CAPTURE AND RELEASE OF ACID GASSES USING TUNABLE ORGANIC SOLVENTS WITH AMINOPYRIDINE
A class of water lean, organic solvents that can bind with various acid gasses to form acid gas bound molecules having a high degree of intramolecular hydrogen bonding which enables their use as regenerable solvents for acid gas capture. Unlike the other devices described in the prior art, the present invention takes advantage of shortened distances between the portions of the molecule that form hydrogen bonds within the structures when loaded with an acid gas so as to create a molecule with a higher internal bonding affinity and a reduced proclivity for agglomeration with other molecules.
CAPTURE AND RELEASE OF ACID GASSES USING TUNABLE ORGANIC SOLVENTS WITH AMINOPYRIDINE
A class of water lean, organic solvents that can bind with various acid gasses to form acid gas bound molecules having a high degree of intramolecular hydrogen bonding which enables their use as regenerable solvents for acid gas capture. Unlike the other devices described in the prior art, the present invention takes advantage of shortened distances between the portions of the molecule that form hydrogen bonds within the structures when loaded with an acid gas so as to create a molecule with a higher internal bonding affinity and a reduced proclivity for agglomeration with other molecules.
CAPTURE AND RELEASE OF ACID GASSES USING TUNABLE ORGANIC SOLVENTS WITH AMINOPYRIDINE
A class of water lean, organic solvents that can bind with various acid gasses to form acid gas bound molecules having a high degree of intramolecular hydrogen bonding which enables their use as regenerable solvents for acid gas capture. Unlike the other devices described in the prior art, the present invention takes advantage of shortened distances between the portions of the molecule that form hydrogen bonds within the structures when loaded with an acid gas so as to create a molecule with a higher internal bonding affinity and a reduced proclivity for agglomeration with other molecules.
CAPTURE AND RELEASE OF ACID GASSES USING TUNABLE ORGANIC SOLVENTS WITH AMINOPYRIDINE
A class of water lean, organic solvents that can bind with various acid gasses to form acid gas bound molecules having a high degree of intramolecular hydrogen bonding which enables their use as regenerable solvents for acid gas capture. Unlike the other devices described in the prior art, the present invention takes advantage of shortened distances between the portions of the molecule that form hydrogen bonds within the structures when loaded with an acid gas so as to create a molecule with a higher internal bonding affinity and a reduced proclivity for agglomeration with other molecules.
CAPTURE AND RELEASE OF ACID GASSES USING TUNABLE ORGANIC SOLVENTS WITH BINDING ORGANIC LIQUIDS
A class of water lean, organic solvents that can bind with various acid gasses to form acid gas bound molecules having a high degree of intramolecular hydrogen bonding which enables their use as regenerable solvents for acid gas capture. Unlike the other devices described in the prior art, the present invention takes advantage of shortened distances between the portions of the molecule that form hydrogen bonds within the structures when loaded with an acid gas so as to create a molecule with a higher internal bonding affinity and a reduced proclivity for agglomeration with other molecules.
Heavy Fossil Hydrocarbon and Upgrading Using Radio-Frequency or Microwave Energy
This invention disclosure report describes alternative methods of direct coal liquefaction for the production of chemicals and fuels. Through utilization of microwave or Rf energies, coal is directly converted to a variety of value-added chemicals and fuels. Direct generation of acetylene, olefins, BTX, naphtha, naphthalenes, and fuel precursors from coal in inert atmospheres are observed. Addition of hydrogen and/or methane can further increases direct fuel production and hydrogenation of the coal-derived liquids is observed at atmospheric pressure and modest temperatures. Modifications of reactants, process parameters, and reactor design can significantly influence the relative product distribution of chemicals and fuels generated.
IN-SITU HEALTH MONITORING SYSTEM FOR REDOX FLOW BATTERIES (iEdison No. 0685901-22-0242)
We designed an acoustic monitoring system to detect hydrogen bubbles in the analyte solution of all-vanadium redox flow batteries (AVFBs). The system has a specially designed ultrasonic probing cell made of borosilicate glass that can be integrated into the flow system on the analyte side (Figure 1). The analyte solution firstly flows through the negative electrode, where the chemical reaction occurs and hydrogen bubbles are generated, and then flows into the ultrasonic probing cell. The ultrasonic transducer transmits signals into the probing cell and collects echoes that propagate through the electrolyte solution in the probing cell. Details about how the signals are transmitted and received are included in Appendix A. The echoes are collected by the ultrasonic receiver and sent to the computer for data analysis. The sound speed and the acoustic attenuation coefficient are calculated from these echoes, with the detailed methods given in Appendix B and C. Bubbles that flow through the acoustic path are reflected as abnormal values in the measurements of the sound speed and the attenuation coefficient. This method not only can detect bubbles in the analyte solution, but also can estimate the bubble flow speed. The monitoring system can continuously monitor bubble amounts in negative electrolytes without interrupting the battery operation, and thus provides a real-time noninvasive surveillance of the health status of flow battery systems. Figure 1. Schematic of the in-situ battery health monitoring system for hydrogen detection in an all-vanadium redox flow battery.
Selective CO methanation catalysis
Carbon monoxide (CO) is selectively reacted with hydrogen (H2) over a ruthenium (Ru) on alumina catalyst at a temperature of about 210 to about 290° C. To be a viable option for micro catalytic fuel processing devices, highly active, selective, and stable catalysts must be demonstrated with as large a temperature window for feasible operation as possible. We have studied the effects of metal loading, preparation method, pretreatment conditions, and choice of support on the performance of Ru-based catalysts for such applications. Catalyst testing results and catalyst characterization using XRD and BET are discussed. In one example, operating at a gas hourly space velocity (GHSV) of 13,500 hr−1, a 3% Ru/Al2O3 catalyst yielded CO outputs less than 100 ppm in a temperature range from 240° C. to 285° C., while not exceeding a hydrogen consumption of 10%. This catalyst was further successfully demonstrated in a microchannel device.
SINGLE-REACTOR CONVERSION OF ETHANOL TO 1-/2-BUTENES
This invention relates to the single step conversion of ethanol (either aqueous or neat) to 1- and 2-butenes. 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 into gasoline, jet, and diesel fuels and/or into valuable fuel additives and lubricants. Currently, producing 1- and 2-butene from ethanol is performed by first dehydrating ethanol into ethylene and then ethylene can be dimerized into 1- and 2-butene in a second step. Here we disclose the methods for producing 1- and 2-butene mixtures directly from ethanol using specially tailored polyfunctional catalysts comprising metal component with relatively weak hydrogenation ability (e.g., Ag) with mildly acidic support materials (e.g., ZrO2 supported on SiO2). In previous work, including the filing of a separate patent, we demonstrated such catalytic materials to be active for converting ethanol into 1,3-butadiene in one reactor. In this disclosure we report these catalysts to be active and selective for converting ethanol to 1- and 2-butenes in one single reactor under mild reducing conditions (e.g., under H2, T = 325 degrees C, P = 7 bar). Furthermore, parameters such as H2 concentration, H2O concentration, space velocity and pressure were demonstrated to have significant effect on conversion, selectivity, and stability. H2-addition to the feed favors the formation of 1- and 2-butene at the expense of butadiene (see Table 1 in Slide 2 of the attached PPT file). For example, for a 4Ag/4ZrO2/SiO2 catalyst operating at 325 degrees C, P = 7 bar, WHSV= 0.23 hr-1, incremental addition of H2 to the feed gas from 0% to 100% (carrier gas content) leads to a decrease of conversion from 99 to 85% accompanied by an increase of the 1- and 2-butene combined selectivity from ~ 16 to 51%. Meanwhile the ethylene selectivity increases from ~ 8.6 to 26% while the butadiene selectivity decreases from 63.7% to 0%. Thus, in general 1- and 2-butene is formed at the expense of 1,3-butadiene when H2 content is added to the feed. We also demonstrated how catalytic stability is enhanced when H2 is added to N2 as the carrier gas for the process (see Slide 9 in the attached PPT summary). Thus, the addition of H2 (to the ethanol feed) not only alters the product distribution favoring a butene product slate but it also significantly suppresses coking resulting in enhanced catalytic stability. We also note that while H2 addition to the feed may add cost to the overall process, hydrogen is usually needed anyhow for fuels production as the final olefin product after oligomerization needs to be hydrotreated. Thus, the added hydrogen can be used in the latter hydrotreatment step and unconverted hydrogen can be recycled to the front end of the process. We further investigated process parameters that affect catalytic performance. For example, higher contact time favors the formation of 1- and 2-butenes (see Table 2 in Slide 3 of the attached PPT file). As shown in Table 2 decreasing the space velocity from 14.6 to 0.23 hr-1 while operating under H2 gas leads to an increase of the conversion from ~ 11 to 85% and an increase of both 1- and 2-butenes and ethylene selectivities from ~13 to 51% and ~15 to 26%, respectively. Meanwhile, both acetaldehyde and butyraldehyde selectivities decrease whereas butadiene selectivity remains negligible. This suggests that the mechanism for butene formation involves the conversion of acetaldehyde to crotyl alcohol, isomerization of crotyl alcohol to butyraldehyde, and butenes formation from butyraldehyde deoxygenation. The effect of operating pressure was also investigated and it was found that higher pressure favors the formation of butenes at the expense of butadiene (see Table 3 in Slide 4 in the attached PPT file). For example, increasing the pressure from atmospheric to 14 bar while operating under H2 gas leads to an increase of the conversion from 52 to 83% and an increase of the C4+ olefins selectivity from 8.1 to 44% while the selectivity toward butadiene and ethylene decreases from 43 to 0% and 22 to 7%, respectively. Addition of water to the feed also leads to a decrease of the conversion, from 94.0%, with 100 % ethanol as a feedstock, and to 76%, with 35% ethanol in H2O as a feedstock (see Table 4 in Slide 5 in the PPT file). The butenes selectivity is only slightly affected by the presence of water since it decreases from 58% to 55%. However, this demonstrates that diluted feeds of ethanol can be used as feedstock and separation of water and ethanol is not required prior to conversion. The product from the ethanol conversion contains primarily butenes and ethylene olefins mixed with H2. Thus, for purpose of producing fuels from the olefin precursors we also demonstrated feasibility for oligomerization by co-feeding ethylene and/or H2 with butene mixtures over zeolite catalysts. Oligomerization of butenes in the presence of H2 was found to be feasible (see Slide 6 in the attached file). Adding H2 to the feed leads to about 20% lower C8+ olefins production. Oligomerization of butenes + ethylene mixture was also investigated to determine the effect of ethylene on the oligomerization of butenes (see Slide 7 in the attached PPT file). Adding ethylene to the feed was also demonstrated to lead to higher paraffins/olefins ratio due to hydrogenation activity but does not affect the production of C8+ olefins since the same quantity of product was obtained w and w/o ethylene addition to the feed. Oligomerization of butenes in the presence of H2 and ethylene was also examined (see Slide 8 in the attached PPT file). The ratio paraffins/olefins is equal to about 0.4 in the presence of H2 + ethylene as opposed to < 0.5 without H 2 + ethylene indicating a significant hydrogenation activity. The quantity of C 8 + olefins produced is about 10% higher in the presence of H 2 and ethylene and is likely due to ethylene oligomerization to C 8 + product occurring in the meantime as butenes oligomerization. Thus, we demonstrate that oligomerization of 1-butene is feasible in the presence of H 2 and/or ethylene co-feed. We also note that in separate experiments (not shown) we show the product distribution for 2-butene oligomerization to be very similar to that of 1-butene. Thus, a feed containing mixtures and 1- and 2-butene would produce a similar product distribution.
CATALYTIC CONVERSION OF ETHANOL TO 1-/2-BUTENES
This invention relates to the single step conversion of ethanol (either aqueous or neat) to 1- and 2-butenes. 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 into gasoline, jet, and diesel fuels and/or into valuable fuel additives and lubricants. Currently, producing 1- and 2-butene from ethanol is performed by first dehydrating ethanol into ethylene and then ethylene can be dimerized into 1- and 2-butene in a second step. Here we disclose the methods for producing 1- and 2-butene mixtures directly from ethanol using specially tailored polyfunctional catalysts comprising metal component with relatively weak hydrogenation ability (e.g., Ag) with mildly acidic support materials (e.g., ZrO2 supported on SiO2). In previous work, including the filing of a separate patent, we demonstrated such catalytic materials to be active for converting ethanol into 1,3-butadiene in one reactor. In this disclosure we report these catalysts to be active and selective for converting ethanol to 1- and 2-butenes in one single reactor under mild reducing conditions (e.g., under H2, T = 325 degrees C, P = 7 bar). Furthermore, parameters such as H2 concentration, H2O concentration, space velocity and pressure were demonstrated to have significant effect on conversion, selectivity, and stability. H2-addition to the feed favors the formation of 1- and 2-butene at the expense of butadiene (see Table 1 in Slide 2 of the attached PPT file). For example, for a 4Ag/4ZrO2/SiO2 catalyst operating at 325 degrees C, P = 7 bar, WHSV= 0.23 hr-1, incremental addition of H2 to the feed gas from 0% to 100% (carrier gas content) leads to a decrease of conversion from 99 to 85% accompanied by an increase of the 1- and 2-butene combined selectivity from ~ 16 to 51%. Meanwhile the ethylene selectivity increases from ~ 8.6 to 26% while the butadiene selectivity decreases from 63.7% to 0%. Thus, in general 1- and 2-butene is formed at the expense of 1,3-butadiene when H2 content is added to the feed. We also demonstrated how catalytic stability is enhanced when H2 is added to N2 as the carrier gas for the process (see Slide 9 in the attached PPT summary). Thus, the addition of H2 (to the ethanol feed) not only alters the product distribution favoring a butene product slate but it also significantly suppresses coking resulting in enhanced catalytic stability. We also note that while H2 addition to the feed may add cost to the overall process, hydrogen is usually needed anyhow for fuels production as the final olefin product after oligomerization needs to be hydrotreated. Thus, the added hydrogen can be used in the latter hydrotreatment step and unconverted hydrogen can be recycled to the front end of the process. We further investigated process parameters that affect catalytic performance. For example, higher contact time favors the formation of 1- and 2-butenes (see Table 2 in Slide 3 of the attached PPT file). As shown in Table 2 decreasing the space velocity from 14.6 to 0.23 hr-1 while operating under H2 gas leads to an increase of the conversion from ~ 11 to 85% and an increase of both 1- and 2-butenes and ethylene selectivities from ~13 to 51% and ~15 to 26%, respectively. Meanwhile, both acetaldehyde and butyraldehyde selectivities decrease whereas butadiene selectivity remains negligible. This suggests that the mechanism for butene formation involves the conversion of acetaldehyde to crotyl alcohol, isomerization of crotyl alcohol to butyraldehyde, and butenes formation from butyraldehyde deoxygenation. The effect of operating pressure was also investigated and it was found that higher pressure favors the formation of butenes at the expense of butadiene (see Table 3 in Slide 4 in the attached PPT file). For example, increasing the pressure from atmospheric to 14 bar while operating under H2 gas leads to an increase of the conversion from 52 to 83% and an increase of the C4+ olefins selectivity from 8.1 to 44% while the selectivity toward butadiene and ethylene decreases from 43 to 0% and 22 to 7%, respectively. Addition of water to the feed also leads to a decrease of the conversion, from 94.0%, with 100 % ethanol as a feedstock, and to 76%, with 35% ethanol in H2O as a feedstock (see Table 4 in Slide 5 in the PPT file). The butenes selectivity is only slightly affected by the presence of water since it decreases from 58% to 55%. However, this demonstrates that diluted feeds of ethanol can be used as feedstock and separation of water and ethanol is not required prior to conversion. The product from the ethanol conversion contains primarily butenes and ethylene olefins mixed with H2. Thus, for purpose of producing fuels from the olefin precursors we also demonstrated feasibility for oligomerization by co-feeding ethylene and/or H2 with butene mixtures over zeolite catalysts. Oligomerization of butenes in the presence of H2 was found to be feasible (see Slide 6 in the attached file). Adding H2 to the feed leads to about 20% lower C8+ olefins production. Oligomerization of butenes + ethylene mixture was also investigated to determine the effect of ethylene on the oligomerization of butenes (see Slide 7 in the attached PPT file). Adding ethylene to the feed was also demonstrated to lead to higher paraffins/olefins ratio due to hydrogenation activity but does not affect the production of C8+ olefins since the same quantity of product was obtained w and w/o ethylene addition to the feed. Oligomerization of butenes in the presence of H2 and ethylene was also examined (see Slide 8 in the attached PPT file). The ratio paraffins/olefins is equal to about 0.4 in the presence of H2 + ethylene as opposed to < 0.5 without H 2 + ethylene indicating a significant hydrogenation activity. The quantity of C 8 + olefins produced is about 10% higher in the presence of H 2 and ethylene and is likely due to ethylene oligomerization to C 8 + product occurring in the meantime as butenes oligomerization. Thus, we demonstrate that oligomerization of 1-butene is feasible in the presence of H 2 and/or ethylene co-feed. We also note that in separate experiments (not shown) we show the product distribution for 2-butene oligomerization to be very similar to that of 1-butene. Thus, a feed containing mixtures and 1- and 2-butene would produce a similar product distribution.