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The Electrolyte Nonrandom Two-Liquid Activity Coefficient model in Aspen PlusTM 2006.5 was used to develop a rigorous and consistent thermodynamic representation for the base sub-component systems associated with aqueous combinations of K₂CO₃, KHCO₃, MEA, and piperazine (PZ) in a mixed-solvent electrolyte system for the application of CO₂ absorption/stripping from coal fired power plants. We developed a new vapor-liquid equilibrium apparatus to measure CO₂, amine, and H2O vapor pressures at 40 and 60 oC. We found that the volatility of MEA and PZ can be approximated at 50 and 20 ppmv at 40°C for any solvent composition studied in this work, over the CO₂ partial pressure range from 0.01 to 0.1 kPa. Very few solvent compositions exhibited a greater differential capacity than 7 m MEA at 60°C; specifically 11 m MEA, 3.5 m MEA + 3.6 m PZ, 7 m MEA + 2 m PZ, 7 m MEA + 3.6 m PZ, and 5 m K+ + 7 m MEA + 3.6 m PZ. Piperazine exhibited a possible maximum differential capacity of 2.21 mole CO₂/kg-H₂O at a concentration of 7.3 m. At the Norwegian University of Science and Technology, Inna Kim determined the differential enthalpy of CO₂ absorption for aqueous combinations of K₂CO₃, KHCO₃, MEA, PZ, and CO₂, based on a consistent experimental method developed for MEA, from 40 to 120°C for use in this work. In addition, we developed a consistent method to measure the specific heat capacity for a number of similar solvent combinations. We found that the enthalpy of CO₂ absorption increased with temperature because the apparent partial heat capacity of CO₂ may be considered small. Finally, by using a differential scanning calorimeter, we determined the dissolution temperature for aqueous mixtures of unloaded piperazine, which inferred an effective operating range for solutions of concentrated piperazine, greater than 5 m PZ, over a loading range between 0.25 to 0.45 mole CO₂/2·mol PZ. Through unit cell x-ray diffraction, we were able to identify and characterize the presence of three solid phases (PZ·6H₂O, KHCO₃, and KvPZ(COO)₂) in aqueous mixture combinations of K₂CO₃, KHCO₃, PZ, and CO₂. / text

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A dissertation submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Master of Science in Engineering September, 2017 / South Africa emits large amounts of carbon dioxide (CO2) due to its reliance on coal. The emission of CO2 needs to be reduced for clean sustainable energy generation. Research efforts have therefore been devoted to reducing CO2 emissions by developing cost-effective methods for capturing and storing it. Amine-based absorption using monoethanolamine solvent is the most mature technique for CO2 capture despite its huge energy consumption, corrosiveness and difficulty in solvent regeneration. However, CO2 removal by solid adsorbents is a promising alternative because it consumes less energy, and can be operated at moderate temperature and pressure. Metal organic frameworks have received attention as a CO2 adsorbent because they have large surface areas, open metal sites, high porosity and they require less energy for regeneration. This research was aimed at optimizing and scaling-up SOD-ZMOF through structural modification for enhanced CO2 adsorption by impregnating it with chitosan. Scaled-up SOD-ZMOF samples were prepared as described elsewhere and impregnated with Chitosan. Physiochemical properties obtained using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and Nitrogen physisorption showed that SOD-ZMOF and SOD-ZMOF-chitosan were successfully synthesized. Qualitatively, the surface area of the SOD-ZMOF synthesized using the scaled up protocol is lower than the one prepared using the non-scaled-up protocol XRD pattern of SOD-ZMOF showed that it was crystalline and was in agreement with literature. The XRD peaks of the SOD-ZMOF decreased after chitosan impregnation showing that chitosan was impregnated on SOD-ZMOF. The FTIR spectrum of SOD-ZMOF showed functional groups present in organic linker used to synthesize SOD-ZMOF, and that of the SOD-ZMOF-chitosan revealed the same functional groups but with disappearance of carboxylic acid functional group. N2 physisorption showed a decrease in BET surface area and pore volume after chitosan impregnation on SOD-ZMOF as well. Performance evaluation of the material was carried out with a demonstration adsorption set-up using a 15%/85% CO2/N2 mixture and as a thermal gravimetric analysis (TGA) using 100% CO2. For both the packed-bed column and the TGA experiments, evaluation was conducted on SOD-ZMOF and SOD-ZMOF with chitosan for comparison. About 50 mg of the adsorbent was used at 25 oC, 1 bar and 25 ml/min for the packed-bed column. For the adsorption with the TGA, 11 mg of adsorbent was used at 25 ℃, 1 bar and 60 ml/min. SOD-ZMOF showed improved adsorption capacity after chitosan impregnation. CO2 adsorption capacity of SOD-ZMOF increased by 16% and 39% using packed-bed column and TGA, respectively, after chitosan impregnation. The increase in adsorption capacity was attributed to the impregnated chitosan that has amine groups that display a high affinity for CO2. A traditional approach was used to investigate the effect of adsorption temperature and inlet gas flowrate on the CO2 adsorption capacity of SOD-ZMOF-chitosan. This was done using both the parked bed column and the TGA. Temperature range of 25-80 ℃ and inlet gas flowrate range of 25-90 ml/min were investigated. Adsorption capacity increased with a decrease in temperature and inlet gas flowrate. For the packed-bed column, maximum of 781 mg CO2/ g adsorbent was obtained at 25℃, 1 bar, 25 ml/min and for the TGA a maximum CO2 adsorption capacity of 23 mg/ g adsorbent at 25 ℃, 1 bar, and 60 ml/min was obtained. / MT2018

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Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2009. / Sequestration of carbon dioxide, CO2, has received large interest as a viable option for mitigating the high atmospheric concentrations of this greenhouse gas. Each year 25 gigatons of anthropogenic CO2 (7.3 GtC/yr) are released into the earth’s atmosphere with the combustion of fossil fuels being the major contributing source. Research in the field of sequestration technology involves evaluating various geological structures as possible reservoirs, determining adsorption capacities of natural formations and developing methods for carbon dioxide injection and the monitoring thereof. Identified potential CO2 reservoirs for geological carbon sequestration (GCS) include saline formations, depleted oil and gas fields and deep coal seams. Carbon dioxide sequestration in coal seams provides the economic opportunity of enhanced coalbed methane (CH4) recovery (ECBM). In South Africa, some coal seams are considered a viable option for long term CO2 sequestration projects as they are abundant and closely situated to South Africa’s largest concentrated CO2 point sources. Many studies have been conducted to determine the sorption capacities for methane and carbon dioxide gases on various coals from around the world; however, similar data have not been recorded for South African coals. The objectives of this study are to determine the adsorption capacities for methane and carbon dioxide of three South African coals over a pressure range of 0 – 50 bar. In the study, single-component gas adsorption experiments were conducted and the absolute adsorption capacities are reported. Isothermal adsorption experiments were conducted using both the volumetric and gravimetric methods with the volumetric apparatus pressure range extending up to 50 bar and the gravimetric apparatus up to 20 bar. Carbon dioxide adsorption capacities are much higher than the methane adsorption capacities, which are expected. Gravimetric experiments produce greater adsorption capacities than the volumetric method. However, the relative CO2/CH4 ratios for each coal, as well as the relative CO2/CO2 ratios between coals, remain almost identical. The difference in adsorption capacity is attributed to the strength of the vacuum pump used on each apparatus. The gravimetric apparatus makes use of a much stronger vacuum pump which can thus evacuate the coal pores more adequately than in the volumetric apparatus. The methane and carbon dioxide adsorption capacities of the three moisture-free coals compare well with literature data. The adsorption isotherms fit conventional adsorption models (the Langmuir and Freundlich adsorption equations) extremely well thus indicating that monolayer adsorption takes place. Since no internationally recognised testing standards are in place regarding adsorption procedures on coal, it is very difficult to compare adsorption results presented in the literature. Respective researchers determine their own experimental conditions for the many variables in coal adsorption studies. It is recommended that international testing standards be set in place to make coal research comparable. Such efforts would aid the development of a coal adsorption database, another recommendation, which would advance sequestration technology exchange and eliminate duplication of research efforts. The objectives of the project were achieved by determining the absolute adsorption capacities for carbon dioxide and methane gas of the three South African coals within a pressure range of 0 – 50 bar. Further work is required to investigate adsorption capacities of South African coals under supercritical conditions (above 73 bar abs and 31.1 oC).

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: The discovery that the reaction of CO2 with primary amines in both aqueous and non-aqueous media provides a viable chemical method for determining the effective interfacial mass transfer area for separation column internals has lead to an increase in the interest of studying the reaction kinetics and determining the governing reaction rate expressions. For the absorption studies conducted on these systems, many authors assumed that power rate law reaction kinetics govern the reaction rate, which simplified the derivation of absorption correlations. This has already been proven to be an over simplifying assumption, since many authors suggest a non-elementary rate expression based on the pseudo-steady state hypothesis for the reactive zwitterion intermediate to be valid. An evaluation of the existing reaction rate expressions for the homogeneous liquid phase reaction of CO2 and mono-ethanolamine (MEA) in a 2-propanol solvent system was performed. The reaction rate profiles of CO2 and MEA at 25ºC, 30ºC and 35ºC, and relative initial concentrations of [MEA]i = [CO2]i, [MEA]i = 2.5[CO2]i, [MEA]i = 4[CO2]i were determined by means of an isothermal CSTR set-up. Scavenging of the unreacted MEA with benzoyl chloride provided the means to be able to stop the reaction in the product stream. This in turn allowed for the construction of concentration- and reaction rate profiles. The reaction rate data was modelled on various rate expressions by means of a MATLAB® non-linear estimation technique, employing the Levenberg-Marquard algorithm for minimizing the loss function. It was concluded that the rate expressions proposed in literature are insufficient and a rate expression derived fundamentally from first principals is proposed: [ ][ ] [ ] [ ][ ] [ ]2 MEA 1 2 2 -r = k CO RNH - k2 Z + k3 Z RNH2 - k4 S where ki are the reaction rate constants, Z is the zwitterion reactive intermediate and S the salt product of the overall reaction mechanism. In order to be able to determine the effective interfacial mass transfer area, the absorption rate per unit area or specific rate of absorption for the solute gas as a rate expression function of species concentration must firstly be determined. This is achieved by performing experimental absorption runs on a gas-liquid contactor of known surface area. This study incorporated the well known wetted wall experimental set-up. The aim was to construct and implement a wetted wall set-up and conduct absorption experiments for a gas side CO2 concentration range stretching from pure CO2 to diluted gas mixtures absorbing into solutions of varying MEA concentrations. Validation of the set-up was done by performing experiments at similar conditions to a previous study. The study then proceeded to determine the absolute and specific absorption rates at CO2 mass percentages of 100%, 78%, 55% and 30% into solutions of MEA concentrations of 0.25 and 0.3 mol/L. These runs were conducted at 25ºC and 30ºC. The wetted wall was designed to facilitate absorption studies at column heights of 60, 90 and 105mm. This allowed the investigation of the effect that surface area and column height has on the absolute rate of absorption as well as the CO2 and MEA concentrations in the liquid phase It was found that the specific absorption rate is independent of contact time, which is consistent with the rapid nature of the reaction. It was furthermore found that an increase in MEA concentration caused an increase in the absorption rate. The effect of temperature is linked with the solubility of CO2 in the solution. As the temperature increases, the solubility of CO2 decreases, but the absorption rate increases. The result is that it seems as if a change in temperature has no effect on the absorption rate, when in actual fact it does. An increase in the amount of CO2 absorbed is noticed for an increase in wetted wall surface area. This is expected and indicates that there is an increase in the amount of CO2 absorbed as the column length increases. Stopping the absorption reaction by means of MEA scavenging with benzoyl chloride at various column heights will allow for the construction of a concentration profile for both CO2 and MEA as a function of column height. These profiles will allow for the derivation of a non-elementary rate expression governing the specific absorption rate. This has been identified as ‘n area of great interest for future investigation. / AFRIKAANSE OPSOMMING: ‘n Groot navorsingsbelangstelling in die reaksiekinetika van CO2 en monoethanolamien (MEA) het ontstaan sedert die ontdekking dat hierdie reaktiewe sisteem ook ‘n goeie metode is vir die bepaling van die effektiewe massaoordragsoppervlakte van gestruktureerde pakkingsmateriaal. Die klem val op die bepaling van eerstens die mees geskikte en akkurate model om die reaksiekinetika te beskryf wat dan gebruik kan word om die absorbsiekinetika deeglik te karaktariseer. Sommige van die vorige navorsers het vereenvoudigende aannames gemaak rakende die reaksiekinetika ten einde die bepaling van geskikte absopsievergelykings te vergemaklik. Ander het gevind dat die nie-elementêre, pseudo-gestadigde toestand hipotese gebasseer op die reaktiewe zwitterioon tussenproduk van die reaksie ‘n meer verteenwoordigende kinetiese model is. Hierdie studie is eerstens gemik op die evaluasie van die bestaande reaksiekinetikavergelykings deur die homogene vloeistoffase reaksie van CO2 met mono-etanolamien (MEA) in die oplosmiddel, 2-propanol te ondersoek. Die studie is uitgevoer in ‘n isoterme CSTR sisteem by onderskeidelik 25ºC, 30ºC en 35ºC en MEA konsentrasies van [MEA]i = [CO2]i, [MEA]i = 2.5[CO2]i en [MEA]i = 4[CO2]i. Die voorgestelde reaksiekinetikavergelykings was gemodelleer met ‘n nie-lineêre datapassingstegniek verskaf deur die sagtewarepakket, MATLAB® wat die Levenberg- Marquard algoritme gebruik om die resfunksie te minimeer. Uit die teorie en datapassing word die volgende vergelyking voorgestel: [ ][ ] [ ] [ ][ ] [ ]2 MEA 1 2 2 -r = k CO RNH - k2 Z + k3 Z RNH2 - k4 S waar ki die reaksietempokonstante voorstel, Z die zwitterioontussenproduk en S die soutproduk. Die eerste stap in die bepaling van die effektiewe massaoordragsarea van gestruktureerde pakkingsmateriaal is om ‘n geskikte vergelyking of korrelasie vir die spesifieke absorpsie van die gas te bepaal. Dit word gedoen deur absoprsie eksperimente te doen op toerusting van bekende oppervlakarea. Hierdie studie het die reeds bekende ‘wetted wall’ opstelling gebruik. Die hoof doelwit van hierdie absorpsiestudie was om ‘n werkende opstelling te bou en absorpsie eksperimente vir CO2 konsentrasies wat strek van suiwer CO2 tot verdunde mengsels uit te voer. Die konsentrasie MEA is ook gevarieër. Die geskiktheid van die opstelling is eerstens getoets deur eksperimentele lopies uit te voer by soorgelyke toestande as ‘n vorige studie. Die doel van die studie is om die absolute en spesifieke absorpsietempos van CO2 by gasfase massapersentasies van 100%, 78%, 55% en 30% in MEA/2-propanol oplossings met MEA konsentrasies van 0.25 en 0.3 mol/L te bepaal. Die lopies is uigevoer by beide 25ºC en 30ºC. Die opstelling is ook ontwerp om absorpsie eksperimente by verskillende kolomhoogtes uit te voer. Hierdie hoogtes is 60, 90 en 105mm. Hierdie studie het tweedens gefokus op die effek wat absorpsiearea en kolomhoogte op die absorpsietempo van CO2 het. Die resultate van die studie toon dat die absorpsietempo onafhanklik is van kontaktyd. Dit stem saam met die vinnige reaksietempo. ‘n Toename in MEA konsentrasie het ‘n toename in spesifieke absorpsietempo tot gevolg, terwyl die effek van temperatuur gekoppel kan word aan die oplosbaarheid van CO2. Soos die temperatuur toeneem, neem die absolute absorpsietempo toe, maar die oplosbaarheid van CO2 neem af, dit het beide ‘n toenemende en afnemende effek op die spesifieke absorpsietempo. Die hoeveelheid CO2 geabsorbeer neem toe met ‘n toename in kolomhoogte. Die konsentrasie MEA in die uitlaatvloeistof toon ‘n skynbare eksponensiële afname met ‘n toename in kolomhoogte. ‘n Studie gemik om die konsentrasieprofiele van CO2 en MEA as ‘n funksie van kolomhoogte te bepaal, word voorgestel. Absorpsiemodelle en korrelasies kan dan afgelei word uit hierdie profiele, wat die berekening van die effektiewe massaoordragsarea akkuraat sal maak. Dit sal deel vorm van toekomstige navorsing.

D. Tech. Polymer Technology. / Addresses the aim of generating new knowledge on: 1) the effect of supercritical CO2 on H-bond behaviour between polymers, and on 2) drug-loaded interpolymer complex preparation in supercritical CO2.

The response to climate change must include decisive and collaborative solutions that minimize global CO₂ emissions and enable a shift to low-carbon energy (renewable electricity) and CO₂-derived chemicals and fuels. A major challenge of minimizing fossil fuel use is producing critical chemicals and fuels for heavy industry and transportation in novel ways. These traditionally fossil-derived products can be derived from CO₂ that is captured from point sources or the atmosphere. Reactive CO₂ capture is an emerging area of research that focuses on developing materials and processes for CO₂ capture and in situ conversion to valuable chemicals or fuels. By combining these two steps, costly and energy-intensive steps of conventional integrated capture and conversion schemes are eliminated, including sorbent regeneration, CO₂ purification, pressurization, and transportation. These operations typically drive up the cost of capture and conversion processes, making them less economically attractive. The dual function material (DFM) is an Al₂O₃-supported, nano-dispersed catalyst and sorbent combination that demonstrates both capture and catalytic conversion properties, making reactive capture possible. Feasibility of the 1% Ru, 10% “Na₂O”/Al₂O₃ DFM for CO₂ direct air capture (DAC) and in situ catalytic methanation (DACM) has been demonstrated in previous work. Recent work has prioritized advanced laboratory testing and laboratory aging of this DFM under a variety of simulated ambient capture climates to assess the advantages and limitations of the material. A monolith was used as a structured support for the DFM to minimize reactor pressure drop, a particularly relevant challenge for DAC applications where large volumes of air must be processed to separate the small volume of CO₂ (~ 400 ppm). Findings from DFM monolith studies (1% Ru, 10% “Na₂O”/Al₂O₃//monolith) were shared with an engineering partner to support scale up efforts. Laboratory-simulated DACM cycles consisted of DAC performed at various real-world simulated ambient conditions followed by catalytic methanation, where the DFM was heated to 300°C in 15% H₂/N₂. Simulated DAC included O2 and humidity, and a surprising finding showed significant enhancement of CO₂ adsorption due to humidity in the capture feed. The maximum CO₂ capture capacity of the DFM monolith was measured to be 4.4 wt% (based on the weight of DFM material) at 25°C with 2 mol% H₂O in the DAC feed. Aging studies revealed consistent CO₂ capture and CH₄ production after over 450 hours of cyclic DACM testing that included simulated ambient conditions. No signs of deactivation of either the “Na₂O” sorbent or Ru catalyst were observed. The light-off temperature (indicative of kinetic control) observed for catalytic methanation was constant between fresh and aged cycles. These findings verified the qualifications of the 1% Ru, 10% “Na₂O”/Al₂O₃//monolith for the DACM application and supported further advanced bench and pilot plant testing by our engineering collaborator. Additional parametric studies were conducted to evaluate the effects of varying humidity during DAC and revealed that a higher H₂O concentration in the DAC feed correlates with greater CO₂ captured and converted with no evidence of competitive adsorption between CO₂ and H₂O. Additionally, it was found that temperature changes within ambient range (0 – 40°C) played little role in varying CO₂ captured under dry conditions, whereas moisture was found to be a major driver of capture capacity. Furthermore, stable performance at a reference condition was always achieved after excursions to varying ambient conditions. DACM tests revealed 30 – 40% of captured CO₂ desorbs during the temperature swing step, which was attributed mainly to the slow heating rate and low H₂ content (15%) required for safe laboratory operation. Unreacted CO₂ was eliminated by shortening the DAC step and engaging partial capture capacity of the DFM. This mode of cycling is more representative of that which would be carried out at scale, as shorter adsorption durations capitalize on the fastest adsorption kinetics exhibited by a capture material. Consistent with reported literature, findings suggest that CO₂ is preferentially adsorbed to stronger capture sites at the onset of DAC that are better able to retain CO₂ during heat up. Though the DFM is not fully utilized, these partial capacity cycles demonstrated higher conversions to CH₄ and a more efficient use of the material that will require less downstream purification at scale.

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