Abstract: Low-temperature waste heat is abundant in the process industries, and large amounts of Liquefied Natural Gas (LNG) cold energy are discarded without being recovered properly in LNG terminals. Power generation is an effective way to utilize low-temperature waste heat and LNG cold energy simultaneously. Organic Rankine Cycles (ORCs) and CO2 power cycles are promising technologies to convert low-temperature waste heat and LNG cold energy into electricity. If waste heat and LNG cold energy are utilized simultaneously in one system, the performance may outperform separate systems utilizing low-temperature waste heat and LNG cold energy, respectively. Low-temperature waste heat acts as the heat source and LNG regasification acts as the heat sink in the combined system. Due to the large temperature difference between the heat source and the heat sink, cascaded power cycle configurations are proposed in this paper. Cascaded power cycles can improve the energy efficiency of the system considerably. The cycle operating at a higher temperature to recover waste heat is called top cycle and the cycle operating at a lower temperature to utilize LNG cold energy is called bottom cycle in this study. The top cycle condensation heat is used as the heat source in the bottom cycle. The top cycle can be an ORC, transcritical CO2 (tCO2) cycle or supercritical CO2 (sCO2) cycle, while the bottom cycle only can be an ORC due to the low-temperature range of the bottom cycle. However, the thermodynamic path of the tCO2 cycle and sCO2 cycle are different from that of an ORC. The tCO2 cycle and the sCO2 cycle perform better than an ORC for sensible waste heat recovery due to a better temperature match with the waste heat source. Different combinations of the tCO2 cycle, sCO2 cycle and ORC are compared to screen the best configurations of the cascaded power cycles. The influence of the working fluid and the operating conditions are also investigated in this study. Each configuration is modeled and optimized in Aspen HYSYS. The results show that cascaded tCO2/ORC performs better compared with cascaded ORC/ORC and cascaded sCO2/ORC for the case study.
Abstract: The process of post-supercritical CO2 electroplating uses the electrolyte solution after being mixed with supercritical CO2 and released to atmospheric pressure. It utilizes the microbubbles that form when oversaturated CO2 in the electrolyte returns to gaseous state, which gives the similar effect of pulsed electroplating. Under atmospheric pressure, the CO2 bubbles gradually diffuse. Therefore, the introduction of ultrasound and/or other agitation can potentially excite the CO2 microbubbles to achieve an electroplated surface of even higher quality. In this study, during the electroplating process, three different modes of agitation: magnetic stirrer agitation, ultrasonic agitation and a combined mode (magnetic + ultrasonic) were applied, respectively, in order to obtain an optimal surface morphology and mechanical properties for the electroplated Ni coating. It is found that the combined agitation mode at a current density of 40 A/dm2 achieved the smallest grain size, lower surface roughness, and produced an electroplated Ni layer that achieved hardness of 320 HV, much higher when compared with conventional method, which were usually in the range of 160 to 300 HV. However, at the same time, the electroplating with combined agitation developed a higher internal stress of 320 MPa due to the lower current efficiency of the process and finer grain in the coating. Moreover, a new control methodology for tailoring the coating’s mechanical property through its thickness was demonstrated by the timely introduction of ultrasonic agitation during the electroplating process with post supercritical CO2 mixed electrolyte.
Abstract: Synthesizing supercritical carbon dioxide (scCO2) soluble precursors would be helpful for many processes of material syntheses based on scCO2. Ligand (amphi-(1Z, 2Z)-N-(2-fluoro-3-(trifluoromethyl) phenyl)-N'-hydroxy-2-(hydroxyimino) were synthesized from chloro glyoxime and flourus aniline and Pd(II) complex (precursor) prepared. For scCO2 deposition method, organometallic precursor was dissolved in scCO2 and impregnated onto the SBA-15 at 90 °C and 3000 psi. Then the organometallic precursor was reduced with H2 in the CO2 mixture (150 psi H2 + 2850 psi CO2). Pd deposited support material was characterized by ICP-OES, XRD, FE-SEM, TEM and EDX analyses. The Pd loading of the prepared catalyst, measured by ICP-OES showed a value of about 1.64% mol/g Pd of catalyst. Average particle size was found 5.3 nm. The catalytic activity of prepared catalyst was investigated over Suzuki-Miyaura C-C coupling reaction in different solvent with K2CO3 at 50 oC. The conversion ratio was determined by gas chromatography.
Abstract: Even its content is rich in antioxidants ϒ-oryzanol, rice bran is not used properly as functional food. This research aims to (1) extract ϒ-oryzanol; (2) determine the solubility of ϒ-oryzanol in supercritical CO2 based on phase equilibrium theory; and (3) study the effect of process variables on solubility. Extraction experiments were carried out for rice bran (5 g) at various extraction pressures, temperatures and reaction times. The flowrate of supercritical fluid through the extraction vessel was 25 g/min. The extracts were collected and analysed with high-pressure liquid chromatography (HPLC). The conclusion based on the experiments are as: (1) The highest experimental solubility was 0.303 mcg/mL RBO at T= 60°C, P= 90 atm, t= 30 min; (2) Solubility of ϒ-oryzanol was influenced by pressure and temperature. As the pressure and temperature increase, the solubility increases; (3) The solubility data of supercritical extraction can be successfully determined using phase equilibrium theory. Meanwhile, tocopherol was found and slightly investigated in this work.
Abstract: Biodiesel, as an alternative renewable fuel, has been
receiving increasing attention due to the limited supply of fossil fuels
and the increasing need for energy. Microalgae are promising source
for lipids, which can be converted to biodiesel. The biodiesel
production from microalgae lipids using lipase catalyzed reaction in
supercritical CO2 medium has several advantages over conventional
production processes. However, identifying the optimum microalgae
lipid extraction and transesterification conditions is still a challenge.
In this study, the quality of biodiesel produced from lipids extracted
from Scenedesmus sp. and their enzymatic transesterification using
supercritical carbon dioxide have been investigated. At the optimum
conditions, the highest biodiesel production yield was found to be
82%. The fuel properties of the produced biodiesel, without any
separation step, at optimum reaction condition, were determined and
compared to ASTM standards. The properties were found to comply
with the limits, and showed a low glycerol content, without any
separation step.
Abstract: This research studies the electroplating of zinc coating
in the zinc chloride bath mixed with supercritical CO2. The sodium
fluoride (NaF) was used as the bath additive to change the structure
and property of the coating, and therefore the roughness and corrosion
resistance of the zinc coating was investigated. The surface
characterization was performed using optical microscope (OM), X-ray
diffractometer (XRD), and α-step profilometer. Moreover, the
potentiodynamic polarization measurement in 3% NaCl solution was
employed in the corrosion resistance evaluation. Because of the
emulsification of the electrolyte mixed in Sc-CO2, the electroplated
zinc produced the coating with smoother surface, smaller grain, better
throwing power and higher corrosion resistance. The main role played
by the NaF was to reduce the coating’s roughness and grain size. In
other words, the CO2 mixed with the electrolyte under the supercritical
condition performed the similar function as brighter and leveler in zinc
electroplating to enhance the throwing power and corrosion resistance
of the coating.
Abstract: There are many difficulties in the purification of raw components and products. However, researchers are seeking better ways for purification. One of the recent methods is extraction using supercritical fluids. In this study, the phase equilibria of benzoic acid -supercritical carbon dioxide system were investigated. Regarding the phase equilibria of this system, the modeling of solid-supercritical fluid behavior was performed using the Perturbed-Chain Statistical Association Fluid Theory (PC-SAFT) and Peng-Robinson equations of state (PR EoS). For this purpose, five PC-SAFT EoS parameters for pure benzoic acid were obtained using its experimental vapor pressure. Benzoic acid has association sites and the behavior of the benzoic acid-supercritical fluid system was well predicted using both equations of state, while the binary interaction parameter values for PR EoS were negative. Genetic algorithm, which is one of the most accurate global optimization algorithms, was also used to optimize the pure benzoic acid parameters and the binary interaction parameters. The AAD% value for the PC-SAFT EoS, were 0.22 for the carbon dioxide-benzoic acid system.
Abstract: In this study, a nickel film with nano-crystalline grains,
high hardness and smooth surface was electrodeposited using a post
supercritical carbon dioxide (CO2) mixed Watts electrolyte. Although
the hardness was not as high as its Sc-CO2 counterpart, the thin coating
contained significantly less number of nano-sized pinholes. By
measuring the escape concentration of the dissolved CO2 in post
Sc-CO2 mixed electrolyte with the elapsed time, it was believed that
the residue of dissolved CO2 bubbles should closely relate to the
improvement in hardness and surface roughness over its conventional
plating counterpart. Therefore, shortening the duration of
electroplating with the raise of current density up to 0.5 A/cm2 could
effectively retain more post Sc-CO2 mixing effect. This study not only
confirms the roles of dissolved CO2 bubbles in electrolyte but also
provides a potential process to overcome most issues associated with
the cost in building high-pressure chamber for large size products and
continuous plating using supercritical method.