ULTRA-STABLE REFERENCE ELECTRODE FOR ENERGY STORAGE AND CONVERSION SYSTEMS (iEdison No. 0685901-22-0172)
The inventors have developed an ultra-stable reference electrode (RE) for energy storage and conversion systems for assessment of energy storage devices, including redox flow batteries. The reference electrode provides improved accuracy, stability, repeatability, and reliability when monitoring batteries. The electrode can be used in situ. More specifically, the newly invented RE, based on a dynamic hydrogen electrode (DHE) with a novel design on the area and surface roughness of platinum electrodes, demonstrates high accuracy and long-term stability that enables in-situ monitoring of individual electrode potentials throughout 500 cycles.
SOLVENT EXTRACTION SYSTEM AND PROCESS FOR HYDROTHERMAL LIQUEFACTION (iEdison No. 0685901-23-0045)
A liquid-liquid extraction process has been developed for the hydrothermal liquefaction (HTL) process to separate biocrude produce from aqueous and solids coproducts. HTL is a general process to convert aqueous biomass to a mixture of hydrocarbon liquids, commonly referred to as 'biocrude" because it has physical properties similar to crude petroleum oil, as well as less desirable aqueous and solid byproducts. The product of the HTL reactor is a stable emulsion of the solid, oil, and aqueous phases that must be separated for downstream processing. The emulsion product generally does not phase separate at ambient conditions for several reasons. The density of the biocrude product is very similar to the aqueous phase, both with a specific gravity of approximately 1. The solids are extremely fine, with many particles less than 10 microns. The solid particles are hydrophilic and stabilize the oil/water mixture. The oil coats a portion of the solid particle and the solid keeps the oil droplet dispersed due to the solid's affinity for water. The biocrude is very viscous and makes freeing the solid particles from the oil suspension difficult. The aqueous phase contains many soluble organic species, which act as natural surfactants and stabilize the oil-water interface. A solvent extraction process was invented to overcome these challenges to efficiently separate the oil, aqueous, and solid phases. A solvent is mixed with the HTL product emulsion and the biocrude is dissolved into the solvent, which then phase separates from the water and solids by traditional gravimetric separation processes (see Figure 1). The extraction process can occur as a single stage, multi-stage, or continuous counter-current step. After the biocrude is extracted from the HTL product emulsion mixture, the solvent and biocrude stream is sent to a distillation tower to separate the more volatile solvent from the heavier biocrude product. The biocrude can then be exported for downstream processing. The aqueous and solids stream is sent to wastewater processing for further treatment. This invention is not limited to the use of a particular solvent, but the solvents presented here were chosen based on their affinity for the biocrude product relative to the aqueous phase, their commercial availability, their compatibility with the downstream fuels process infrastructure, and energy efficiency for purifying and recycling the solvent. Figure 2 illustrates the solvent extraction process design in more detail than Figure 1, however some equipment is still omitted for clarity. A two-stage solvent extraction process is shown in this example, but this invention is not limited to this exact process configuration. 'HTL emulsion product" enters the unit from the HTL reactor section. The emulsion composition can vary, but it is generally around 77% water, 13% biocrude, and 10% solids. The HTL reactor product is typically at an elevated temperature relative to the optimal temperature for the solvent extraction process, so the emulsion stream passes through a cooler to reach the target temperature. The emulsion is then mixed with the extraction solvent, which contains a small amount of residual biocrude. Note the extraction shown here is staged in a countercurrent fashion. This means the fresh solvent is introduced to the second extraction stage and cascaded to the first stage. Countercurrent flow was chosen to optimize extraction efficiency, but it is not a requirement of the invention. The combined solvent and HTL product emulsion stream then passes through a mixing device ('1st Stage Mixer") to ensure good surface area contact between the solvent and emulsion. The mixture enters a settling vessel, which provides residence time under calm conditions allow the oil (solvent+biocrude) and aqueous phases to settle. There may be internals inside of the settling vessel to enhance the settling process. The oil phase is less dense than the aqueous phase, which will rise and can be withdrawn near the top of the vessel. The aqueous phase and solids will sink to the bottom of the settling vessel and can be withdrawn from the bottom. The solvent must be separated from the biocrude so it can be recycled. The solvent is chosen to be more volatile than the biocrude to allow it to be separated by distillation. The design of the Solvent Recovery Tower is independent of this invention. Relatively few fractionation stages will be required in practice if there is a large volatility difference between the selected solvent and biocrude. A large volatility difference between the solvent and biocrude allows the solvent to be separated at a lower temperature, which has several advantages. Distillation at lower temperature saves energy and allows cheaper energy sources to be used for heating (low pressure steam, etc). More importantly, lower distillation temperatures reduce the temperature of the biocrude in the bottom of the tower. Biocrude can break down (crack) or leave fouling deposits at high temperatures. The cracking products are corrosive and degrade the biocrude quality. The solvent is boiled overhead and recycled. A small amount of makeup solvent is added to the recycle stream to account for the solvent that leaves the system. The recycled solvent is mixed with the aqueous + bottoms stream leaving the bottom of the 1st Extraction Stage. The purpose of adding the recycle solvent at this point is to extract any remaining biocrude in the aqueous stream. The mixture of solvent and Aqueous stream then enters another settling vessel, which functions the same as the 1st Stage settling vessel. Solvent with the extracted residual biocrude exits the top portion of the 2nd Stage settling vessel. Note that the oil stream exiting the 2nd Stage settling vessel is mostly solvent with only a very minor amount of biocrude present. Because the steam is mostly solvent in composition, it can be used for the 1st Stage extraction. The Aqueous + Solids stream leaving the bottom of the 2nd Stage Separator vessel is nearly free of biocrude. Some solvent will remain in this stream due to solubility in water or minor entrainment. A desirable solvent will have a low solubility in water to minimize the amount of solvent leaving the bottom of the 2nd Stage Separator. Solvent leaving the bottom of the 2nd Stage Separator is reclaimed in the Water Product Stripper. The design of the Water Product Stripper is independent of this invention. In practice, the tower will likely have simple internals that are resistant to fouling. A resistance to fouling will be important because of the high solids concentration of the feed stream ( > 10%wt solids). The minor amount of solvent is boiled overhead and recycled to the extraction process. The ability to boil the solvent from the aqueous stream is another driver for a relatively high volatility solvent. Solvents with a low vapor pressure will not volatilize before water. Therefore, the boiling point of the selected solvent should not be significantly above the boiling point of water (100 degC). Figure 3 details a more specific application of the invention. This figure represents the application of this invention to the published 'State of Technology" business case detailing a 110 dry ton per day HTL plant (PNNL-32731) using toluene as the extraction solvent. The following information is available in the figure: Heat and Material Balance Auxiliary equipment required for reliable operation and energy efficiency Approximate stream compositions Process operating conditions Equipment sizing
METHOD AND SYSTEM EMBODIMENTS FOR CONVERTING ETHANOL TO PARA-XYLENE AND ORTHO-XYLENE (iEdison No. 0685901-19-0012)
In collaboration with LanzaTech we have developed a chemistry to generate p-xylene from ethanol. The innovation involves the conversion of ethanol derived acetaldehyde to p-methylbenzaldehyde over mixed oxide catalyst followed by the conversion to p-xylene via hydrogenolysis (ethanol → acetaldehyde → p-methyl benzaldehyde → p-xylene). Among aromatics, the production distribution contains only p-xylene, o-xylene and benzene. Typical p-xylene synthesis (both conventional and renewable) process contains range of aromatics (e.g. benzene, toluene, o-xylene, ethyl benzene, m-xylene, p-xylene etc.) that needs to be purified via the expensive separation process. The simple aromatic stream provides to major advantages over the conventional and other renewable technologies. 1) The aromatic mixture to p-xylene separation/purification steps become simpler and cheaper 2) Enables to build a modular plant to meet the local renewable feedstock availability and reduces the feedstock transportation cost
Functional Sorbent for Chemical Separations and Sequential Forming Process
This invention describes novel methodology for making a nanoporous composite materials that have higher functional density than is possible using standard self-assembly methods. In addition, this methodology also provides greater access to the sorbent binding sites than is possible using “standard” polymer deposition methods.
Metal Fluoride Electrode Protection Layer and Method of Making Same
The present invention discloses a method to modify the titanium oxide based anode materials by coating a thin layer of AlF3 on the particle surface and the excellent battery performance for the thus obtained surface-modified titanium oxide based materials. This method is simple and cost effective. The key aspect of the present invention is to keep the AlF3 coating at low content particularly between 0.1% and 10% and more particularly between 1% and 5%. The thin AlF3-coating layer significantly improves the power performance, capacity retention at elevated temperatures and long term cycle life of the lithium-ion batteries using these surface-modified anode materials.
Sulfur-Tolerant Catalyst Systems
The addition of Pr and Ru to the Ni-YSZ anode has shown in the button cell test to significantly improve the sulfur tolerance against the 1st stage degradation caused by H2S in the fuel.
MULTI-DOMAIN SITUATIONAL AWARENESS FOR INFRASTRUCTURE MONITORING
Apparatus and methods are disclosed for a monitoring system that integrates multi-domain data from weather, power, cyber, and/or social media sources to greatly increase situation awareness and drive more accurate assessments of reliability, sustainability, and efficiency in infrastructure environments, such as power grids. In one example of the disclosed technology, a method includes receiving real-time data from two or more different domains relevant to an infrastructure system, aggregating the real-time data into a unified representation relevant to the infrastructure system, and providing the unified representation to one or more customizable graphical user interfaces.
METHOD OF COMBINED SEPARATION AND CONVERSION OF AN OXYGENATE AND MICROCHANNEL REACTIVE DISTILLATION APPARATUS (iEdison No. 0685901-20-0041)
Here we demonstrate the proof-of-concept for microchannel reactive distillation for alcohol-to-jet application: combining ethanol/water separation and ethanol dehydration in one unit operation. Ethanol is first distilled into the vapor phase, converted to ethylene and water, and then the water co-product is condensed to the shift reaction equilibrium. Process intensification is achieved through rapid mass transfer - ethanol stripping from thin wicks using novel microchannel architectures - leading to lower residence time and improved separation efficiency. Energy savings are realized with integration of unit operations. For example, heat of condensing water can offset vaporizing ethanol. Furthermore, the dehydration reaction equilibrium shifts towards completion by immediate removal of the water byproduct upon formation while maintaining aqueous feedstock in the condensed phase. Conversion of 40% ethanol in water to ethylene was demonstrated with 91% ethylene selectivity and 71% ethanol conversion at 220oC, 600 psig, and 0.28 hr-1. Almost three stages of separation (2.7) were also demonstrated, under these conditions, using a device length of 9.1 cm. This provides a height equivalent of a theoretical plate (HETP), a measure of separation efficiency, of ~ 3.3. By comparison, conventional distillation packing provides an HETP of ~ 30 cm. Thus, 9X reduction in HETP was demonstrated over conventional technology, providing a means for significant energy savings.
SELECTIVE RECOVERY OF RARE EARTH ELEMENTS FROM PERMANENT MAGNETS BY ELECTROCHEMICAL LEACHING AND ELECTRODEPOSITION (iEdison No. 0685901-22-0028)
Rare earth elements (REEs) are the 15 metals in the lanthanide series of the periodic table. They have very similar properties and are often found together in geologic deposits. Most of the REE today are produced outside the United States ( > 80% being produced in China) and given that they are a key component in permanent magnets (PMs) used in clean energy technologies such as wind turbines, hybrid and electric vehicles, and other electromagnetic-to-mechanical conversion systems, as well as an essential component for optical drives and smartphones, they are deemed critical elements. As we work to rapidly transition to clean energy technologies, there is need for building a reliable domestic REE supply. One approach to sustainably increasing REE supply is through recycling of spent PMs. Existing methods for recycling magnets rely on pyrometallurgical or hydrometallurgical methods which need energy-intensive pretreatments or significant amounts of acid and chemical inputs—making them not sustainable. In contrast we report a promising new electrochemical method that is performed at room-temperature and without need for corrosives and can selectively recover REE from used PMs. We demonstrate the approach using a commercial neodymium-iron-boron (NdFeB) permanent magnet—one of the most widely used variety of magnets. We show selective Nd recovery, but the approach is also relevant to selective recovery of other REEs used in PMs. Our method involves selective electrochemical leaching of Nd from NdFeB permanent magnet followed by subsequent Nd electrodeposition on an electrode. Both steps are conducted using commercial organic electrolytes (Dimethylformamide, DMF) to ensure process scalability. We conducted experiments using commercial magnets to ensure results are transferable to industry. There are very few reported electrochemical methods for recycling, and they are all limited to aqueous acid based electrolytes—clearly distinguishing our work.