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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Aliphatic Amines from Waste Polyolefins by Tandem Pyrolysis, Hydroformylation, and Reductive Amination

Pyrolysis of waste plastics can produce a product mixture with a high concentration of olefins (>50 wt%). The olefins, as building blocks in the petroleum industry, are potential precursors for valuable commodity chemicals with higher values (>$2000 per ton). In this work, we produce aldehydes by hydroformylation of the olefins present in pyrolysis oil from colored post-consumer recycled high-density polyethylene (PCR-HDPE). The obtained aldehydes in the oil are then converted into aliphatic amines via reductive amination with a Ru/C catalyst. The aminated oil was characterized by multiple analytical chemistry techniques including elemental analysis, nuclear magnetic resonance spectroscopy, high-resolution liquid chromatography-mass spectrometry, and gas chromatography-mass spectrometry with a Polyarc flame ionization detector. The concentration of metals in the PCR-HDPE and oil changes during the tandem processes, showing limited effects of these elements (e.g., Al, Ca, Fe, Mg, Ti, Zn) on hydroformylation and reductive amination. Additionally, we demonstrated that reductive amination of aldehydes with varied carbon numbers and branching properties can be achieved in the presence of a complex mixture, including paraffins and aromatics. The results indicate that waste plastics have the potential to serve as a renewable source for mono and di aliphatic amines, thereby diminishing reliance on fossil feedstocks as the current primary amine source.

aliphatic amines↗
NASA NTRS1973

CO2 removal by solid amine sorbents. 1: Experimental studies of amine resin IR-45 with regard to spacecraft applications. 2: Computer program for predicting the transient performance of solid amine sorbent systems

The sorbent behavior of solid amine resin IR-45 with regard to potential use in regenerative CO2-removal systems for manned spacecraft is considered. Measurements of equilibrium sorption capacity of IR-45 for water and for CO2 are reported, and the dynamic mass transfer behavior of IR-45 beds is studied under conditions representative of those expected in a manned spacecraft. A digital computer program was written for the transient performance prediction of CO2 removal systems comprised of solid amine beds. Also evaluated are systems employing inorganic molecular-sieve sorbents. Tests show that there is definitely an effect of water loading on the absorption rate.

Wright, R. M.↗
NASA NTRS1983

Synthesis and characterization of bisimide amines and bisimide amine-cured epoxy resins

An attempt is made to develop tough, moisture resistant, high char yield epoxy resins by means of novel bisimide amine (BIA) hardener curing agents and a state-of-the-art epoxy resin system. The BIAs are isolated as mixtures containing monomer, oligomer, and polymeric species, and then characterized by elemental analysis and high pressure liquid chromatography. The bisimide amine-cured epoxies (IMEs) were characterized with respect to moisture absorption, thermal properties, and physical and mechanical properties, as well as in the role of matrices in Celion 6000/IME composites. The relative toughness characteristics of each IME formulation was measured by the 10 deg off-axis tensile test, measuring the uniaxial tensile strength, shear strength, and shear-strain-to-failure of the composite systems.

Scola, D. A.↗
DOE OSTI2021

New reactions of diazene and related species for modelling combustion of amine fuels

Potential energy surfaces for reactions involving N 2 H 2 isomers of diazene (diimide) have been explored using density functional theory, with energies based on coupled-cluster theory. A focus is on processes that create or consume these species, and isomerisation between the E (trans) and Z (cis) forms of HNNH. Furthermore, these include isomerisation and dissociation pathways for HNNH, addition of H atoms to form N 2 H 3 , abstraction by H atoms yielding short-lived NNH, and abstraction reactions of H with N 2 H 3 . Transition state and capture theories are applied for high-pressure-limiting behaviour, while low-pressure and falloff regions are characterised via the methods of Troe and coworkers. Rate constants and thermochemistry are provided to improve models of diamine chemistry, relevant to the combustion of NH 3 especially at high concentrations, high pressures or under reducing conditions. Results indicate that amine radical recombination mainly yields the E HNNH isomer, while H-abstraction from N 2 H 3 results in E HNNH and H 2 NN. However, at elevated temperature E → Z isomerisation becomes competitive, and Z HNNH, being more reactive, acts to enhance the diazene consumption rate.

10 SYNTHETIC FUELS↗
NASA NTRS1982

Synthesis and characterization of bisimide amines and bisimide amine-cured epoxy resins

A study has been conducted with the objective of developing tough, moisture resistant, high char yield epoxy resins using novel bisimide amine (BIA) hardeners as curing agents with MY-720, a commercial state-of-the-art epoxy resin system. BIA cured epoxies are shown to have lower moisture absorption than MY-720 and other state-of-the-art epoxy resins; the tensile strengths and strain-to-failures of several of the bisimide epoxy resins (IME's) are higher than those of the state-of-the-art epoxies. Most IME's have compression properties equivalent to those of state-of-the-art epoxies. Two resin systems, IME-10 and IME-12-3, have better overall properties than other resin systems investigated.

Scola, D. A.↗
NASA NTRS2016

Reliability and Maintainability Analysis for the Amine Swingbed Carbon Dioxide Removal System

I have performed a reliability & maintainability analysis for the Amine Swingbed payload system. The Amine Swingbed is a carbon dioxide removal technology that has gone through 2,400 hours of International Space Station on-orbit use between 2013 and 2016. While the Amine Swingbed is currently an experimental payload system, the Amine Swingbed may be converted to system hardware. If the Amine Swingbed becomes system hardware, it will supplement the Carbon Dioxide Removal Assembly (CDRA) as the primary CO2 removal technology on the International Space Station. NASA is also considering using the Amine Swingbed as the primary carbon dioxide removal technology for future extravehicular mobility units and for the Orion, which will be used for the Asteroid Redirect and Journey to Mars missions. The qualitative component of the reliability and maintainability analysis is a Failure Modes and Effects Analysis (FMEA). In the FMEA, I have investigated how individual components in the Amine Swingbed may fail, and what the worst case scenario is should a failure occur. The significant failure effects are the loss of ability to remove carbon dioxide, the formation of ammonia due to chemical degradation of the amine, and loss of atmosphere because the Amine Swingbed uses the vacuum of space to regenerate the Amine Swingbed. In the quantitative component of the reliability and maintainability analysis, I have assumed a constant failure rate for both electronic and nonelectronic parts. Using this data, I have created a Poisson distribution to predict the failure rate of the Amine Swingbed as a whole. I have determined a mean time to failure for the Amine Swingbed to be approximately 1,400 hours. The observed mean time to failure for the system is between 600 and 1,200 hours. This range includes initial testing of the Amine Swingbed, as well as software faults that are understood to be non-critical. If many of the commercial parts were switched to military-grade parts, the expected mean time to failure would be 2,300 hours. Both calculated mean times to failure for the Amine Swingbed use conservative failure rate models. The observed mean time to failure for CDRA is 2,500 hours. Working on this project and for NASA in general has helped me gain insight into current aeronautics missions, reliability engineering, circuit analysis, and different cultures. Prior my internship, I did not have a lot knowledge about the work being performed at NASA. As a chemical engineer, I had not really considered working for NASA as a career path. By engaging in interactions with civil servants, contractors, and other interns, I have learned a great deal about modern challenges that NASA is addressing. My work has helped me develop a knowledge base in safety and reliability that would be difficult to find elsewhere. Prior to this internship, I had not thought about reliability engineering. Now, I have gained a skillset in performing reliability analyses, and understanding the inner workings of a large mechanical system. I have also gained experience in understanding how electrical systems work while I was analyzing the electrical components of the Amine Swingbed. I did not expect to be exposed to as many different cultures as I have while working at NASA. I am referring to both within NASA and the Houston area. NASA employs individuals with a broad range of backgrounds. It has been great to learn from individuals who have highly diverse experiences and outlooks on the world. In the Houston area, I have come across individuals from different parts of the world. Interacting with such a high number of individuals with significantly different backgrounds has helped me to grow as a person in ways that I did not expect. My time at NASA has opened a window into the field of aeronautics. After earning a bachelor's degree in chemical engineering, I plan to go to graduate school for a PhD in engineering. Prior to coming to NASA, I was not aware of the graduate Pathways program. I intend to apply for the graduate Pathways program as positions are opened up. I would like to pursue future opportunities with NASA, especially as my engineering career progresses.

Dunbar, Tyler↗
DOE OSTI2025

Optimizing CO 2 -Loaded Aqueous Amine Solutions for Higher Electrocatalytic CO 2 Reduction Activity

The activity of aqueous-based carbon dioxide reduction (CO 2 R) reactions is often limited by the solubility of CO 2 . The addition of amines can increase the total dissolved carbon in water through the formation of bicarbonate and carbamate species, which has been used to a great effect to capture CO 2 from dilute streams. Here, in this study, we explore the effect of 12 primary and secondary amines of varying Brønsted basicity, steric profile, and hydrogen-bonding capabilities on the aqueous CO 2 R to CO activity of a molecular Ni(cyclam)Cl 2 catalyst with a Hg electrode. Addition of some of the amines results in greater activity and selectivity for CO production compared to equivalent aqueous solutions without added amines. Under optimal conditions (0.4 M 3-amino-propionitrile), there is an over sevenfold increase in partial current density and greater selectivity for CO compared to equivalent conditions with no amine. Interestingly, the increase in activity did not correlate to any single property across the 12 amines. To elucidate the effect of the amine additives on catalysis, we used vapor–liquid equilibrium modeling (VLE), 13 C NMR spectroscopy, and computational analysis to determine the carbon speciation of the solutions. These results indicate that for amines without ethylalcohol functionalities, CO 2 R activity correlates with carbamate concentration, which is in turn governed by amine basicity and steric effects. However, this correlation does not persist for amines with ethylalcohol functionalities, which can form more stable carbamates through intramolecular-hydrogen bonding. These studies demonstrate that amine additives can enhance aqueous CO 2 R activity and selectivity and describe amine properties that lead to these higher performance metrics.

Amines↗
DOE OSTI2023

Gradient Amine Sorbents for Low Vacuum Swing CO 2 Capture at Ambient Temperature

The growing concerns over CO 2 emissions have led to the development of various methods for CO 2 capture. CO 2 capture by amine-based sorbents has been achieved by temperature (thermal) swing adsorption (TSA) process, pressure swing adsorption (PSA) process, and temperature pressure or vacuuming swing adsorption (TPSA or TVSA) process for CO 2 capture. Amine sorbents for energy-efficient TSA, PSA, VSA, TPSA or TVSA CO 2 capture should possess a capability which allow adsorbed CO 2 to desorb and amine sorbent to be regenerated at low temperatures or low vacuums. Development of such amine sorbents would significantly decrease energy consumption and sorbent degradation during the regeneration step. The objective of this project is to develop a low vacuum swing adsorption (VSA) process for the capture of CO 2 from air. The focus is on the development of amine sorbent which allows CO 2 to adsorb in the form of weakly adsorbed CO 2 . The weakly adsorbed CO 2 species can be collected from the sorbent by applying a low vacuum at ambient temperature. Specifically, no heating (i.e., thermal energy) is needed for regeneration of amine sorbents. This novel sorbent allows VSA to be operated at ambient temperature without a significant energy demand. This process eliminates the energy-intensive heating and cooling process in temperature swing adsorption (TSA) process. Ambient temperature operation could prolong the lifetime of sorbent and minimize the maintenance cost. Extensive sorbent studies with in-situ infrared spectroscopy have revealed the modifications of conventional amine sorbents with additives can increase the fraction of weakly adsorbed CO 2 . The amine sorbents with loaded CO 2 can be regenerated in part by the following approaches: (i) mild heating to temperatures below 70 °C, (ii) flowing purging gas over modified amine sorbents at temperatures below 40 °C, (iii) vacuuming at pressure below 0.2 atm and temperatures below 40 °C. The performance of these modified amine sorbents has been tested in a 60 grams VSA unit at ambient temperatures. The results show that weakly adsorbed CO 2 which can be desorbed from modified amine sorbents with purging gas at 100 cc/min can also be evacuated at a vacuum of 1 psia at room temperature. A preliminary techno- economic analysis indicates the major cost of the VSA process with modified amine sorbents stems from the operation of vacuum pumps. Thus, developing an excellent sealing with minimum leakage for the VSA unit is the most critical task for further the development of this VSA technology.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Theoretical and Experimental Insights into CO 2 Capture and Methanation over Amine-Grafted Ru-Based Catalysts

Carbon capture and storage (CCS) technologies, along with CO 2 capture and conversion methods, have emerged as crucial research areas to address rising CO 2 emissions. In this study, we seek to understand the mechanistic role of amines in enabling lower-energy pathways for CO 2 conversion. Our research focuses on the development and analysis of dual-functional materials (DFMs) engineered for the reactive capture and conversion (RCC) of CO 2 into methane, utilizing Ru catalysts grafted with amine groups. We employ Density Functional Theory (DFT) calculations using methylamine as a model amine to investigate the impact of amine groups on CO 2 methanation on a Ru(0001) surface, both in the presence and absence of amine groups. The amine ligand alters the carbon coordination environment, promoting direct C–O dissociation and potentially destabilizing the CO* adsorbate, thereby reducing the risk of CO poisoning. Additionally, we observe a preference for hydrogenation, although it becomes more energetically uphill in the amine-bound scenario. Our experiments, however, report similar CO 2 conversion and CH 4 production rates over the synthesized catalysts “Ru/TiO 2 ” and the amine (N-(2-aminoethyl)-3-aminoproplytrimethoxysilane (“diaminosilane”)) deposited catalyst “Diamine−Ru/TiO 2 ”. By constructing comparative reaction-free energy diagrams and performing microkinetic modeling (MKM) simulations, we link our theoretical findings with experimentally observed CO 2 uptake, conversion, and methane production rates. A microkinetic model was employed to investigate the anomaly, showing reduced amine–carbon complex coverage and increased CO 2 coverage at all temperatures. The MKM simulations consistently confirmed these trends. In conclusion, this comprehensive approach offers key insights into the role of the amine-CO 2 bond in methanation, highlighting a pathway toward lower-energy, more efficient CO 2 capture and conversion processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗