January 16, 2022

It's nice to see papers about industrial technetium to start out 2022.

Starting out the New Year with the first issue of the new volume of one of my favorite journals, I was pleased to see this paper appear in the table of contents: Distribution Coefficient Model for Zirconium and Technetium Extraction from Nitric Acid Solution (Hongyan Chen, Megan Jobson, Robin J. Taylor, Dave A. Woodhead, Andrew J. Masters, and Clint A. Sharrad Industrial & Engineering Chemistry Research 2022 61 (1), 786-804)

Technetium is a remarkable metal in many ways, although it does not occur on Earth except in extremely low concentration from spontaneous fission in uranium ores; all of its isotopes are radioactive. It is however, a prominent component among fission products found in used nuclear fuel.

It's value derives from the fact that owing to the lanthanide contraction effect between the 5th and 6th periods of the periodic table, technetium's atomic radius and valence electron configuration are nearly identical with its valuable congener rhenium, a very, very rare and expensive metal with outstanding alloying and catalytic properties.

Many of the "superalloys" which have extreme resistance to corrosion and temperatures contain rhenium. Rhenium at 3180°C is the second highest melting metal element after tungsten ( 3407°C) Technetium is the eighth highest melting metal at 2200°C, but melts higher than metals like titanium, zirconium, chromium, vanadium, iron and nickel, the latter being the base metal of many superalloys utilized in high temperature turbines (albeit with thermal barrier coatings). Since the supply of rhenium is limited to ores subject to depletion, and technetium can be accumulated indefinitely - at least to the point of a Bateman equilibrium - it is worth considering the element as a rhenium substitute in superalloys, particularly those in closed systems such as power plant turbines. As technetium is a pure beta emitter and a reasonably long half-life, and in many applications would be contained in self-shielding in alloys, one can imagine many valuable structural uses for it. (It's main use today is to utilize its nuclear isomer 99mTc in medical imaging; basically people drink technetium solutions.) Because of the high price of rhenium, the quantities of rhenium in superalloys is small

The current mentality is, however to throw it away, which is tragic to my thinking.

But here's the really cool thing about this paper: The fact that the consideration it involves is taking place at all. It's evidence that the world is waking up and understanding that we need nuclear energy if we are to survive. It's that simple. It's would be nice to have, as a side product, to have this metal for the applications it can preform.

This paper is all about Zr/Tc separations, a pretty good thing to understand if we are to have a sustainable future.

The most widely used process for recycling used nuclear fuels is the Purex process and variants; these are solvent extraction processes. The work like this: These processes rely on chopping up the cladding of the fuel rods and dissolving everything in concentrated nitric acid. Complexing agents are added to solvents that do not dissolve in aqueous acid, the presence of the complexing agents allows them to become hydrophobic and thus they are extracted into the organic layer. These types have been in industrial use for more than half a century. The down side is that they generate a significant amount of chemical waste, some of which is radioactive.

I personally think there are better processes, many of which are pyroprocessing or electrochemical processing or hybrid processing.

This is a paper about the old ways though, but comes with the benefit of stripping radioactive materials, the metals zirconium and technetium, from the solvents and acids, thus allowing for their recovery. It also contains one interesting note reading between the lines.

From the paper's introduction:

The bold is mine. What these authors are discussing is apparently recycling fresh nuclear fuel shortly after removal from the reactor. This is obviated by the fact that the half-life of 95Zr is on the order of 64 days. This means that used fuels that are five years only 2.6 billionths of the radioactivity from 95Zr would remain, the rest having decayed to stable Molybdenum. Since they are concerned with the properties of this isotope, this means they have been thinking about the recycling of hot fuels. By contrast, many people think only of reprocessing fuels that have experienced long cooling periods; there is an impressive inventory of these long cooled fuels and admittedly, recovering the valuable materials in them is simpler than it would be for hot fuels. Reprocessing cooled fuels offers some advantages, but there are also good reasons, I think, for recycling hot fuels, but that's a topic for another day.

Nevertheless, to repeat, this subtle point strikes me as good news, an implication that we need to consider recycling fuels while still hot.

Again, I think there are better approaches for approaching fuel recycling, especially for hot fuels, but solvent extraction has a long industrial history and is well characterized. To the extent we rely on used nuclear fuels, the less mining will be required. Uranium mining companies might not like this, but to the extent we use our already mined uranium stocks, we offer hope to future generations.

My only point is this: It's good to see the chemistry of technetium processing discussed in the current fresh literature, because it is a sign post that the scientific community is beginning to focus on the value of used nuclear fuels as we enter 2022. I am not shy about stating that I regard the use of the materials found in used nuclear fuels as essential to human survival.

Have a pleasant Sunday.

January 15, 2022

If we are dying...

This the second half of a beautiful little poem I came across in this anthology for one of the books I'm reading, this one:

All We Can Save: Truth, Courage and Solutions for the Climate Crisis.

The book is described on its website thusly:



I'm reading the book for a Zoom book club in which I'm trying to find time.

The participants in the anthology are cultural commentators, poets, artists, pundits and even some scientists.

It's an interesting little read; I'm not sure I agree with all of the writers therein, and thus far it seems weak on "solutions" but although I'm not far in, I recommend the book highly.

Then again, I'm from the demographic that is largely responsible for this terrible mess, old, fat, bald, white men.

Any book that contains a poem this beautiful is worth reading, I think.

January 15, 2022

New word: Stiction.

I came across this word in the title of this paper: Practical Linear Regression-Based Method for Detection and Quantification of Stiction in Control Valves, (Seshu K. Damarla, Xi Sun, Fangwei Xu, Ashish Shah, Joseph Amalraj, and Biao Huang, Industrial & Engineering Chemistry Research 2022 61 (1), 502-514)

It means the friction that prevents bodies from movement, in this case in valves.

I feel like I should have seen this word before somewhere, and perhaps I did but ignored it.

It's a cool word. It rhymes with "friction."

I'll try it in a sentence: "The United States is failing because of stiction."

January 15, 2022

Temperature attributable mortality projections due to previously unobserved extreme heat in Europe

This "comment" is here: Seasonality reversal of temperature attributable mortality projections due to previously unobserved extreme heat in Europe (*Marcos Quijal-Zamorano,Èrica Martínez-Solanas,Hicham Achebak,Desislava Petrova,Jean-Marie Robine,François R Herrmann,Xavier Rodó,Joan Ballester, Lancet, Planetary Health VOLUME 5, ISSUE 9, E573-E575, SEPTEMBER 01, 2021)

The article is open sourced, and it refers to predicted deaths through the rest of this century.

Some text:

I have referred to reference three on DU, which is from a French publication. Maybe you've heard of France. It's a prominent European Country powered by nuclear energy, so powered for more than 40 years with no major radiation related death toll. As of this writing, (10:11 PM EST (US) 01/14/22) France is providing electricity with a carbon dioxide intensity of 115 g CO2/kwh, with 18.27% of those emissions (21 g CO/kwh) resulting from the fact that France is currently importing 4.18% of its electricity from its rather dirty neighbor, Germany, where the carbon dioxide intensity of electricity produced therein is 501 g CO/kwh as of this writing.

https://app.electricitymap.org/zone/FR

The Lancet Countdown, reference 1, is here: Nick Watts, Markus Amann, Nigel Arnell, Sonja Ayeb-Karlsson, Jessica Beagley, Kristine Belesova, Maxwell Boykoff, Peter Byass, Wenjia Cai, Diarmid Campbell-Lendrum, Stuart Capstick, Jonathan Chambers, Samantha Coleman, Carole Dalin, Meaghan Daly, Niheer Dasandi, Shouro Dasgupta, Michael Davies, Claudia Di Napoli, Paula Dominguez-Salas, Paul Drummond, Robert Dubrow, Kristie L Ebi, Matthew Eckelman, Paul Ekins, Luis E Escobar, Lucien Georgeson, Su Golder, Delia Grace, Hilary Graham, Paul Haggar, Ian Hamilton, Stella Hartinger, Jeremy Hess, Shih-Che Hsu, Nick Hughes, Slava Jankin Mikhaylov, Marcia P Jimenez, Ilan Kelman, Harry Kennard, Gregor Kiesewetter, Patrick L Kinney, Tord Kjellstrom, Dominic Kniveton, Pete Lampard, Bruno Lemke, Yang Liu, Zhao Liu, Melissa Lott, Rachel Lowe, Jaime Martinez-Urtaza, Mark Maslin, Lucy McAllister, Alice McGushin, Celia McMichael, James Milner, Maziar Moradi-Lakeh, Karyn Morrissey, Simon Munzert, Kris A Murray, Tara Neville, Maria Nilsson, Maquins Odhiambo Sewe, Tadj Oreszczyn, Matthias Otto, Fereidoon Owfi, Olivia Pearman, David Pencheon, Ruth Quinn, Mahnaz Rabbaniha, Elizabeth Robinson, Joacim Rocklöv, Marina Romanello, Jan C Semenza, Jodi Sherman, Liuhua Shi, Marco Springmann, Meisam Tabatabaei, Jonathon Taylor, Joaquin Triñanes, Joy Shumake-Guillemot, Bryan Vu, Paul Wilkinson, Matthew Winning, Peng Gong, Hugh Montgomery, Anthony Costello.

The 2020 report ofThe Lancet Countdown on health and climate change: responding to converging crises, The Lancet, Volume 397, Issue 10269, 2021, Pages 129-170,

I'm not sure if this paper is open sourced, so here's an excerpt:



The bold for the 2018 death toll is mine.

Germany, a prominent country in Europe is arguing with the rest of Europe that nuclear energy is "too dangerous." Yet is is difficult to record 296,000 deaths from nuclear energy on the entire planet over nearly 70 years of commercial nuclear energy operations, never mind one year.

The argument that the Germans make, that's it's OK to dump 500 g CO2/kwh on all of humanity, including future generations, given that there is no known industrial process to remove it, because nuclear power is "too dangerous" strikes me as a Trumpian scale distortion of something called "reality."

Climate change is "too dangerous," and there's real data behind this determination. The Germans seem to be out of their minds.

January 14, 2022

The World Accumulated 16 Zetajoules of Additional Heat in Its Oceans in 2021.

The article is open sourced apparently: Cheng, L., Abraham, J., Trenberth, K.E. et al. Another Record: Ocean Warming Continues through 2021 despite La Niña Conditions. Adv. Atmos. Sci. (2022).

A Zetajoule is 10^21 Joules.

For reference, all of the energy produced by humanity in 2020 amounted to 584 Exajoules, 584 X 10^18 Joules.

The full paper is not available as HTML text, but can be downloaded as a PDF file.

This is very bad news, but don't worry, be happy.

Watch car ads showing wind turbines and electric cars, and virgin wilderness turned into huge solar arrays. Then you'll feel better. All of this hype isn't doing shit to address climate change, but pretend that it is. You'll feel better.

January 14, 2022

We're number 1! (Really) Publications on Supercritical CO2 Brayton Cycles

So I'm reading this bibliographic review of CO2 Brayton cycles:

Aofang Yu, Wen Su, Xinxing Lin, Naijun Zhou, Recent trends of supercritical CO2 Brayton cycle: Bibliometric analysis and research review, Nuclear Engineering and Technology, Volume 53, Issue 3, 2021, Pages 699-714.

I often feel as if our country is terminally ill, not just politically with a major fascist party working to obstruct everything, but also that our respect for and ability in many sciences is decaying.

Then of course, there is the Webb telescope, apparently flawless engineering, and of course, the rapid development of RNA vaccines and then this comment in this paper:

I added the bold.

I sort of agree with the concept that nationalism is the refuge of fools, but it's nice to see that we (USA! USA! USA!) have become the world leader in this important area.

We're not dead yet, not by a long shot.

A little patriotism in the evening...

January 13, 2022

Yesterday my son drove me to pick up a new keyboard, when my keyboard failed.

I wasn't feeling well, and I asked him to drive.

On the way I asked him about processes to form silicon carbide for various applications and he gave me this neat little lecture on the subject, suggesting various routes for various purposes and the properties the material would have depending on the route of preparation and its behavior in different kinds of settings.

He was my teacher; after all these years, he was my teacher.

Life is beautiful and then you die.

January 13, 2022

Phytoremediation of soils contaminated with heavy metals and the production of biooils.

I came across this paper this evening: Hydrothermal Treatment of the Pristine and Contaminated Cd/Zn Hyperaccumulators for Bio-Oil Production and Heavy Metal Separation (Xiaoqiang Cui, Xiangming Li, Jianwei Zhang, Qiang Lin, Hui Xiao, Zhanjun Cheng, Beibei Yan, Xiaoe Yang, and Guanyi Chen ACS Sustainable Chemistry & Engineering 2022 10 (1), 603-612).

It contains this wonderful text to which I have added the bold and italicization of a single word in the introduction:

Unconscionable, that would be the right word.

As is the case with many metals, China is a large contributor to sources of cadmium, a highly toxic element because of the ability of cadmium to substitute for zinc in important metalloproteins, rending them ineffective.

Cadmium telluride solar cells are the second most common type of solar cells after silicon based solar cells. Tellurium isn't good for you either.

Distributed energy is distributed pollution.

As for biooils, a great deal has been written about hydrothermal production of biooils, potentially a cleaner and less water intensive alternative to fermentation. Biooils generally need to be deoxygenated before use as fuels, a process that is also carried out by thermal means. It is possible they may represent a minor component of recovery of carbon dioxide from the air.

Have a nice day tomorrow.

January 13, 2022

For the first time in 5 days, German electricity carbon intensity has fallen below 400 g CO2/kwh.

Accessed 12:33A 01/13/22. https://app.electricitymap.org/zone/DE

I've been monitoring German electricity during the recent 5 days of dunkelflaute. For most of this period, the much vaunted "more than 60 GW" of wind power capacity when I checked in was at around 10% or lower, with the carbon intensity of Germany often rising above 500 g CO2/kwh owing to the reliance on coal. There were multiple occasions when all the wind turbines in Germany were producing less or merely equivalent, more or less, electricity than Germany's three remaining nuclear reactors.

For the first time in 5 days, German carbon intensity for electricity is below 400 g CO2/kwh, 381 g CO2/kwh to be exact. Neighboring France was high (for France) for about two days, between 90 - 100 g CO2/kwh apparently because France sipped the wind energy Koolaid, and thus found it necessary to burn some gas because the wind wasn't blowing there either. However the more than 50 nuclear plants operating in France kept its carbon dioxide dumping to 1/4th to 1/5th of Germany's. As of this writing France is producing 99 g CO2/kwh. (Generally France's carbon intensity for electricity is on the order of 40-70 g CO2/kwh)

When the wind wasn't blowing, the Germans burned coal. Lots of it. There is no industrial process for removal of the coal waste generated by this event from the atmosphere into which it was dumped. This waste is the problem of every generation that comes after us.

As of this writing, the wind seems to be blowing again in Germany, and the capacity utilization of the "more than 60 GW" of wind capacity has risen to 32.84% as of this writing. Germany is still producing more electricity from coal (22.9 GW) than it is from wind (21.0 GW) and solar combined, since solar is producing zero energy in the dark.

The waste from the decision to close 14 of Germany's 17 nuclear plants, and thus rely on coal, is totally uncontained, and this coal waste will remain with humanity, free and uncontained, more or less for eternity.

Recent scientific literature has correlated death rates from Covid to intensity of air pollution in Germany, but even without Covid, German air pollution kills people, regularly and continuously.

(For example, among others : Aloys L. Prinz, David J. Richter, Long-term exposure to fine particulate matter air pollution: An ecological study of its effect on COVID-19 cases and fatality in Germany, Environmental Research, Volume 204, Part A, 2022,

Congrats to the anti-nuke so called "renewable energy" champions here and elsewhere, especially in Germany, where nuclear energy is "too dangerous" but murder by coal is not. Heckuvjob.

History will not forgive us; nor should it.

January 12, 2022

Cool paper on the preparation of nickel doped carbon electrocatalysts from CO2.

One interesting way to deal with carbon dioxide recovered from air, in direct air capture scenarios (using, perhaps, seawater as an extractant) is to actually reverse combustion by reducing the carbon dioxide back to carbon in such a way that the carbon has economic value in materials setting.

Last March, I wrote here about a paper on this topic that caught my eye and about which I think quite a bit, because of its potential side value in performing certain otherwise difficult chemical separations. That post is here: Electrolysis of Lithium-Free Molten Carbonates

Today I came across yet another paper along the same lines. It's this one: Nickel and Nitrogen-Doped Bifunctional ORR and HER Electrocatalysts Derived from CO2 (Anna-Liis Remmel, Sander Ratso, Giorgio Divitini, Mati Danilson, Valdek Mikli, Mai Uibu, Jaan Aruväli, and Ivar Kruusenberg, ACS Sustainable Chemistry & Engineering 2022 10 (1), 134-145).

The "HER" is the hydrogen evolution reaction, and ORR is oxygen reduction reaction.

HER is useful in electrolysis of water, which is not necessarily the best pathway for generating hydrogen for captive use, but is OK if extra electricity is available as a side product of high temperature driven chemistry, where the electricity is produced as a side product to recovery exergy from a thermal system.

By contrast, the ORR is useful in fuel cells as in hydrogen (or metal)/air systems.

This paper is about a molten carbonate system. I can't spend a lot of time discussing this paper here, but perhaps a few excerpts from the full text are in order.

The beginning text is about hydrogen fuel cells for cars, an idea I actually oppose, since I regard "hydrogen economy" nonsense as jus that, nonsense, but I do believe that hydrogen is an excellent captive industrial reagent for many important processes.

The opening text:

Further on in the introduction a description of the novel feature, carbonate reduction to carbon is advanced:



It is important to note that the reduction of carbon dioxide to carbon requires adding all of the energy that was released in the combustion that oxidized it to CO2, plus some, particularly in air capture, to overcome the entropy of mixing. Basically it means producing all of the energy ever released by the use of dangerous fossil fuels plus some.

Nevertheless, with clean energy, of which there is as a practical matter only one source, nuclear energy, these types of processes have much to recommend themselves, as they introduce an economic benefit for removing carbon dioxide from the air..

One reagent in the synthesis is dicyanamide, a cyanoguanidine. This is made via a route involving reacting calcium carbide with nitrogen gas at high temperatures. Calcium carbide, which can be used as a source of acetylene, can be made by heating biochars with molten calcium metal.

The molten carbonate system here is a eutectic of lithium carbonate and potassium carbonate. The paper I discussed in March utilized alkaline earth molten carbonates.

This is a cool paper that might be useful to future generations as the work under extreme duress to clean up the mess we are leaving them.