生特性，因此具有更好的工业应用前景。
对所研制的络合吸附剂，测定了乙烯、乙烷纯组分及其二元混合气吸附平衡数据，依据络合吸附剂的吸附机理，建立了分别考虑物理吸附和化学吸附的吸附平衡模型，模型不仅可以很好地关联乙烯、乙烷纯组分在络合吸附剂上的吸附平衡数据，参数物理意义明确，而且可以实现从单组分模型参数预测二元
南京工业大学博士学位论文 摘要
混合组分在络合吸附剂上的吸附平衡，为络合吸附剂工业应用提供了必要的基
础数据和设计依据。
研究了乙烯／乙烷及其二元混合体系在络合吸附剂上的吸附动态性能，比较
了浓度、温度、压力和流量对穿透曲线的影响，并实验测定了在惰性气吹扫的
条件下络合吸附剂的再生流出曲线，结果对乙烯乙烷混合气体循环吸附分离过
程的设计提供了重要的数据。在实验的基础上建立了孔扩散模型，模型不仅可
以比较好地拟合乙烯、乙烷在络会吸附剂上的吸附透过曲线，而且可以预测其
再生透过曲线，为络合吸附剂的工业应用提供了设计优化工具。
在上述研究工作基础上，本文从络合吸附剂的工业应用可行性角度，考察
了络合吸附剂对工业实际排放气的适应性，研究了络合吸附剂对N卜CH八CO。、
O。等气体的吸附选择性以及变温、变压循环吸附特性，并提出采用真空变压吸
附（VPSA）工艺回收环氧乙烷尾气中乙烯的方法。结果表明，由于本文研制的
络合吸附剂具有常温真空再生的稳定性和可行性，装置规模不大，操作方便，
运行成本低，经济效益显著。进一步表明本文开发的络合吸附剂具有良好业应
用前景。
Some separation processes based chemical action could bring higher selectivity, separation efficiency and transfer rate. Because of these characteristics, this method was becoming the one of important ways to improve the traditional separation techniques with high energy consumed.
The separation process of ethylene and ethane by traditional rectification at low temperature consumed a great deal of energy. Adsorption separation via complexation was a method which combined both -complexation reaction and the process of adsorption. This method could be used on the process of ethylene and ethane's separation because of the potential superiority of economizes on energy, and this would focus on development of complexation adsorbent. In this paper, current situation of adsorption separation via complexation in industry application and complexation adsorbent research were summarized. At the same time, adsorption mechanism and preparation of new adsorbents with high adsorption selectivity of ethylene were studied respectively, so did both adsorption equilibrium of the prepared sorbent and behavior of adsorption on fixed bed. All of these studies established a solid foundation of application in industry scale that the new process of ethylene and ethane's separation had lower economizes on energ
y.
Both carbon monoxide and ethylene could form complexation with some transition metal cations such as Cu+ and Ag+. Separation via complexation of CO had already been used in industry scale, but there had no report about that of ethylene as yet. On the basis of the differences between carbon monoxide and ethylene in their adsorption behaviors, the molecular configurations of the complex compounds were studied by using calculation tool of quantum chemistry combined with the theory of molecular orbit. In addition, carbon monoxide, ethylene and propylene could react with copper chloride and silver chloride respectively, and from study of these reactions, it could be concluded that the order of complexation abilities was: CO>C2H4>C3H6, and to the same ligand, CuCl > AgCl. Moreover, the structure of the complex of CO and CuCl was linear, and that of alkenes and AgCl was planar three-member ring. These results could offer theoretical guidance to preparation of complexation adsorbent.
Through comparing the different characteristics of adsorption via complexation and the separation systems of carbon monoxide and ethylene, it had been put forward that surface qualities of active carbon carrier could be modified by oxidation during the course of preparation. At the same time the microcosmic characteristics of active carbon modified by load of CuCl had also been studied. Besides of that, monolayer
dissipation of CuCl on the surface of active carbon was characterized by BET, XRD and TEM. Preparation techniques of CuCl-loaded active carbon adsorbent were also discussed and new complexation adsorbent for ethylene/ethane separation was obtained. Compared to the ethylene complexation adsorbent, which reported on other documents, CuCl-loaded active carbon adsorbent had higher ethylene selectivity, smaller adsorption heat and more stable regenesis of pressure swing. Therefore, it had better industry application foreground.
Adsorption equilibrium data of ethylene, ethane and their mixture had been determined after the preparation of complexation adsorbent. An adsorption equilibrium model with physical adsorption and chemical adsorption was established respectively, which according the mechanism of complexation adsorption. Physical meanings of the model parameters were authentic. The adsorption equilibrium of binary mixture on complexation adsorbent could be predicted from the mono component pattern. Thus, necessary data of industry application and design-foundation of the complex adsorbent had been obtained.
The adsorption dynamic performance of ethylene, ethane and their binary mixture on complexation adsorbent had been studied. The effects of concentration, temperature, pressure and flow rate on breakthrough curve were compared. T
引文
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