Sterically hindered amine based absorbents and application for CO₂ capture in membrane contactors

Authors: Bougie, Francis
Advisor: Iliuta, Maria-Cornélia
Abstract: Gas separation in membrane contactors (MC) is a forefront technology offering several advantages over traditional packed columns, but very few efforts have been made to develop new absorbent solutions optimized specifically for application in MC. Currently, no available absorbent meets all required characteristics for the implementation of membrane contactors for acid gas separation (CO2 in particular) in industrial units. The main objective of this work was to develop a dedicated sterically hindered alkanolamine (SHA) based absorbent with improved characteristics for application in MC (good absorption capacity and reaction kinetics, regeneration facility, resistance to degradation, compatibility with membranes and high surface tension) and to investigate its efficiency for CO2 capture in different membrane contactor configurations and operation conditions. Although low kinetics characterizes highly sterically hindered alkanolamines, their potential to reduce the energy consumption during the regeneration step brings us to focus on AHPD (2-amino-2-hydroxymethyl-1,3-propanediol). To improve the absorption rate, piperazine (Pz) was found to be a very effective activator; the addition of small amounts of Pz to aqueous AHPD solutions has significant effect on the enhancement of the CO2 absorption rate. The blend AHPD-Pz was also found to present very good absorption capacity. The investigation of the regeneration of loaded (CO2 containing) amine solutions revealed that highly hindered SHA based solutions (AHPD in particular) are much easier to regenerate compared to MEA, the benchmark amine industrially used in acid gas separations. Moreover, the addition of small amount of Pz into AHPD aqueous solution allowed to obtain almost the same cyclic capacity and regeneration efficiency as non-activated solutions, but for half of the absorption time. Besides the liquid absorbent properties, the performances of MC for CO2 separation strongly depend on the compatibility between absorbent and membrane. Based on wetting-related properties like liquid surface tension, contact angle, membrane breakthrough pressure and chemical stability, a new graphical surface tension estimation method for aqueous amine, alcohol or alkanolamine solutions was developed to select the best conditions to elude the unwanted membrane wetting phenomenon. AHPD-based solutions (like the AHPD + Pz solution) were found to have a strong potential for use in MC because of their very high surface tension. In addition, the developed method allowed to identify new potential amines for use in MC. A good stability and resistance to degradation is another important feature of CO2 absorbents. The investigation of the stability of different aqueous amine solutions to thermal and oxidative degradation, in the absence and the presence of CO2, revealed that SHA are more resistant to thermal degradation than conventional amines, but the presence of oxygen degraded them more significantly in the absence of CO2. However, the presence of CO2 is beneficial to SHA as the preferential bicarbonate formation in solutions reduces by a large extent the oxidative degradation rate. The low degradation degree of the AHPD + Pz aqueous solution reaffirms its potential as CO2 absorbent. Finally, the performance of the AHPD + Pz aqueous solution for CO2 capture in MC was investigated in different operational conditions and module configurations (hollow fibers and flat sheets membranes, PTFE, PP and laminated PTFE/PP membranes, various liquid flow rates, gas compositions and flow orientation (co- and counter-current)). Excellent performance was found for AHPD + Pz solutions. Based on experimental data, a modeling study of CO2 capture in PTFE hollow fiber MC revealed the positive effect of solutions presenting high surface tension on the reduction of membrane wetting. In summary, the results of this thesis showed that AHPD + Pz aqueous solution possess good absorption capacity, reaction kinetics, regenerative potential, and degradation resistance, as well as high surface tension and showed excellent performance for CO2 capture in MC, representing an interesting alternative to MEA.
Document Type: Thèse de doctorat
Issue Date: 2014
Open Access Date: 20 April 2018
Grantor: Université Laval
Collection:Thèses et mémoires

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