• Energy Research

Abstract Membrane contactors offer a promising alternative to conventional CO2 absorption processes using columns. In a membrane contactor the advantages of absorption technology and membrane technology are combined as direct contact of the solution and gas feed stream is avoided by membrane barrier. In this study, the possibility of employing the enzyme carbonic anhydrase (CA) for the acceleration of CO2 reaction in MDEA and MEA solution in combination with the use of a membrane contactor was investigated in a lab scale module. The membranes employed in this study were microporous and specifically chosen to have both hydrophobic (bulk) and hydrophilic (surface) properties in order to avoid wetting of solution and reduce fouling by the enzymes simultaneously. By adding the enzyme carbonic anhydrase (CA), a significant improvement of CO2 absorption rate was observed in MDEA solution while a negative effect was observed in MEA solution. Meanwhile the porous hydrophobic membranes were coated with a highly selective poly(ionic liquids) layer increasing the affinity of CO2 towards the interfacial area and hence also the driving force. The concept may initially appear counter intuitive, as the dense membrane layer introduces an added resistance, however the active membrane material gave promising results and was observed to accelerate CO2 transport in MDEA solution. The combination of both enzyme and PILs resulted in synergies, which significantly improved CO2 absorption in MDEA solution.

Due to the increasing world population and industrialization the worldwide energy requirement is also increasing. About 82% of the world's total primary energy supply stems from fossil sources and coal combustion in power plants accounted for 46% of the 32.4 Gt global carbon dioxide (CO2) emissions in 2014 (International Energy Agency, Key CO2 Emissions Trends: Excerpt from CO2 Emissions from Fuel Combustion (2016 edition)). The reduction of CO2 emissions from power plant flue gases is therefore essential to enable reliable and ecologically benign energy supply. An efficient technology to reduce CO2 emissions is reactive absorption in packed columns with aqueous amine-based absorption solvents, herein also called absorbents. The major drawback of conventional amine absorbents is their high absorption enthalpy, which causes high energy requirements during solvent regeneration. Alternative solvents that offer significantly lower absorption enthalpies suffer from lower absorption rates. To compensate for low absorption rates the enzyme carbonic anhydrase (CA) can be added to the absorbent to accelerate absorption kinetics by catalyzing the reaction between CO2 and water. For industrial applications, it can be desirable to immobilize CA which extends enzyme longevity by confining the enzyme to favorable process conditions, prevents unnecessary exposure to high process temperatures, and enables enzyme reuse. The CO2 absorption characteristics and handling properties of an innovative immobilized CA in the form of microparticles, called biocatalyst delivery system (BDS), were evaluated together with aqueous MDEA solvent. Operational feasibility parameters were validated in lab scale, followed by replicated CO2 absorption performance tests in a small demonstration scale counter-current packed column. A sixfold enhancement in total absorbed mole flow of CO2 in the presence of BDS was demonstrated versus blank MDEA solvent. Recyclability and longevity of BDS were validated.

Membrane contactors offer a promising alternative to conventional CO2 absorption processes using columns. In a membrane contactor the advantages of absorption technology and membrane technology are combined as direct contact of the solution and gas feed stream is avoided by membrane barrier. In this study, the possibility of employing the enzyme carbonic anhydrase (CA) for the acceleration of CO2 reaction in MDEA and MEA solution in combination with the use of a membrane contactor was investigated in a lab scale module. The membranes employed in this study were microporous and specifically chosen to have both hydrophobic (bulk) and hydrophilic (surface) properties in order to avoid wetting of solution and reduce fouling by the enzymes simultaneously. By adding the enzyme carbonic anhydrase (CA), a significant improvement of CO2 absorption rate was observed in MDEA solution while a negative effect was observed in MEA solution. Meanwhile the porous hydrophobic membranes were coated with a highly selective poly(ionic liquids) layer increasing the affinity of CO2 towards the interfacial area and hence also the driving force. The concept may initially appear counter intuitive, as the dense membrane layer introduces an added resistance, however the active membrane material gave promising results and was observed to accelerate CO2 transport in MDEA solution. The combination of both enzyme and PILs resulted in synergies, which significantly improved CO2 absorption in MDEA solution.

Abstract Within this work, the combination of an energetically favorable aqueous N-Methyldiethanolamine (MDEA) solution and the enzyme carbonic anhydrase is investigated in a packed column pilot plant. The use of aqueous MDEA solution for CO2 separation is already known from natural gas applications, for which an increased driving force due to the higher partial pressures of CO2 overcompensates reaction kinetic limitations. The objective of the addition of carbonic anhydrase is to countervail the loss of separation efficiency caused by the lower driving force in CO2 capture from power plant flue gases. Hence, carbonic anhydrase acts as a key to harness the energetic advantage of these solvent systems. However, application of the enzyme also poses restrictions on the process. Especially compliance with the enzyme stability limits is challenging for desorption, which is generally performed at high temperatures. In order to determine an optimal implementation of the enzyme into the process the current work presents different strategies how to apply CA as a biocatalyst in reactive absorption processes and shows how absorption efficiency is influenced. For introducing the enzyme to a packed column two approaches are investigated in this study. The simplest way of application is to dissolve the enzyme in the solvent. This allows the enzyme to work exactly where the reaction kinetic limitation can be found, in the liquid boundary layer. However, due to the temperature sensitivity of the enzyme an additional enzyme recovery step prior to the desorber might be necessary if desorption is to be performed at high temperatures. The immobilization of the enzyme inside the absorption column presents an alternative to prevent this additional separation, but may cause additional mass transfer limitations at the solid particles in which the enzyme is immobilized. The immobilization and the necessity of a suitable packing in which the enzyme particles can be filled, also makes this strategy more complicated but allows placing the enzyme at a location of most suitable process conditions in the column. But most importantly it completely avoids that the enzymes experience high temperature in the desorber. Systematic investigations of the influence of specific liquid load, liquid inlet temperature, MDEA-concentration and enzyme immobilization on absorption performance are conducted. Dissolved enzyme showed a nearly three times higher absorption performance than the immobilized enzyme under equivalent operating conditions, however the immobilized enzyme concentration used was effectively 50 times lower, meaning the result is actually quite promising for immobilized CA. From the investigated operating conditions, a liquid inlet temperature of 20 °C, a MDEA concentration of 30 wt.-% and a liquid flow rate of 24 m3 m-2 h-1 showed the best absorption performance with the dissolved enzyme. The measured absorption rate was 7.57 times higher than without enzyme added.

The separation of azeotropic mixtures is of particular importance for bio-based processes in the chemical industry. Extractive and heteroazeotropic distillation are oftentimes the favored solution for medium to large scale processes due to their proven robustness and the economics of scale. The feasibility as well as economic efficiency of these processes depends strongly on the selection of a suitable mass separating agent (MSA). Furthermore, energy integration can increase the energy and economic efficiency of these thermal processes. Since, MSA selection, process design and energy integration are usually performed as consecutive steps in process design, potential synergies are easily missed, resulting in sub-optimal choices. In order to determine an optimal process design, including solvent selection and energy integration, an efficient optimization-based approach for the design of extractive distillation processes is proposed. The application of the method is illustrated for the separation of the azeotropic mixture of acetone and methanol. The results highlight that the optimal MSA choice under consideration of energy integration differs from the selection without energy integration.

With growing interest in the biomass value chain, a multitude of reactions are proposed in literature for the conversion of biomass into a variety of biofuels. In the early design stage, data for a detailed design is scarce rendering an in‐depth analysis of all possibilities challenging. In this contribution, the screening methodology process network flux analysis (PNFA) is introduced assessing systematically the cost and energy performance of processing pathways. Based on the limited data available, a ranking of biorefinery pathways and a detection of bottlenecks is achieved by considering the reaction performance as well as the feasibility and energy demand of various separation strategies using thermodynamic sound shortcut models. PNFA is applied to a network of six gasoline biofuels from lignocellulosic biomass. While 2‐butanol is ruled out due to a lack in yield and selectivity, iso‐butanol and 2‐butanone are identified as economically promising fuels beyond ethanol. : Process Systems Engineering. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3096–3108, 2016

Solvent-based separation processes, such as extractive distillation, show large potential for the separation of azeotropic mixtures. However, these processes are rather complex to design and optimize since the overall process performance depends strongly on the choice and amount of solvent and can only be evaluated for a process flowsheet with closed recycles. It is important to note that the potential for heat integration also depends strongly on the solvent choice. Consequently, a successive selection of a suitable solvent followed by process design and optimization and finally energy integration likely results in suboptimal choices. In order to allow for direct optimization of an extractive distillation process, including solvent selection and different means for energy integration, the current study proposes the use of a hybrid evolutionary-deterministic algorithm. The application is demonstrated for the separation of an azeotropic acetone-methanol mixture, considering six solvent candidates and up to four alternative means for energy integration. The results illustrate the existence of a multitude of suboptimal local solutions and demonstrate the capability of the proposed method to effectively overcome these limitations.

The separation of azeotropic mixtures is of particular importance for bio-based processes in the chemical industry. Extractive and heteroazeotropic distillation are oftentimes the favored solution for medium to large scale processes due to their proven robustness and the economics of scale. The feasibility as well as economic efficiency of these processes depends strongly on the selection of a suitable mass separating agent (MSA). Furthermore, energy integration can increase the energy and economic efficiency of these thermal processes. Since, MSA selection, process design and energy integration are usually performed as consecutive steps in process design, potential synergies are easily missed, resulting in sub-optimal choices. In order to determine an optimal process design, including solvent selection and energy integration, an efficient optimization-based approach for the design of extractive distillation processes is proposed. The application of the method is illustrated for the separation of the azeotropic mixture of acetone and methanol. The results highlight that the optimal MSA choice under consideration of energy integration differs from the selection without energy integration.

Efficient processes for carbon dioxide (CO2) capture from post-combustion flue gases are required to combat global climate change. A key stage in post-combustion capture is selective CO2 separation from the flue gas stream. Separation of CO2 from mixed gases using countercurrent gas–liquid absorption in packed columns is a well-established technology for treatment of industrial gas streams. This approach can be adapted to remove CO2 from post-combustion flue gas, however, process improvements are needed to minimize the corresponding capital costs and energy requirements. Special challenges for CO2 recovery from flue gas arise from the very large volumes of gas to be processed, the need to operate the process with an inlet flue gas stream at atmospheric pressure, and the high amount of energy required to regenerate the absorption liquid. Aqueous solutions of the tertiary amine N-methyldiethanolamine (MDEA) are commercially used for high pressure CO2 separation due to high loading capacity for CO2, relatively good chemical and thermal stability and low volatility. Application of MDEA-based solutions to ambient pressure separations, such as CO2 capture from flue gases, is challenging since high reaction rates are required. High reaction rates for the MDEA system are achievable at high temperatures, which is conflicting with the preference of low temperatures to exploit high absorption capacity. This conflict can be overcome with the addition of a rate enhancing catalyst that enables high reaction rates at low temperatures. To put this innovative breakthrough technology closer to industrial application CO2 absorption in 30–50 wt.% aqueous solutions of MDEA in absence and presence of the CO2 absorption enhancing enzyme carbonic anhydrase (CA) was evaluated in pilot scale. The pilot scale investigation employed a packed column for parametric testing. Test variables included the liquid phase composition (30–50 wt.% MDEA), the column liquid load (8–24 m3 m−2 h−1), the absorber temperature (20–40 °C), and the application of CA in a dissolved or immobilized form. The CO2 absorption mass transfer enhancement provided by CA was measured. In the presence of dissolved CA, 30 wt.% aqueous MDEA showed superior performance in terms of absorption rates compared to operation using 50 wt.% MDEA(aq). No significant change in the CO2 absorption rate was observed for operation at given loads between 20 °C and 40 °C with dissolved CA present. At 20 °C with 30 wt.% MDEA the absorption rate with dissolved CA increased by more than 9 times compared to the absorption rate without enzyme. These results broaden the operation window for efficient CO2 absorption using MDEA solutions and allow for the exploitation of new process regimes, wherein high equilibrium loadings are achievable by applying lower absorption temperatures. Based on the experimental results obtained with dissolved CA, a simplified rate-based model of enzymatic reactive absorption (ERA), accounting for enzyme accelerated reaction kinetics, was developed which was capable of accurately predicting CO2 absorption rate when compared with experimental data. Implemented in a process simulator the model allows for the detailed investigation of the process behavior and the complex interactions of ab- and desorption operations in the presence of the CA. The validated model is intended to guide future experimental work as well as further performance optimization. In addition to the work exploiting the catalyst in its free form, the utilization of CA immobilized in a granular form and held in the pockets of Katapak-SP packing was successfully demonstrated.