Canola meal was used as an adsorbent in a pressure swing adsorption (PSA) apparatus for ethanol dehydration. The experiments were conducted at different pressures, temperatures, vapor superficial velocities, vapor concentrations and particle sizes. Adsorption experiments were performed at equilibrium and breakthrough points. The results demonstrated that canola meal can break the azeotropic point 95.6 wt% and produce over 99 wt% ethanol. At elevated temperature, feed water concentration, and vapor superficial velocity, it was found that the mass transfer rate increased. In addition, the mass transfer rate decreases when either the total pressure or the size of the adsorbent particles are increased. Breakthrough curves were simulated and the overall mass transfer resistance was evaluated at all experimental runs. The internal mass transfer resistance was identified as the relevant mass transfer mechanism. For canola meal, the equilibrium water/ethanol uptake was achieved at 100, 105, and 110˚C. The Frenkel-Halsey-Hill (FHH) and Guggenheim-Andrson-de-Boer (GAB) models perfectly simulated the water adsorption isotherms. By applying Dubinin-Polanyi model to the experimental data, canola meal was identified as a large pore (non-porous) material. The heat of adsorption on canola meal with particle size of 0.43-1.18 mm was determined to be -32.11 kJ/mol. The result confirms that the adsorption process is an exothermic phenomenon and is of physical type due to the fact that the value obtained as the heat of adsorption is negative and its magnitude is within the range 20–80 kJ/mol. The equilibrium water uptake on canola meal was similar to that reported for other starchy and cellulosic adsorbents, while the ethanol uptake was higher. Water saturated canola meal was successfully regenerated by passing nitrogen at 110˚C which is lower than that for molecular sieves commonly used in industry for bioethanol dehydration. The canola meal bio-adsorbent was re-used for more than 32 cycles and no significant change in adsorption capacity was observed.

A significant challenge in large scale industrial production of butanol is its low product titer. Butanol needs to be purified to higher than 99% purity in order to be used for fuel applications. The focus of this study is to selectively remove water from butanol-water vapor to achieve fuel grade butanol in a pressure swing adsorption (PSA) system using biosorbents developed from agricultural byproduct canola meal (CM). CM was characterized by Fourier Transform Infrared Spectroscopy (FTIR) that CM contains polar groups such as hydroxyls, carboxyls, and amines in cellulose, hemi-cellulose and protein that have the potential for water adsorption. Physico-chemical characterizations were also done to understand the major composition, elemental make-up, devolatilization characteristics and particle size distribution of the CM used. The results demonstrated that biosorbent based on CM was able to successfully dry lower grade butanol and generate fuel grade butanol of over 99 v/v%. Five operating parameters were studied at two different levels to get the optimum process conditions for butanol drying, including temperature (95 and 111°C); pressure (135 and 201 kPa); feed butanol concentration (55 and 95 v/v %); feed flow rate (1.5 and 3 mL min-1) and particle size of adsorbent (0.425-1.18 mm and 4.7 mm pellets). Orthogonal array design (OAD) tool was used to design experiments and to evaluate the effects of these parameters. The performance of butanol dehydration was evaluated using five indices - water uptake; butanol uptake; water selectivity; butanol recovery; and maximum effluent butanol concentration in the effluent. The results demonstrated that feed butanol concentration, temperature and pressure were found to be the most significant factors overall, affecting most of the indices. The effects of individual operating parameters on each butanol dehydration index were determined and a set of optimum operating conditions were proposed by the range analysis of the orthogonal array design at 111oC, 135 kPa, feed butanol concentration of 55 v/v%, feed butanol-water liquid flowrate of 3 mL/min and biosorbent particle size of 0.43-1.18 mm. The experiments conducted at the above mentioned optimum conditions resulted in water uptake of 0.48 g/g-ads, water selectivity of 5.4, butanol recovery of 90%, and the maximum butanol concentration in the effluent being over 99 v/v% , which are better than that obtained at any other conditions investigated in this work. The Dubinin–Polanyi model based on adsorption potential theory displayed a goodness of fit to the water adsorption isotherm data with a r2 value of 0.95 and average relative error of just 3.5%. The mean free energy determined from the model was 0.02 kJ/mol indicated the adsorption is physical. Thermodynamic parameters were also evaluated which revealed that the water adsorption is exothermic and spontaneous. Water saturated adsorbent was regenerated at 110°C under vacuum and reusability was studied. The contribution of two major components of CM namely cellulose and protein were also examined for their capability to selectively remove water from butanol. The results showed both of them were able to dry water, however cellulose was found to have a higher water uptake and water selectivity than protein, indicating that it plays a major role in drying butanol. In order to compare the performance of CM on drying of butanol with other biomaterials, adsorption experiments were done using corn meal as adsorbent, which is one of the most common starch based biosorbents for ethanol drying. The results demonstrated that canola meal had a higher water uptake and water selectivity than corn meal. Use of CM over corn meal adsorbent is also desirable so as to avoid placing pressure on food consumption. In addition, drying of butanol using other cellulose based biosorbents such as oat hull was also explored. Oat hull demonstrated a potential to adsorb water and dehydrate butanol, which requires further in-depth investigation.

Strong dependency on fossil fuels and the associated price and supply chain risk increase the need for more efficient utilisation of existing non-renewable energy sources. Carbon capture and hydrogen purification technologies are expected to play a key role in the future low-carbonised energy matrix. Integrated Gasification Combined Cycles (IGCCs) are one of the emerging clean coal technologies which pave the way for producing power from coal with a higher net power efficiency than conventional PC-fired boiler power plants. It is also advantageous that in an IGCC power plant a carbon capture unit can be applied to a stream having a very high CO2 partial pressure ahead of gas combustion that would not be available in case of a PC-fired boiler power plant, leading to less energy penalty involved in carbon capture. At the same time, the production of ultrapure hydrogen is both a sought target and an appropriate environmental solution because it is commonly utilised as feedstock in refineries’ hydrotreaters and hydrocrackers as well as energy carrier in fuel cells. A high purity of hydrogen has been commercially produced out of raw synthesis gas using a Hydrogen Pressure Swing Adsorption (H2 PSA) process. In this thesis, it was aimed to design and optimise a bespoke H2 PSA system tailored for a decarbonised syngas feed originating from a carbon capture unit. Therefore, a novel H2 PSA has been studied that is applied to an advanced IGCC plant for cogenerating power and ultrapure hydrogen (99.99+ mol%) with pre-combustion CO2 capture. In designing the H2 PSA, it is essential to increase the recovery of ultrapure hydrogen product to its maximum since the power consumption for compressing the H2 PSA tail gas up to the gas turbine operating pressure should be minimised to save the total auxiliary power consumption. Hydrogen recovery was raised by increasing the complexity of the PSA step configuration that allows a PSA cycle to have a lower feed flow to one column being used for adsorption and more pressure equalisation steps. An in-depth economic analysis was carried out and discussed in detail. The industrial advanced IGCC performances have also been improved by process integration between the H2 PSA unit and other units in the plant.

Carbon capture and storage technologies (CCS) are expected to play a key role in the future energy matrix. Different gas separation processes are under investigation with the purpose of becoming a more economical alternative than solvent based post combustion configurations. Previous works have proved that pressure swing adsorption (PSA) cycles manage to reach similar carbon capture targets than conventional amine process but with approx. a 50% lower specific energy consumption when they are applied at lab scale. These encouraging results suggest that research must be undertaken to study the feasibility of this technology at a low to medium power plant scale. The simulation of PSA cycles is a computationally challenging and time consuming task that requires as well a large set of experimentally measured data as input parameters. The assumption of Equilibrium Theory reduces the amount of empirically determined input variables that are necessary for modelling adsorption dynamics as well as enabling a simpler code implementation for the simulators. As part of this work, an Equilibrium Theory PSA cycle solver (Esim) was developed, the novel tool enables the quantification of the thermodynamic limit for a given PSA cycle allowing as well a pre-selection of promising operating conditions and configurations (high separation efficiency) for further investigation by using full governing equation based software The tool presented in this thesis is able to simulate multi-transition adsorption systems that obey any kind of equilibrium isotherm function without modifying its main code. The second part of this work is devoted to the design, simulation and optimisation of two stage two bed Skarmstrom PSA cycles to be applied as a pre-combustion process in a biomass gasification CHP plant. Simulations were carried out employing an in house software (CySim) in which full governing equations have been implemented. An accurate analysis of the operating conditions and cycle configurations was undertaken in order to improve the performance of the carbon capture unit. It was estimated that the energy penalty associated with the incorporation of the adsorptive pre combustion process was lower for a conventional post combustion solvent unit, leading as well to lower specific energy consumption per unit of captured CO2 and higher overall efficiencies for the CHP plant with installed pre-combustion PSA cycles. This work is pioneer in its kind as far as modelling, simulation, optimisation and integration of PSA units in energy industries is concerned and its results are expected to contribute to the deployment of this technology in the future energy matrix.

京都大学 / 0048 / 新制・論文博士 / 博士(工学) / 乙第13089号 / 論工博第4150号 / 新制||工||1675(附属図書館) / (主査)教授 北川 進, 教授 杉野目 道紀, 教授 宮原 稔 / 学位規則第4条第2項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24645号 / 工博第5151号 / 新制||工||1983(附属図書館) / 京都大学大学院工学研究科化学工学専攻 / (主査)准教授 渡邉 哲, 教授 佐野 紀彰, 教授 河瀬 元明 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

An experimental pressure swing adsorption unit has been constructed and used to investigate the separation of carbon dioxide from carbon dioxide enriched air using both an activated carbon and a type 5A molecular sieve adsorbent. Continuous, cyclic operation was achievedusing a pair of fixed bed adsorbers. At any one time the feed gas entered one bed at a high pressure and part of the purified gas was returned to the other bed at a reduced pressure to provide countercurrent regeneration of the adsorbent. The beds of adsorbent used were each nominally 0.165m diameter and Im. deep. Separations were carried out at approximately ambient temperature using air flow rates in the range 0.15 to 0.95 kg/m2s and inlet carbon dioxide concentrations'in the range 0.1 to 1.5% v/v. Adsorption pressures of 2 to 6.4 bar were examined, the desorption pressure being maintained throughout at essentially 1.0 bar. The period time was varied from 30 to 900 seconds and the revert ratio (i. e. the ratio of the product gas returned for desorption to the total feed rate to the unit) was varied from 0 to 1.0. The carbon dioxide separation efficiency was found to increase markedly as the adsorption pressure and the revert ratio were increased whereas it was relatively insensitive to variations in feed rate and, more particularly, feed concentration. The performance of the molecular sieve adsorbent was found to be very sensitive to the presence of moisture in the feed gas. In contrast the carbon dioxide efficiencies observed with Lhe activated carbon were unaffected by the presence of small amounts (circa 100 ppm) of moisture in the feed. A theoretical model has been proposed for predicting the performance of pressure swing adsorption systems of the type investigated and approximate analytical equations and more precise numerical techniques have been established to represent its solution. The approximate analytical solutions were found to give close agreement with the more precise methods examined under conditions corresponding to low values of a dimensionless period time parameter. The proposed theoretical model incorporates an effective irean mass transfer coefficient to represent the diffusion process within the adsorbent particles. Methods for estimation of the value of this coefficient based on the limiting conditions of a periodic constant surface flux or a periodic constant surface concentration are presented. The experimental performance data were analysed in terms of the proposed analytical solution to give values of the apparent solid phase mass transfer coefficient for comparison with those predicted theoretically. In general the apparent experimental values were consistently less than the predicted values. In addition the relationship between the experimental and predicted coefficients was found to be dependent on both the nature of the adsorbent and a parameter formed by the product of the revert ratio and the adsorption to desorption pressure ratio. Empirical correlating equations which incorporate this dependence are presented.

No description available.

An investigation was undertaken to determine the feasibility of increasing the hydrogen production rate by coupling the water gas shift (WGS) process to the hybrid sulphur process (HyS). This investigation also involved the technical and economical analysis of the water gas shift and the H2 separation by means of Pressure swing adsorption (PSA) process. A technical analysis of the water gas shift reaction was determined under the operating conditions selected on the basis of some information available in the literature. The high temperature system (HTS) and low temperature system (LTS) reactors were assumed to be operated at temperatures of 350ºC and 200ºC, respectively. The operating pressure for both reactors was assumed to be 30 atmospheres. The H2 production rate of the partial oxidation (POX) and the WGS processes was 242T/D, which is approximately two times the amount produced by the HyS process alone. The PSA was used for the purification process leading to a hydrogen product with a purity of 99.99%. From the total H2 produced by the POX and the WGS processes only 90 percent of H2 is recovered in the PSA. The unrecovered H2 leaves the PSA as a purge gas together with CO2 and traces of CH4, CO, and saturated H2O. The estimated capital cost of the WGS plant with PSA is about US$50 million. The production cost is highly dependent on the cost of all of the required raw materials and utilities involved. The production cost obtained was US $1.41/kg H2 based on the input cost of synthesis gas as produced by the POX process. In this case the production cost of synthesis gas based on US $6/GJ for natural gas and US $0/Ton for oxygen was estimated to be US $0.154/kg. By increasing the oxygen and natural gas cost, the corresponding increase in synthesis gas has resulted in an increase in H2 production cost of US $1.84/kg. / Thesis (M.Sc. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2006.

A new concept of a "fiber sorbent" has been investigated. The fiber sorbent is produced as a pseudo-monolithic material comprising polymer (cellulose acetate, CA) and zeolite (NaY) by applying hollow fiber spinning technology. Phase separation of the polymer solution provides an appropriately porous structure throughout the fiber matrix. In addition, the zeolite crystals are homogeneously dispersed in the polymer matrix with high loading. The zeolite is the main contributor to sorption capacity of the fiber sorbent. Mass transfer processes in the fiber sorbent module are analyzed for hydrogen recovery and compared with results for an equivalent size packed bed with identical diameter and length. The model indicates advantageous cases for application of fiber sorbent module over packed bed technology that allows system downsizing and energy saving by changing the outer and bore diameters to maintain or even reduce the pressure drop. The CA-NaY fiber sorbent was spun successfully with highly porous structure and high CO2 sorption capacity. The fiber sorbent enables the shell-side void space for thermal moderation to heat of adsorption, while this cannot be applied to the packed bed. The poly(vinyl alcohol) coated CA-NaY demonstrated the thermal moderation with paraffin wax, which was carefully selected and melt at slightly above operating temperature, in the shell-side in a rapidly cycled pressure swing adsorption. So this new approach is attractive for some hydrogen recovery applications as an alternative to traditional zeolite pellets.