Cascaded Transcritical/Supercritical CO2 Cycles and Organic Rankine Cycles to Recover Low-Temperature Waste Heat and LNG Cold Energy Simultaneously

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.

Nickel Electroplating in Post Supercritical CO2 Mixed Watts Bath under Different Agitations

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.

Synthesis of Vic-Dioxime Palladium (II) Complex: Precursor for Deposition on SBA-15 in ScCO2

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.

Using Phase Equilibrium Theory to Calculate Solubility of γ-Oryzanol in Supercritical CO2

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.

Properties of Biodiesel Produced by Enzymatic Transesterification of Lipids Extracted from Microalgae in Supercritical Carbon Dioxide Medium

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.

The Effects of NaF Concentration on the Zinc Coating Electroplated in Supercritical CO2 Mixed Zinc Chloride Bath

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.

Prediction of the Solubility of Benzoic Acid in Supercritical CO2 Using the PC-SAFT EoS

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.

Current Density Effect on Nickel Electroplating Using Post Supercritical CO2 Mixed Watts Electrolyte

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.