NNadir

NNadir's Journal

December 31, 2019

A massive wind turbine in New York City crashes down onto a car

(CNN)A recently installed wind turbine came crashing down in a New York City neighborhood, causing a chain reaction on Monday.

As the turbine in the Bronx partially collapsed, it smashed into an adjacent three-sided illuminated billboard, causing that also to break apart and come tumbling down to the street and cars below.
Pictures from the scene shot by Tori McCauseland with The Co-op City Times show a massive pole lying across a mangled car.
"Thankfully we can report that there are no injuries, and everyone is safe and sound," New York Mayor Bill de Blasio told CNN affiliate WABC. "An investigation into how this incident happened is underway."
The wind turbine, which is more than 150 feet tall, was installed in mid-December but had not yet been activated, according to WABC.

December 31, 2019

The Nature of the Thermal and Electrochemical Degradants in Lithium Battery Electrolytes.

The two papers from the primary scientific literature that I'll discuss in this post are these:

Reaction Product Analyses of the Most Active “Inactive” Material in Lithium-Ion Batteries—The Electrolyte. I: Themal Stress and Marker Molecules (Sascha Nowak et al, Chem. Mater. 2019, 31, 24, 9970?9976)

...and...

Reaction Product Analysis of the Most Active “Inactive” Material in Lithium-Ion Batteries—The Electrolyte. II: Battery Operation and Additive Impact (Sascha Nowak et al, Chem. Mater. 2019, 31, 24, 9977?9983)

Chemistry of Materials is a publication of the American Chemical Society, the world's largest professional scientific organization.

The cartoon graphics for introducing the papers are these:

...and...

There is a widespread belief, particularly in the Western World, that somehow, batteries, with which we are all familiar, and which we all use, will save the world. A belief in a concept, of course, is very different than facts related to a concept. Batteries will not save the world. A battery is a device that wastes primary energy. The fastest growing source of primary energy on this planet has been, in this century as in the last, dangerous fossil fuels. The world was utilizing, as of 2018, the last year for which we have complete compiled data, 599.34 exajoules of primary energy. This compares to 420.19 exajoules of primary energy utilized in the year 2000. (So much for the widespread belief that energy conservation would save the world.) Of the increase of 179.15 exajoules, 148.34 exajoules has been provided by increases in the use of the three dangerous fossil fuels, lead by dangerous coal, (63.22 exajoules) and dangerous natural gas, (50.33 exajoules).

The belief that batteries would save the world, is connected with the associated belief that so called "renewable energy" would save the world, a belief that has not been borne out by experiment: Despite an investment of over 2.1 trillion dollars in the last ten years alone, so called renewable energy has not saved the world; it isn't saving the world; and - I keep trying to burst this toxic fantasy with only limited success - it won't save the world. In this century, all the primary energy produced by wind, solar, geothermal and tidal energy on this planet grew by 9.76 exajoules. In the "percent talk" so favored by advocates of vast expenditures (and destruction) associated with so called "renewable energy," all the world's solar, wind, geothermal, and tidal output grew by 15.4% as fast as the most lethal and dangerous of all the dangerous fossil fuels, coal.

That's a fact. Facts matter.

Here's another fact: On this planet, when one charges a battery, whether its for your computer, your phone, or for Elon Musk's silly electric car for millionaires and billionaires, there is an overwhelming probability that one is storing, and wasting, almost in its entirety, dangerous fossil fuel generated primary energy.

Here's another fact: The existence of the most efficient batteries known, lithium batteries, for the discovery of which Nobel Prizes were awarded this year, is very much dependent on the use of energy generated by dangerous fossil fuels and materials dependent, for their manufacture, by dangerous fossil fuels. Further, there is not, on this planet, enough lithium, nor for that matter and considerably more important and dire, not enough cobalt on this planet to store more than 600 exajoules of primary energy.

Before going into more detail about the two papers cited at the outset, let's look at the graphic of figure 1 of the first of the two papers, which looks at the common formulation of electrolytes in most of the world's lithium batteries.

The caption:

Figure 1. Common electrolyte formulations used in state-of-the art LIB cells. In this study, ternary mixtures of varying linear carbonates (DEC, DMC, EMC) in combination with EC and LiPF6 were investigated by means of LC–MS.

DEC here is diethyl carbonate. DMC is dimethyl carbonate. EMC is ethyl methyl carbonate. EC is ethylene carbonate. Historically, and in many cases, still these organic carbonates are obtained by the use of phosgene, a war gas, made from dangerous natural gas and chlorine gas, that killed tens of thousands of soldiers in the First World War and organic alcohols. Most of the world's methanol is produced from dangerous natural gas. Ethanol for DMC is obtained from corn, a "renewable fuel" that has been responsible for the destruction of the Mississippi Delta's ecosystem. Ethylene glycol, the starting material for EC, the cyclic carbonate in the paper is made via the thermal cracking, at temperatures of around 700°C , of dangerous petroleum to give ethylene (aka "ethene&quot

, and epoxidation of this highly flammable gas with oxygen under controlled conditions. The most common use of ethylene glycol is for use as antifreeze in dangerous automobiles, combusting largely dangerous petroleum products.

Other abbreviations that come up in these papers.

LC-MS often written as LC/MS/MS and written in this case as LC-IT-MS or (as the case actually involved here, LC-HRMS or LC-IT-TOF-MS) refers to liquid chromatography (LC) coupled to various permutations of mass spectrometry, ion trap (IT), high resolution (HR) and Time of Flight (TOF).

The authors here, all of whom work in Germany, have studied what happens to these electrolyes in use, storage, and upon exposure to heat. Lithium batteries, as most of us know, do generate heat on charge and discharge, this heat representing the wasted primary energy that their use involves.

From the introduction of the first paper:

Today’s applications of lithium-ion batteries (LIBs) ranging from small consumer electronics (e.g., smartphones, watches) to large battery systems in electric vehicles (xEVs) are accompanied by new challenges regarding heat generation at the cell level.(1) On the one hand, various novel, for example, inductive charging, techniques are rising in popularity; on the other hand, fast-charging capabilities for xEVs are the considered key for consumer acceptance and will be affected by overpotentials.(2) Both requirements, combined with ambient temperature fluctuations, and in particular direct insolation, will result in an increased thermal stress for LIBs.(3) As a consequence, the most susceptible cell component in terms of thermal stability, the LIB electrolyte, is prone to decomposition at elevated temperatures.(4?8)

Manifold aging phenomena have been described for LIB cell components in recent years.(9,10) In detail, the thermal decomposition represents one possible electrolyte degradation pathway. Part 1 of this study focuses solely on the thermal influence on the electrolyte decomposition; Part 2 involves electrochemical influences such as interphase formation reactions and varying the applied voltage at room temperature. The most commonly applied electrolyte formulations consist of lithium hexafluorophosphate (LiPF6) as conducting salt dissolved in a mixture of cyclic ethylene carbonate (EC) and at least one linear carbonate (e.g., dimethyl carbonate, DMC; diethyl carbonate, DEC; ethyl methyl carbonate, EMC) (Figure 1).(5,11) Numerous analytical techniques were applied for the identification and quantification of electrolyte degradation products.(12,13) Particularly, the LiPF6 decomposition route was studied intensively, leading to the identification of potentially toxic organo(fluoro)phosphates (O(F)Ps) in a high structural variety.(14?22) Electrolyte degradation products originating from carbonate solvents have been reported in literature(23,24) as well as their impairing effect on LIB performance.(25) According to Lee et al. and Ariga et al., a ring-opening reaction of EC (via nucleophilic attack or cationic activation) results in polymerization with occasional decarboxylation.(26,27) Consequently, reliable structural elucidation of the decomposition product variety enables the understanding of reaction pathways and represents the initial step for the development of prevention strategies. Eventually, deciphering the pathway of decomposition products might enable the definition of marker molecules in the electrolyte to identify prior thermal strain for the LIB, enhancing the capabilities of post-mortem analysis and the validity of analytical investigations in terms.

Since I regard mass spectrometry as the most important of all analytical chemistry methods, please indulge me as I describe the experimental procedure:

For LC–MS investigations, a Nexera X2 UHPLC system (Shimadzu, Kyoto, Japan) hyphenated to a LCMS-IT-TOF (Shimadzu) was used. Reversed-phase chromatography was conducted on a ZORBAX SB-C18 column (100 × 2.1 mm, 1.8 ?m; Agilent Technologies, Inc., Santa Clara, CA, USA) at 40 °C and a flow rate of 0.5 mL min–1. The mobile phase consisted of water (A) and acetonitrile (B). The gradient started with 5% B from 0 to 1.8 min and increased to 60% B within 12.2 min. Subsequently, the mobile phase was kept constant at 60% B for 2 min. Finally, the column was equilibrated at 5% B for 4 min. The injection volume was 5 ?L. To protect the IT-TOF mass spectrometer from high concentrations of conducting salt LiPF6 and thermally induced acidic decomposition products, the flow line switched to the MS after 1.8 min. Ionization was performed in the ESI(+) mode at 4.5 kV. The curved desolvation line and heat block temperature were 230 °C. The drying gas pressure was set to 100 kPa, and the nebulizer gas flow was 1.5 L min–1. The ion trap was operated in an automatic MS2 mode with an ion accumulation time of 10 ms in MS1 and 40 ms in MS2, leading to a loop time of 260 ms. The mass range was set to a mass-to-charge ratio (m/z) of 100–400 in MS1 and 50–400 in MS2 for the low-mass window, an m/z of 200–1000 in MS1 and 150–1000 in MS2 for the high-mass window.

Trust me, it's cool.

Figures 2 and 3 show the mass chromatograms of the products of the forced degradation studies, conducted at at 80 °C (accelerated conditions) on the electrolytes:

The caption:

Figure 2. Identification of decomposition product signals via the formed adduct pattern of species (H+, NH4+, and Na+) with RPLC-HRMS in ELDMC. The excerpt shows the average mass spectrum between 8.0 and 11.0 min. Coeluting compounds resulting in chromatographic interferences with the same nominal mass (*) and spectral interferences (**) are indicated.

The caption:

Figure 3. Chromatographic separation (c) of five compounds with the same nominal mass in ELDMC electrolyte. MS2 experiments (a, b, d, e, f) show differences in fragments formed and intensity pattern. An m/z shift of 0.036 was observed between chromatographic peaks (c) and within almost all fragment signals exemplarily shown in (d).

In mass spectrometry, mass transitions for different compounds can result in similar or identical "first pass" signals, a factor that is subject to clarification by the LC component's orthogonality (differences in the retention time in the chromatographic column). An ion trap, allows for further orthogonality, resulting in a deeper understanding of the precise structures, further elucidated by the high resolution achievable by the use of time of flight techniques.

Table 1 in the paper reflects differentiation of these similar (isobaric) fragments to give the structures of different molecules using these powerful techniques:

The next figure shows the thermal degradants putative structures:

The caption:

Figure 4. MS2 fragmentation of the precursor m/z 416.2126 (Figure 3d). Obtained information was used for fragment and precursor structure predictions. Cleavage positions are indicated in the precursor structure suggestion, and incongruous fragments are highlighted in red.

The final graphic suggests a nomenclature for the decomposition products:

The caption:

Figure 5. Copolymer scheme based on carboxylate and ethylene oxide linkages. Different terminal groups formed depending on the thermally degraded electrolyte formulation are shown (R1, R2). The copolymer scheme for m/z 416.2126 is shown exemplarily.(sic)

From the conclusion to the paper:

LIB electrolyte decomposition products formed during exposure to elevated temperatures were studied in this Part 1 of a two-part study. The identification of oligomeric compounds led to the generation of a target list of 206 unique species with an upper molecule mass border of 602 u. Optimal confidence for structure elucidation was achieved via consideration of HRMS, MS2, chromatographic correlation, as well as the interrelation of findings. In electrolytes containing either DMC, DEC, or EMC, 140 different species were identified and structures suggested. In this regard, a classification of solvent-based degradation products was developed, overcoming the structural uncertainties of possible isomers. Terminal hydroxy groups were scarcely detected, which is good agreement with the postulated correlation to water contamination. Furthermore, a statistical distribution of the decomposition product formation process was postulated. Overall, thermal aging revealed a conducting salt degradation to O(F)Ps, distinctly separated from solvent decompositions to oligomeric carbonates, ethylene glycols, and co-oligomers. Consequently, no intermixtures of O(F)Ps and oligomeric compounds, or in other words no mixed compounds of conducting salt and electrolyte solvent entities, were detected in these thermal aging experiments.

Part II gives rise to some products that are of a little more concern to me, since there are clear toxicological implications. It involves the degradation related to charge and discharge, which is, of course, what batteries are all about.

From the introduction:

Since their market introduction in the early 1990s, the requirements for lithium-ion batteries (LIBs) extended with its fields of application.(1,2) The competition for enhanced energy densities(3?5) yields, high-voltage materials,(6?8) large-capacity negative-electrode materials,(9?12) and high-energy/capacity battery cells drift further apart. In contrast, the electrolyte remained almost unchanged for three decades.(13)

Lithium hexafluorophosphate (LiPF6) dissolved in linear and cyclic organic carbonates still represents the state-of-the-art electrolyte. The limited redox stability of the electrolyte toward electrode potentials results in parasitic (aging) and beneficial (interphase formation) decomposition reactions.(14,15) With regard to electrode materials, carbonaceous negative electrodes in combination with a lithium metal oxide (LiMO2; M: Mn, Co, Ni, Al) as positive electrode, spatially separated by polyolefin layers, are commonly used in commercial LIB cells. One crucial step for LIB cell performance is the generation of a solid electrolyte interphase (SEI) on the negative electrode surface during the first cycles.(16?21) On the positive electrode surface, the cathode electrolyte interphase (CEI) is formed. The interphase composition and variability during charge/discharge are still under discussion in literature.(16,22,23) The reductive degradation at the negative electrode leads to organic and inorganic parts within the SEI.(24) The SEI is a first-order electronic insulator while being lithium-ionconductor. This represents the starting point of the film-forming electrolyte additives, which decompose reductively at higher potentials than ethylene carbonate (EC); thus, the products of the additive (e.g., vinylene carbonate; VC) integrate into the SEI. Consequently, the properties of the SEI can be modified by electrolyte additives and its passivation capabilities toward electrolyte components.(25) The structure elucidation of decomposition products soluble in the electrolyte after parasitic reactions are the focus of this Part 2 of the study.

Approaches for the characterization and structure elucidation of the electrolyte decomposition in LIB cells started in the late 1990s(26) and culminated in structure predictions in combination with reaction pathway suggestions mainly by the working group of Laruelle and others.(27?34) Gachot et al. described the formation of compounds incorporating carbonates and phosphates,(32) which was extended by more complex structures and oligo phosphates in 2015.(35) The picture of electrolyte decomposition products with molecular weights exceeding those of the solvents became increasingly clear via the application of liquid chromatography-mass spectrometry (LC-MS) with high-resolution mass spectrometry (HRMS), fragmentation (MS2) information and hydrophobic retention on reversed-phase (RP) chromatography.(35?38) To generate optimum structural confidence with LC-MS, these features were considered in highly complex LIB electrolyte samples. Nonetheless, quadrupole-based low-resolution studies can lead to less dependable results and misleading structure suggestions.(39)

The authors constructed some typical types of cells (of a type making components available for examination using analytical chemistry, again LC/MS. They ran the cells through 1000 charge and discharge cycles.

Some graphics:

The caption:

Figure 1. Overview of products identified after thermal (gray) and electrochemical decomposition. Compounds with a maximum phosphate (P) content of 3 and carbonate (C) count of 3 were identified and are shown in the Supporting Information

The caption:

Figure 2. RPLC-IT-TOF-MS chromatogram of diphosphates (top) with varied alkylation in ELEMC+VC after >1000 cycles. Isobaric interferences are indicated in gray. Fragmentation spectra of the proton (m/z 307.0706) and lithium (m/z 313.0756) adducts of double methylated and ethylated diphosphate are allocated to specific fragments. The fragmented peak is highlighted with (I).

The caption:

Figure 3. RPLC-IT-TOF-MS chromatogram of a phosphate–carbonate compound (top) with different alkylations in ELEMC+VC after >1000 cycles. Chromatographic peak splitting of double-methylated or -ethylated compounds can be deciphered via MS2 experiments of the [M + H]+ adduct (bottom), forming carbonate fragments. The specific fragmented peaks are highlighted with (I) and (II).

The caption:

Figure 4. RPLC-IT-TOF-MS chromatogram of isomers of phosphate with three carbonate groups (top) in ELEMC+VC after >1000 cycles. Three different chromatographic peaks were obtained and allocated to the shown configuration via MS2 experiments, identifying characteristic fragments (bottom, green). The fragmented peaks are highlighted with (I), (II), and (III).

The caption:

Figure 5. RPLC-IT-TOF-MS chromatogram of three cyclic ether carbonate oligomers in ELEMC after >1000 cycles (top). MS2 experiments were applied for structure confirmation (bottom), including structure suggestions of formed fragments. The fragmentated peak is highlighted with (I).

This table from the paper compares the results of the number and types of compounds found in each of the two types of experiments from Part 1 and Part 2 of the series.

Organophosphate esters are widely utilized compounds. They have been utilized as flame retardants, replacing the halogenated aromatic ethers that have resulted in a huge environmental contamination problem, particularly for people recycling electronic waste, most of whom are in the third world where we do not have to pay attention to the consequences on their lives. It is not entirely clear that the replacement organophosphates are totally benign. Organophosphates are also utilized as chemical warfare agents, in particular, sarin, which probably has a precursor similar the anion to in the lithium batteries, the perfluorophosphium ion. (There is no evidence of sarin or closely related compounds in this paper.) Sarin is an acetylcholine esterase inhibitor, and thus a nerve agent. Similar nerve agents are widely used as insecticides. The closest isosteric compound to an insecticide found in this paper is the compound having a mass of 167.0472 amu in figure 2. It is nearly isosteric with dichlorovos, a halogenated analogue, which was an insecticide banned in Europe in 1998, also a neurotoxic compound.

I have written in the past in this space on the subject of recycling of lithium batteries, and some of the issues connected with doing so.

Trust me, this kind of recycling may not fall under the rubric of "green." Things that sound good in the abstract have real consequences. The most destructive distributed energy device ever invented, the automobile, was originally promoted as an alternative to the very serious historical problem of horse manure accumulations in cities, a health, environmental and aesthetic problem of consequence. If we take our hippie rose colored glasses off, arguably the cure was far worse than the problem.

I wish you a successful, happy and healthy New Year.

December 30, 2019

Direct Air Capture of CO2 with Aqueous Amino Acids and BIG (bis-aminoguanidines).

The paper I'll discuss in this post is this one: Direct Air Capture of CO2 with Aqueous Amino Acids and Solid Bis-iminoguanidines (BIGs) (Radu Custelcean,* Neil J. Williams, Kathleen A. Garrabrant, Pierrick Agullo, Flavien M. Brethomé, Halie J. Martin, and Michelle K. Kidder Ind. Eng. Chem. Res. 2019, 58, 51, 23338-23346).

The authors work at Oak Ridge National Laboratory.

The figure for concentrations of the dangerous fossil fuel waste carbon dioxide's concentration in the planetary atmosphere, as reported yesterday at the Mauna Loa CO2 Observatory are as follows:

Up-to-date weekly average CO2 at Mauna Loa:

Week beginning on December 22, 2019: 412.21 ppm
Weekly value from 1 year ago: 409.24 ppm
Weekly value from 10 years ago: 388.17 ppm
Last updated: December 30, 2019

This concentration is thus 2.97 ppm higher than one year ago, and 24.04 ppm higher than ten years ago. The average rate of the accumulations of the dangerous fossil fuel waste carbon dioxide is thus, as represented by this particular figure, 2.4 ppm per year. On the week beginning on December 26, 1999, the figure comparing the carbon dioxide with that measured 10 years earlier, December 24, 1989, was 15.64 ppm higher, implying an average of 1.5 ppm per year at the end of the 20th century.

Things are getting worse, not better.

I have made pretty clear in my posts here, why I think this is, a refusal to "go nuclear" to address climate change coupled with an unwarranted belief that so called "renewable energy" would save the day. It didn't. It isn't saving the day. It won't save the day.

A smarter generation than the one to which I belong may therefore need to remove our waste from the atmosphere, where we have let it accumulate with severe and unconscionable indifference to reality, a willing to be impervious to facts, both on the political right and on the political left.

As I have approached the end of my life, I have worked to make myself familiar with possible approaches to addressing the very challenging issue of removing carbon dioxide from the atmosphere. Hence this paper which came up in my regular reading caught my eye.

I'll let some excerpts and graphics from the paper speak for themselves. Full access to the paper may be found at a good academic library or by subscription.

From the introduction:

With the projected increase in the world’s population, the global energy demand will continue to grow for decades to come. Given our continuing reliance on fossil fuels as a major source of energy, effective emission reductions through large-scale deployment of carbon capture and storage (CCS) technologies have become critical for mitigating climate change.(1) While CCS technologies have traditionally been implemented at point sources of CO2 emissions, such as coal- or gas-fired power plants, recent integrated assessment models have increasingly emphasized the need for negative emission technologies (NETs), that is, technologies that remove CO2 out of the atmosphere, to limit global warming below 2 °C by 2100.(2?4) NETs have a unique place among the various technological solutions to the climate change problem, as they provide the only means to cut past emissions and restore the atmospheric composition to an optimal level with respect to the CO2 concentration. Furthermore, NETs can capture the CO2 from dispersed emitters involved in transportation, which currently account for about 50% of the annual greenhouse gas emissions. Finally, when coupled with efficient methods to convert the CO2 removed from air into fuels using renewable energy sources, NETs have the potential to close the carbon cycle and generate carbon-neutral fuels.(5)

I oppose giant carbon dioxide waste dumps which appears under the rubric of carbon dioxide capture and storage (CCS), but am enthusiastic about carbon dioxide capture and utilization (CCU). Reference 5 is to a National Academy Press Monograph on the latter subject. Gaseous Carbon Waste Streams Utilization

The introduction continues:

Most existing DAC processes fall into one of the two categories, employing either aqueous solutions of strong alkaline bases (e.g., NaOH, KOH) or solid-supported amines for CO2 capture.(2,6,8?10) The aqueous alkaline DAC systems consist of two cycles.(11) In the first cycle (absorption), the aqueous base is contacted with air, so the hydroxide anions react with CO2 and convert it into sodium or potassium carbonate salts. In the second cycle (regeneration), the carbonate anions are reacted with Ca(OH)2 and precipitated as CaCO3, thereby regenerating the hydroxide base. The CaCO3 solid is then heated to 900 °C in a pure oxygen atmosphere to release the CO2 and regenerate the calcium oxide.(11) This regeneration process is very energy intensive, requiring 6–9 GJ/t CO2 and high-grade heat that needs to be supplied from a low-carbon source to make the overall process net carbon negative.(2,10) On the other hand, the solid-sorbent DAC approach employs primary or secondary amines on porous organic or inorganic supports, which are loaded by contacting with air at ambient conditions, then regenerated by applying heat, vacuum, or a combination of the two.(12?15) These systems typically require less energy than the aqueous bases (5–7 GJ/t CO2) and significantly lower temperatures (80–150 °C) that can be supplied from low-grade waste heat,(2,10) but they tend to have slower CO2 sorption kinetics compared to aqueous sorbents.(16) A remaining challenge with solid-supported amines is their tendency to thermally and chemically degrade with repeated capture/regeneration cycles, though polyimine and polyamine adsorbents with improved resistance to oxidation have been recently reported.(17,18) Water vapor condensation in the pores from the ambient air can also increase the energy demand for sorbent regeneration.(19) Another DAC approach has been developed using ammonium-based anion exchange resins as solid adsorbents, which involve a completely different mechanism of CO2 adsorption and release driven by swings in the ambient humidity rather than temperature changes.(20,21) While lower-energy requirements have been reported for this moisture-swing process, as the sorbent regeneration is done passively using ambient wind conditions, its performance is inherently weather-dependent.(21) Furthermore, as with other solid adsorbents, the kinetics of CO2 adsorption and desorption are relatively slow.(22)

The bold here is mine, and reflects the energy cost of capturing carbon dioxide from the air. Each year at current rates, humanity dumps about 35 billion tons of CO2 into the planetary atmosphere, with another 7 to 10 tons additional being added because of land use changes, such as those involved in the destruction of rain forests to develop palm oil plantations for the production of "renewable" biodiesel. If direct air capture requires an intermediate figure for the two processes, ignoring the carbon cost of constructing plants to accomplish this task, the capture of 35 billion tons of dumped waste, a single year's worth, the energy required would be about 245 exajoules of energy. For comparison purposes, world energy demand for all purposes was, according to the IEA 2019 World Energy Outlook, was 599.34 exajoules.

2019 Edition of the World Energy Outlook Table 1.1 Page 38] (I have converted MTOE in the original table to the SI unit exajoules in this text.)

Thus were we to begin capturing carbon dioxide from the air to reverse climate change, we would need to consume 845 exajoules of energy from carbon free sources. For comparison, all the world's solar, wind, geothermal and tidal energy produced, after more than half a century of increasingly mindless cheering, produced, as of 2018, according to the source immediately above, 12.27 exajoules.

Facts matter.

The authors have proposed a new and interesting scheme. They use amino acid salts, amino acids being the building blocks of proteins, to capture the carbon dioxide - biologically carbon dioxide is captured in plants using the amino acids lysine and/or arginine - and then regenerate the carbonated salts by passing the solution over an insoluble organic compound featuring two of the functional group that is found on the amino acid arginine, guanidyl groups.

The amino acids they use are the simplest proteogenic amino acid, glycine, and its N-methyl derivative known as sarcosine.

The scheme below shows how the system works, showing just glycine and not sarcosine:

The caption:

Scheme 1. DAC of CO2 by Absorption with Aqueous Amino Acids (Potassium Glycinate is Shown as a Representative Example) and (Bi)carbonate Formation, Followed by Crystallization with BIGs

This scheme shows how the "BIGs" were synthesized:

The caption:

Scheme 2. Synthesis of m-BBIG and the Interconversion between the Free Base and the Chloride and Carbonate Salts

Here is how the experiment was run:

Direct Air Capture Cycles
For the multicycle experiments, 2 L of 1 M Sarcosine and 1 M KOH were loaded with CO2 for 24 h using an Envion HumidiHeat humidifier. The solution level was kept at 2 L by pumping in freshwater using a minipump to compensate for the water evaporation. The solution pH was monitored in situ using a pH probe dipped into the reservoir. After 24 h, the loaded amino acid solution was transferred to a 4 L beaker and stirred with a mechanical stirrer set at 200 rpm. Solid m-BBIG (147.8 g, 0.6 mol) was then added to the solution, and the resulting slurry was stirred for 1 h, monitoring the pH throughout the regeneration. The suspension was subsequently vacuum-filtered to separate the solid mixture of m-BBIG and its carbonate salt from the regenerated amino acid solution. The regenerated amino acid solution was then measured with a graduated cylinder to record its volume, then transferred back into the humidifier’s reservoir for the next cycle. The filter cake was transferred to a crystallizer dish and broken up into smaller pieces, then placed in the oven at 120 °C for 2 h. The regenerated m-BBIG was weighed and reused in the next cycle. To measure the CO2 cyclic capacities for each cycle, 50 ?L of samples was drawn with a 1 mL syringe equipped with a 0.22 ?m syringe filter, diluted with 450 ?L of D2O, and left at room temperature for 24 h prior to being analyzed by 1H NMR spectroscopy to measure the carbamate concentrations. The (bi)carbonate concentrations were subsequently measured by IC, taking 20 ?L of the NMR solutions and further diluting them with 980 ?L of H2O before the IC analyses. The DAC cycles were run in triplicate, and average values and standard deviations are reported.

Some additional graphics from the paper tell much of the story:

The caption:

Figure 1. X-ray crystal structure of m-BBIG (50% ellipsoids shown), viewed orthogonal (top) and parallel (bottom) to the benzene ring.

The caption:

Figure 2. X-ray crystal structure (50% ellipsoids shown) of (m-BBIGH22+)(?OOC–CH2–NH–COO–)(H2O)4, obtained by crystallization of m-BBIG from an aqueous potassium glycinate solution loaded with CO2 by DAC. The water molecules included in the crystal are not shown.

The caption:

Scheme 3. CO2 Capture by Absorption with Aqueous Potassium Sarcosinate Followed by Carbonate Crystallization with m-BBIG

The caption:

Figure 3. CO2-loading curves for DAC with 1 M potassium glycinate (red squares) and potassium sarcosinate (blue dots), using an air humidifier (shown on the left) as the air–liquid contactor.

The caption:

Figure 4. Time-dependent regeneration of 1 M glycine (red squares) and sarcosine (blue dots) with m-BBIG. The molar amounts of CO2 removed relative to the amino acid concentrations (mol/mol) were monitored by measuring the concentrations of carbamate and (bi)carbonate left in solution by 1H NMR spectroscopy and IC. The error bars are defined as the standard deviations from three separate experiments.

The caption:

Figure 5. Time-dependent regeneration of 1 M glycine (red squares) and sarcosine (blue dots) by refluxing. The molar amounts of CO2 removed relative to the amino acid concentrations (mol/mol) were monitored by measuring the concentrations of carbamate and (bi)carbonate left in solution by 1H NMR spectroscopy and IC. The error bars are defined as the standard deviations from three separate experiments.

The caption:

Figure 6. Consecutive loading/regeneration DAC cycles with sarcosine/m-BBIG. The error bars are defined as the standard deviations from three separate experiments.

The caption:

Figure 7. Comparison of regeneration energies (kJ/mol) for m-BBIG, PyBIG, and the CaCO3 and aqueous sodium glycinate (30 wt %) benchmarks.

The caption:

Figure 8. Proposed flow diagram for the overall DAC process based on the amino acid/BIG system.

This is a lab scale process, and helpfully, the authors sketch the requirements of scaling the process:

While this study has focused mostly on the fundamental and early-applied aspects of DAC, such as the design, synthesis, and characterization of the BIG/amino acid sorbents, thermodynamic analysis, and the bench-scale process, considerations of future R&D needs for further developing and improving the DAC technology are appropriate here. First, the prototype system needs to be scaled up a few orders of magnitudes, from the current scale of about 100 g of CO2/day, to the pilot scale of 1 ton of CO2/day, and finally to the full scale of 1 Mt of CO2/year. Before that can be achieved, the various components of the DAC process need to be optimized, starting with the air–liquid contactor, continuing with the crystallizer unit, and finishing with the CO2 stripping unit. While the air humidifier used in this early study offered a simple and economical set-up for comparing different sorbents and CO2 loading conditions, better contactors need to be designed to maximize the air–liquid interfacial area and minimize water evaporation. Along this line, different real-world conditions need to be tested, including variable air temperatures and humidity levels. Next, the crystallizer unit needs to be designed so that it can handle large volumes of solids and operate under continuous crystallization conditions. That will require an effective solid–liquid separator, such as a filter-press or a cyclone, and an effective mode of moving the solids between the crystallizer and the stripper units, using for example extruders. The CO2 release from the carbonate solid inside the stripping unit also needs to be optimized, to minimize the time, temperature, and energy required, improve the heat flow, and maximize the pressure of the CO2 output. The use of renewable or waste-heat sources of energy can be explored to increase the sustainability of the process. Finally, all of the components need to be integrated into the overall DAC process, which ideally would be operated in a continuous mode. Figure 8 illustrates a proposed flow diagram for the overall DAC process.

Note that it would require 1000 1MT/year capacity plants just to capture 1/35th of the carbon dioxide waste we dump each year, and having been dumping for decades.

From the author's conclusions:

A bench-scale direct air capture process has been demonstrated, comprising CO2 absorption with aqueous amino acid salts (i.e., potassium glycinate, potassium sarcosinate), followed by room-temperature regeneration of the amino acids by carbonate crystallization with a readily available and inexpensive bis-iminoguanidine (m-BBIG). Finally, CO2 release by mild heating (60–120 °C) of the m-BBIG carbonate crystals regenerated the m-BBIG solid quantitatively, thereby closing the DAC cycle. Three consecutive absorption/regeneration cycles have been run, with observed cyclic capacities of 0.12–0.20 mol/mol and a measured regeneration energy of 360 kJ/mol (8.2 GJ/ton). While the energy requirement is higher than the corresponding energy for the CaCO3 DAC benchmark (278 kJ/mol, 6.3 GJ/ton CO2), a significant advantage of the m-BBIG/amino acid system is that it requires much lower temperatures of regeneration (60–120 °C) compared to CaCO3 (900 °C), which can be easily supplied from low-grade waste heat or carbon-free renewable energy sources (i.e., solar, geothermal). Alternatively, the amino acid can be regenerated by boiling under reflux, with a measured cyclic capacity as high as 0.64 mol/mol and a regeneration energy as low as 253 kJ/mol (5.8 GJ/ton).

While the energy requirement of this system is higher than other approaches, the low temperatures required may make it possible to use heat routinely rejected to the atmosphere, thus lacking much a requirement for new energy, and perhaps moderately improving the thermal efficiency of nuclear reactors that might drive the carbon capture.

I hope you're having a very pleasant holiday season. I know I am, since I am having the joy of studying the equations of state for syn gas hydrogen and carbon dioxide/carbon monoxide mixtures.

December 29, 2019

I seldom go to the movies, but I saw one that was really, really well done and fun last night.

The Movie was "Knives Out."

It's a fun updated version of an old fashioned whodunnit with some barely hidden Trump jokes in it (including a "self-made" business woman who was self made with a small loan of a million dollars) and a good bit of understated social commentary.

My sons are home for the holidays, and the four of us, my two sons and my wife, went to a late show. We all loved it.

I just thought I'd mention it.

December 29, 2019

Remembering a President Who Knows How to Read: Obama's 2019 Reading list.

We may compare this with the functional illiterate currently in the White House.

Obama's 2019 list of favorite books:

"The Age of Surveillance Capitalism: The Fight for a Human Future at the New Frontier of Power" by Shoshana Zuboff
"The Anarchy: The Relentless Rise of the East India Company" by William Dalrymple
"Furious Hours: Murder, Fraud, and the Last Trial of Harper Lee" by Casey Cep
"Girl, Woman, Other" by Bernardine Evaristo
"The Heartbeat of Wounded Knee: Native America from 1890 to the Present" by David Treuer
"How to Do Nothing: Resisting the Attention Economy" by Jenny Odell
"Lost Children Archive" by Valeria Luiselli
"Lot: Stories" by Bryan Washington
"Normal People" by Sally Rooney
"The Orphan Master's Son" by Adam Johnson
"The Yellow House" by Sarah M. Broom
"Say Nothing: A True Story of Murder and Memory in Northern Ireland" by Patrick Radden Keefe
"Solitary" by Albert Woodfox
"The Topeka School" by Ben Lerner
"Trick Mirror: Reflections on Self-Delusion" by Jia Tolentino
"Trust Exercise" by Susan Choi
"We Live in Water: Stories" by Jess Walter

https://www.cnn.com/2019/12/28/politics/barack-obama-2019-favorite-books-list-trnd/index.html

December 18, 2019

I gave my sister-in-law advice on her love life.

I've known her since she was a girl, the "baby" in my wife's family.

I don't know where she finds these men, these strange and shallow guys on whom she obsesses and all of whom run her down.

After all these years of trying to help her to see that not all men are creatures from the deep, all I could do in the way of advice was to offer one of my favorite Eleanor Roosevelt quotations:

"No one can make you feel inferior without your consent."

Good advice?

Again, I don't know where she finds these guys...

December 18, 2019

Electric Dreams, Electric Sighs.

December 18, 2019

A Child Should Be A Fish.

December 17, 2019

Biochar-Assisted Water Electrolysis

The paper I'll discuss in this brief post is this one: Biochar-Assisted Water Electrolysis (Jun-ichiro Hayashi* et al, Energy & Fuels 2019, 33, 11246?11252)

The paper comes from a journal, Energy and Fuels, from which I have been reading papers for many years; since 2013 I have at least opened, if not actually read, every paper listed in the Table of Contents, and back issues from that time forward are in my personal library. Better than half, and sometimes as much as three quarters of the papers I encounter in this journal are about forms of energy I oppose vehemently, dangerous fossil fuels. There is usually a section, sometimes fair sized, and sometimes not, on biofuels, and usually a few papers on carbon capture, more or less lip service to the rest.

Speaking of lip service, there are a few papers on solar and wind energy, which many people keep saying will save the world, even though the haven't saved the world, aren't saving the world, and won't save the world. And then there's magic hydrogen, which bourgeois moral and intellectual Lilliputians like the Rocky Mountain Institute's Chief (self declared) Scientist, Amory Lovins, thinks might save the world or at least his precious cars, thus assuring he can drive from his luxury "super efficient" "green" 4000 square house in the upscale suburbs of Aspen to the offices of his ignorance factory located in Basalt, Colorado, just outside the upscale ski resort town of Aspen.

Here's a picture of Amory and his monument to boomer excess and contempt for humanity, especially that part of humanity, all 800 million, who go to bed every night wondering if they'll have food the next day:

?w=1200&h=748

Here's a picture of the Chief Idiot at RMI with a girlfriend/wife/whatever in front of this moral hell, both wearing insipid grins:

&updated=201904101124&MaxW=900&maxH=900&noborder&Q=80

What an ass! OK Boomer?

Anyway, the reason I read Energy and Fuels has nothing to do with uneducated and mindless brats like Amory Lovins who know nothing at all about energy and the environment, and nothing to do a fondness for either hydrogen or wind and solar power, both of which are topics, at least nominally, of the paper I cited at the outset. The reason I read them is to separate, as they say metaphorically, the wheat from the chaff.

As practiced right now, nominally "renewable" biomass is responsible for slightly less than half of the seven million air pollution deaths that take place each year, but biomass has one thing to recommend it: It is self replicating in such a way as it can, without too much input, cover vast surface areas, marine areas, land areas, lacustrine areas, fluvial areas. This allows it to make use of sunlight, even though it is diffuse, and more importantly, to capture dilute gases, notably, of course carbon dioxide.

Although the total amount of carbon dioxide captured by biomass each year is less than an order of magnitude higher than the amount of carbon dioxide dumps each year, it does have the capability to concentrate carbon in such a way as it is recoverable for technological purposes, assuming, probably without justification, that it is done judiciously. As currently practiced, there is nothing judicious about it. Destroying South East Asia's rain forests for "renewable" diesel fuel is not a good idea, nor was destroying the Mississippi River Delta's ecosystem for the gasoline additive ethanol a good idea.

I couldn't care less who wins the Iowa primary. Winning it, as far as I'm concerned, involves a paean to destruction, going back, as much as I hate to say it, to the days of Jimmy Carter. Corn ethanol is not sustainable.

I believe that the only feasible way to make a stab at - success cannot be guaranteed - is via the agency of high temperatures. Biomass utilization can be made safer than the unfortunate and deadly way in which it is practiced now by heating in closed, unvented systems. Two such approaches are reformation, one wet, and one dry. The first utilizes supercritical water, known as SCWO, for supercritcal water oxidation; the water is the oxidant that oxidizes biomass to either carbon monoxide or more generally carbon dioxide and is, in turn reduced to hydrogen. The second is "dry" reforming, where the oxidant is carbon dioxide and the reduced substance is the carbon dioxide which is reduced to carbon monoxide even as the biomass is oxidized to the same thing. If, despite the "dry" designation, water is injected into this system at some point as high temperature steam, the water will be reduced to hydrogen, and the carbon monoxide oxidized back to the dioxide for potential reuse.

A third safer way to recover carbon from biomass is by pyrolysis, which is heating the biomass in the absence of air.

If the heat to drive any of these processes is nuclear heat, the system can be very clean and, depending on the fate of the recovered carbon, carbon negative. In general, pyrolytic products, many of which come under the general rubric of "biooils" have marginal stability. However these oils can be converted via processing to more stable and usable fuels and/or materials.

Any system that produces pure carbon dioxide has the potential to be clean. The process described in the paper can do just that, produce pure carbon dioxide. It is actually a hybrid system; part electrolysis and part carbon "burning," albeit under water.

Hydrogen (H2), as a most promising candidate for an energy carrier as well as a fuel for fuel cell electric vehicles and power generation, is expected to play a key role in the route to a greener future.(1) Although most currently available H2 is produced from fossil fuels, such as natural gas, the introduction of solar/wind power gives hope for the production of H2 renewably and largely through water electrolysis. The voltage-based energy efficiency of alkaline electrolysis cell systems is 62–82%,(2,3) while its further increase is challenging.

Hydrogen is stored energy and not primary energy, irrespective of what morons like Amory Lovins represent with nonsense like "hydrogen hypercars." As I often point out, the second law of thermodynamics - which is not subject to repeal - requires that the storage of energy wastes energy. The introduction of this paper, while evoking the nonsense "expectation" for solar and wind about which we've been hearing for half a century with no meaningful result other than the trashing of pristine wilderness areas, points this out. Via existing electrolysis, between 38% and 18% of energy is lost as entropy, expressed as heat.

Anytime you read that hydrogen is "green" you are reading nonsense.

However, in a world powered by very high temperature processes, electricity could be a side product, particularly in times of low demand, and thus it may be, under these circumstances, to store energy.

Pyrolysis, and to a lesser extent, both wet and dry reformation can produce either biochar, or asphaltenes (tars) that can be converted to biocoke.

The paper suggests that these can work as assists to electrolysis.

The text continues:

The water electrolysis produces H2 and oxygen (O2), following an overall stoichiometry of 2H2O ? 2H2 + O2. The presence of solid carbon (C) in water, if it is electrochemically active, alters stoichiometry(4):

(3)This electrolysis system is called “carbon-assisted water electrolysis” (CAWE). A most particular feature of CAWE is integration of electric and chemical energies into that of H2. In theory, CAWE requires a standard potential (°E) as small as 0.21 V, which is about 1/6 of the normal water electrolysis (°E = 1.23 V). In other words, with the introduction of carbon, it is possible to reduce the power consumption for H2 production ideally to 1/6. This means that the chemical energy of H2 from CAWE is theoretically 600% of electricity input, while 500% originates from the chemical energy of carbon. CAWE is also recognized as a type of electrochemical gasification of carbon at an ambient or near-ambient temperature, and it can convert the chemical energy of carbon fully to that of H2.

CAWE was reported for the first time by Coughlin and Farooque.(4?7) They electrolyzed a coal–water slurry with sulfuric acid as a supporting electrolyte and found H2 evolution at a required potential of ?0.9 V. Later studies showed that Fe2+/Fe3+ species leached from coal had a catalytic role between an anode and coal particles, accelerating CAWE.(8?13) However, the continuous energy conversion from coal to H2 was difficult possibly because of the formation of stable iron-containing solids from those ions.(14?17) Carbon materials other than coal have rarely been used in CAWE. Seehra et al. applied a type of carbon black to CAWE and reported H2 evolution at an interelectrode potential well below 1.0 V.(18) They also applied nanosized carbon and cellulose-derived carbon-rich material to water electrolysis and reported their activities higher than that of carbon black.(19,20)...

...The present authors herein report that biomass-derived char (biochar) is an excellent material for high-performance CAWE. Biochar is a major product from the pyrolysis of lignocellulosic biomass.(21?24) The present authors applied the biochar to CAWE as a result of the following three reasons. First, it is expected that the biomass has not only chemical but also electrochemical reactivity higher than well-carbonized or graphitized carbon materials, such as carbon black as well as graphite. As shown in Table 1, standard potentials for water electrolysis with aromatic hydrocarbons are clearly smaller than that with C as graphite. Biochar is generally rich in aromatic hydrocarbons, and the structure is far from that of graphite.

The authors post a table of putative theoretical "kicks" that aromatic species (those in the table are not really conductive, and most are derived from dangerous fossil fuels):

Biochar, as the authors note, generally is quite porous, and thus has a large surface area relative to its mass. In electrolysis where pure oxygen is produced, the anode introduces inefficiency owing to the fact that the production of oxygen is a 4 electron process. (One can read many papers discussing this point and looking at ways to address the problem, but this another way.

Much of the rest can be approached by looking at the pictures:

The caption:

Figure 1. Conceptual diagram of a system of biomass conversion. This system consists of syngas production by endothermic CO2 gasification that integrates the biomass chemical energy and renewable-power-derived joule heat and H2 production by BAWE that integrates the biochar chemical energy and renewable power. CO2 gasification and BAWE supply biochar with a high specific surface area and CO2 to each other.

Two terms in the captions below are LSV which is "linear sweep voltammetry" and CE, "continuous electrolysis" each referring to a difference in the way the voltage is applied in these systems:

The temperature at which the biochar is formed has an effect on the voltages at which electrolysis (measured as current density) occurs:

The caption:

Figure 2. LSV profiles of BAWE with biochar carbonized at different TC ranging from 550 to 1050 °C and that without biochar (shown as the reference). Electrolyte = 3 mol/L H2SO4 aqueous.

I attended a lecture this evening by Nobel Laureate and activist, Richard Roberts.

It was just fabulous, not a scientific lecture, but an activist lecture.

Anyone who bashes Greenpeace's contempt for science is fine with me. He drove it hard, noting that Greenpeace has raised half a billion dollars to spread ignorance that he clearly characterized as a "Crime against humanity."

When I told him during Q&A I consider myself a liberal and an environmentalist, he interrupted me to say, "so am I," and I answered, "Indeed you are."

His chief concern: Human poverty. He's very active in Africa and in Bangladesh, fighting ignorance for the benefit of the poor.

An outstanding lecture, along with a few good Trump jokes.

The best joke was not his, but was our outgoing section President who obliquely referred to "Self made" "Daddy made me a small loan of a million dollars" fool when he said, "I'm glad you're self made; it absolves God of the responsibility."

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