ELECTROCATALYTIC BIO-OIL AND WASTEWATER TREATMENT
Carbon and nitrogen containing molecules (e.g., carboxylic acids, ammonia, amides) present in wastewater streams can be valorized into hydrogen (H2) and volatile hydrocarbons (VHC's) using an catalytic process at room temperature powered by electricity (i.e., electrocatalytic wastewater treatment). The reaction products (i.e., H2 and VHC) are converted back into electricity, CO2 and H2O using gas turbines or solid oxide fuel cells, providing between 10 and 35% of the electricity demand for the electrocatalytic wastewater treatment
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.
METHOD OF CONVERTING ETHANOL TO HIGHER ALCOHOLS
In this invention we have developed a catalyst and process to convert ethanol to higher alcohols via Guerbet condensation chemistry at high selectivity (~90% selectivity to higher alcohols at ~50 percent one pass ethanol conversion). The unconverted ethanol will be easily recycled back to the reactor for further conversion so the ideal over all yield will be ~90%. The uniqueness of this invention is we can achieve this in one single catalytic bed over hydrogen atmosphere at 325 degrees C and 300psig (very mild condition) and also shown the catalyst steady life time greater than 200hrs with consistent selectivity and conversion.
SYSTEMS AND METHODS FOR PREPARING BUTENES
This invention relates to the single step conversion of ethanol and/ or aldehydes (i.e. acetaldehyde, butyraldehydes, crotonaldehyde) (either aqueous or neat) to 1- and 2-butenes-rich olefins. 1-Butene itself a commodity chemical can be converted into polybutene, its main application is as a comonomer in the production of certain kinds of polyethylene, such as linear low-density polyethylene (LLDPE). 1-Butene has also been used as a precursor to polypropylene resins, butylene oxide, and butanone. Mixtures of 1-butene and 2-butene, as produced by the methods disclosed in this invention, can be oligomerized and hydrogenated into gasoline, jet, and diesel fuels and/or into valuable fuel additives and lubricants. For the current alcohol-to-jet process, producing 1- and 2-butene from ethanol is performed in two separate steps by first dehydrating ethanol into ethylene and then dimerizing e thylene into 1- and 2-butene in a second step. Here we disclose the methods for producing 1- and 2-butene mixtures directly from either ethanol, acetaldehyde, butyraldehyde, corotonaldehyde or mixture of ethanol with one of these aldehydes. This is done using specially tailored polyfunctional catalysts comprising metal component with relatively weak hydrogenation ability (e.g., Cu) with mildly acidic support materials (e.g., ZrO2 supported on SiO2). In previous work, including a separate patent, we demonstrated such catalytic materials to be active for converting ethanol into 1,3-butadiene in one reactor. In a separate patent, we demonstrated supported Ag catalysts to be active for (aqueous) ethanol conversion into a mixture of 1 and 2-butenes. Direct conversion of aldehydes or mixture of aldehydes and ethanol into 1 and 2-butenes rich olefins has not been reported before. In this disclosure, we report these catalysts to be active and selective for converting ethanol and/ or aldehydes to 1- and 2-butenes in one single reactor under mild reducing conditions (e.g., under H2, T = 400 degrees C, P = 7 bar). Furthermore, catalyst formulation (i.e. effect of the nature of the support, promoters addition, Cu loading and ZrO2 loading) and process parameters such as H2 concentration, ethanol partial pressure, space velocity were demonstrated to have significant effect on conversion, selectivity, and stability. Results are shown in separate word document with experimental data included in Tables and Figures Here we also demonstrate how catalytic stability is enhanced for the Cu-based catalyst as compared to the Ag-based catalyst. The Cu-based catalyst presents higher resistance to coking and oxidation which enables superior durability. The product from the ethanol and or aldehyde(s) conversion contains primarily butenes and ethylene olefins mixed with H2. We previously demonstrated in a separate patent how these butenes-rich olefins can be oligomerized into gasoline, jet, diesel range hydrocarbons.
SYSTEMS AND METHODS FOR PREPARING BUTENES
This invention relates to the single step conversion of ethanol and/ or aldehydes (i.e. acetaldehyde, butyraldehydes, crotonaldehyde) (either aqueous or neat) to 1- and 2-butenes-rich olefins. 1-Butene itself a commodity chemical can be converted into polybutene, its main application is as a comonomer in the production of certain kinds of polyethylene, such as linear low-density polyethylene (LLDPE). 1-Butene has also been used as a precursor to polypropylene resins, butylene oxide, and butanone. Mixtures of 1-butene and 2-butene, as produced by the methods disclosed in this invention, can be oligomerized and hydrogenated into gasoline, jet, and diesel fuels and/or into valuable fuel additives and lubricants. For the current alcohol-to-jet process, producing 1- and 2-butene from ethanol is performed in two separate steps by first dehydrating ethanol into ethylene and then dimerizing e thylene into 1- and 2-butene in a second step. Here we disclose the methods for producing 1- and 2-butene mixtures directly from either ethanol, acetaldehyde, butyraldehyde, corotonaldehyde or mixture of ethanol with one of these aldehydes. This is done using specially tailored polyfunctional catalysts comprising metal component with relatively weak hydrogenation ability (e.g., Cu) with mildly acidic support materials (e.g., ZrO2 supported on SiO2). In previous work, including a separate patent, we demonstrated such catalytic materials to be active for converting ethanol into 1,3-butadiene in one reactor. In a separate patent, we demonstrated supported Ag catalysts to be active for (aqueous) ethanol conversion into a mixture of 1 and 2-butenes. Direct conversion of aldehydes or mixture of aldehydes and ethanol into 1 and 2-butenes rich olefins has not been reported before. In this disclosure, we report these catalysts to be active and selective for converting ethanol and/ or aldehydes to 1- and 2-butenes in one single reactor under mild reducing conditions (e.g., under H2, T = 400 degrees C, P = 7 bar). Furthermore, catalyst formulation (i.e. effect of the nature of the support, promoters addition, Cu loading and ZrO2 loading) and process parameters such as H2 concentration, ethanol partial pressure, space velocity were demonstrated to have significant effect on conversion, selectivity, and stability. Results are shown in separate word document with experimental data included in Tables and Figures Here we also demonstrate how catalytic stability is enhanced for the Cu-based catalyst as compared to the Ag-based catalyst. The Cu-based catalyst presents higher resistance to coking and oxidation which enables superior durability. The product from the ethanol and or aldehyde(s) conversion contains primarily butenes and ethylene olefins mixed with H2. We previously demonstrated in a separate patent how these butenes-rich olefins can be oligomerized into gasoline, jet, diesel range hydrocarbons.
Uncovering the Details of Proton Relays Vital to Creating New Catalysts for Energy Storage
In their invited review for Chemical Communications, Dr. R. Morris Bullock, Dr. Aaron Appel, and Dr. Monte Helm at PNNL describe how proton relays and other factors influence the catalysts that produce the desired chemical bonds.
Deoxygenation of fatty acids for preparation of hydrocarbons
Embodiments of methods for making renewable diesel by deoxygenating (decarboxylating/decarbonylating/dehydrating) fatty acids to produce hydrocarbons are disclosed. Fatty acids are exposed to a catalyst selected from a) Pt and MO3 on ZrO2 (M is W, Mo, or a combination thereof), or b) Pt/Ge or Pt/Sn on carbon, and the catalyst decarboxylates at least 10% of the fatty acids. In particular embodiments, the catalyst consists essentially of 0.7 wt % Pt and 12 wt % WO3, relative to a mass of catalyst, or the catalyst consists essentially of a) 5 wt % Pt and b) 0.5 wt % Ge or 0.5 wt % Sn, relative to a mass of catalyst. Deoxygenation is performed without added hydrogen and at less than 100 psi. Disclosed embodiments of the catalysts deoxygenate at least 10% of fatty acids in a fatty acid feed, and remain capable of deoxygenating fatty acids for at least 200 minutes to more than 350 hours.).
Nick Barilo
Catalyst Structure And Method Of Fischer-Tropsch Synthesis
The use of microchannel chemical reactors has led to the development of engineered catalysts for reaction systems with intrinsically rapid surface reaction kinetics. By removing or suppressing heat and/or mass transfer limitations and operating under short residence times, a much smaller process system is needed to achieve high product throughput. In addition, the use of short residence times can lead to non-equilibrium product distributions. In this work, engineered catalytic strucures have been developed for carbon monoxide hydrogenation (Fischer-Tropsch Synthesis). The engineered structures must be designed in such a way as to allow for rapid heat removal for the exothermic reaction so that formation of the undesired side paroduct, methane, will be limited. In addition, they must be thermally stable and resistant to deactivation. At the same time, the catalyst structures must provide sufficient dispersion of active metal constituents and they must not produce significant pressure drops through ractor systems.
ELECTRO-FENTON DEPOLYMERIZATION OF WASTE PLASTICS INTO VALUE-ADDED CHEMICALS (iEdison No. 0685901-23-0174)
We have developed an electrochemical process to convert waste polyolefins such as polyethylene (PE) and polypropylene (PP) into mono- and di-carboxylic acids via the electro-Fenton reaction at room temperature and atmospheric pressure. The polymers are fist functionalized with sulfonic groups and then grafted with co-catalysts (FeCl3). The treated polymer is then placed in an electrochemical cell contained carbon electrodes (cathode) that in-situ generated H2O2 via the oxygen reduction reaction (ORR: O2 + 2e- + 2H+ → H2O2) and H2 via the hydrogen evolution reaction (HER: 2e- + 2H+ → H2)as well as regenerated the co-catalysts ( Fe3+ + e- → Fe2+). We used a Pt-mess anode to perform the oxygen evolution reaction (OER: 2H2O → O2 + 4e- + 4H+); however, other non-precious anodes can be used as well. Hydroxyl radicals (·OH) were generated in situ via the Fenton reaction (Fe2+ + H2O2 → Fe2+ + OH- + ·OH) and depolymerized PE selectively into oxalic acid. The excess H+ and e- are recombined into H2.