NNadir
NNadir's JournalHighly Efficient Plutonium Extraction Using a Phosphonium Phosphinate Task-Specific Ionic Liquid
The paper to which I'll refer in this post is this one: Highly Efficient Plutonium Extraction from Nitric Acid Feeds Using a Phosphonium Phosphinate Task-Specific Ionic Liquid Surekha D. Chowta, Arijit Sengupta, and Prasanta K. Mohapatra Industrial & Engineering Chemistry Research 2025 64 (2), 1252-1264.
The paper was published by Indian scientists.
As an advocate of the expanding use of nuclear energy, it behooves me to note, as India is a nation operating PHWRs, pressurized heavy water reactors, which as is the case with Canada, where the reactors are known as CANDUs, that dominate their nuclear power fleet, that this paper, does have nuclear weapons proliferation value, as CANDU type reactors allow for operando refueling. This said, nuclear weapons seem to have the advantage that people who possess them are generally afraid to use them. This said, there has always been a risk of the weapons falling into the hands of some of the most awful people on the planet, such as we have to our surprise, observed in the United States, where the slime mold in the White House can definitely be characterized as a "most awful person." Operando fuel replacement does allow for the preparation of weapons grade plutonium, although it can also be used to produce denatured plutonium not suitable for use in nuclear weapons, in fact, instantaneous denaturation by making reactor grade plutonium readily available in pure form.
Nevertheless, despite its risk of destroying the world, plutonium, in my view - this is unchanged despite the aforementioned caveat - essential to have any hope of saving the world and possibly even restoring what is possible to restore. Thus, risks involving easily observed human stupidity notwithstanding, this paper has much to recommend it.
From the paper's introduction:
Ionic liquids have been termed by some as “green” diluents, as they can be potential alternatives to the volatile organic compounds (VOCs), i.e., the molecular diluents due to favorable characteristics like low vapor pressure, high degree of thermal, chemical, and radiation stabilities, a wide range of electrochemical window, high solubility of several inorganic, organic, and polymeric materials, etc. (1−8) In nuclear fuel cycle activities, molecular diluents have been used in solvent extraction processes. However, lab-scale studies with ionic liquids have shown promise with much enhanced metal ion extraction. (9−12) The most attractive property of an ionic liquid diluent is the latter’s high degree of tunability. The metal ion extraction by n-butyl-substituted methyl imidazolium ionic liquids exhibited a “cation exchange” mechanism involving cationic species, while in the case of higher homologue, i.e., n-octyl-substituted methyl imidazolium-based ionic liquids, the extraction was found to predominantly proceed via a “solvation” mechanism involving neutral species. (13−16) Tuning of the extraction mechanism from “cation exchange” to “solvation” to “anion exchange” was reported to be successful, employing different variants of the ionic liquids, i.e., methyl imidazolium, pyridinium, and pyrrolidinium for the extraction of the uranyl ion using the same amide-based ligands. (17) Using appropriate combination of cations and anions of ionic liquids; the viscosity of the same can be modified and hence, the extraction kinetics can be tuned. (18−20) A proper understanding of the structure–activity relationship was found to be useful in fine-tuning the desired properties of the ionic liquids by minute structural modifications. (21,22) While the imidazolium- and pyridinium-based ionic liquids are often studied by researchers, the phosphonium-based ionic liquids are not well studied, though some of those are commercially available.
Nonaqueous processing techniques, frequently based on molten salts or ionic liquids, are capable of minimizing the volume of radioactive liquid wastes; while also mitigating corrosion issues arising in aqueous systems. Additionally, these methods are less susceptible to the generation of hydrogen gas, which is a safety hazard in aqueous reprocessing. The ability to achieve a more efficient separation of valuable materials such as uranium, plutonium, and minor actinides represents another significant advantage, as it promotes better recycling practices. (23−30) Overall, nonaqueous reprocessing offers a more sustainable, safer, and efficient solution for the management of nuclear waste. Membranes utilizing ionic liquids offer multiple advantages, including enhanced chemical stability, high ionic conductivity, and the potential for customization for specific applications. (31,32) Compared with traditional organic solvent-based membranes, these membranes are more resistant to degradation under harsh conditions. Moreover, ionic liquids can be specifically designed to possess unique properties, making them adaptable for various separation processes. (33,34) However, there are notable disadvantages such as their high cost, possible toxicity, and the challenges associated with their preparation and scalability. Additionally, the viscosity of ionic liquids may create complications in certain applications, and their long-term stability and environmental impact are areas that require further research.
Though the cation exchange mechanism (vide supra) facilitates metal ion extraction involving ionic liquid-based diluents, it has a major disadvantage of the loss of ionic liquid components via aqueous solubility. In this context, functionalized task-specific ionic liquids (TSILs) have been synthesized and employed with encouraging results. The functionalized ionic liquids reportedly induced the metal ion selectively by reducing the total number of components during their biphasic extractive mass transfer. (35−38) A phosphine oxide-based functionalized ionic liquid has been exploited for the extraction of UO22+. (39) The diglycolamide and CMPO-functionalized ionic liquid has been employed for the highly efficient extraction of trivalent lanthanides/actinides like Am3+/Eu3+. (40−43) In a separate study, a malonamide-functionalized ionic liquid has been employed for the extraction of uranyl ions and rare earth elements from lamp phosphor. (44−46) The crown ether-functionalized ionic liquids have also exhibited highly efficient and selective separation of lithium ions. (47) Several attempts were also made to include the functional group into the anionic part of the ionic liquid or as constituent anions. (48−50) In the case of β diketonate-functionalized ionic liquids, mainly with a TTA moiety, a similar highly efficient extraction of trivalent lanthanides has been evidenced...
Here is the structure of the ionic liquids being discussed:
The caption:
Figure 2. Structural formula of trihexyl tetradecyl phosphonium bis (2,4,4) trimethylpentylphosphinate (Cyphos IL 104).
Some distribution coefficients - note the logarithmic ordinate - showing the separation from uranium and americium are shown in the next figure. Americium separations are only necessary in cases where the nuclear fuel contains reactor grade, rather than weapons grade plutonium. (I have been thinking a lot about americium lately - a potentially very cool reactor fuel is certain physics issues can be addressed.)
The figure:
The caption (modified to address the limitations of the DU editor):
The ionic liquid was evaluated for recyclability, with only slight losses in the distribution coefficients.
Similarly, in irradiation experiments it was shown to have reasonable stability with respect to radiation doses up to 1000 Gray.
The system depends upon nitric acid dissolution, which for various reason, I personally find less than desirable. I'm a fluoride volatility kind of guy, but nonetheless the paper is interesting. Regrettably I will not have time to discuss it on a deeper level.
Have a nice day tomorrow.
I woke up this morning expecting a "bad day at the office" and...
...I'm having one, but at least I'm not a financial adviser explaining to my clients what happened to their portfolio.
New Weekly CO2 Concentration Record Set at the Mauna Loa Observatory, 428.15 ppm & 1st daily reading to exceed 430 ppm.
As I've indicated repeatedly in my DU writings, somewhat obsessively I keep spreadsheets of the of the daily, weekly, monthly and annual data at the Mauna Loa Carbon Dioxide Observatory, which I use to do calculations to record the dying of our atmosphere, a triumph of fear, dogma and ignorance that did not have to be, but nonetheless is, a fact.
Facts matter.
When writing these depressing repeating posts about new records being set, reminiscent, over the years, to the ticking of a clock at a deathwatch, I often repeat some of the language from a previous post on this awful series, as I am doing here with some modifications. It saves time.
A recent post (not my last on this topic) reflecting updating this on going disaster (last week) is here:
The Disastrous 2024 CO2 Data Recorded at Mauna Loa Stretches Further and Deeper into 2025.
This week's readings are not dramatically higher, than those recorded in the same week of 2024, week 9, "only" 2.94 ppm, which would have been extremely shocking in the 1980's or early 1990's but these days, with things getting worse faster, is only "ho hum."
The readings are, as of this morning as follows:
Week beginning on March 02, 2025: 428.15 ppm
Weekly value from 1 year ago: 425.18 ppm
Weekly value from 10 years ago: 401.57 ppm
Last updated: March 09, 2025
Weekly average CO2 at Mauna Loa
What is worthy of remark is that 428.15 ppm is the highest ever recorded for any week going back to 1959.
Here is a post of mine from April 2023 when the highest value ever recorded was lower:
New Weekly CO2 Concentration Record Set at the Mauna Loa Observatory, 424.40 ppm.
As this is early March, the 428.15 ppm "highest ever" reading weekly reading at Mauna Loa. As I always remark in this series of posts, if one looks, one can see that the rate of accumulation recorded at the Mauna Loa CO2 Observatory is a sine wave superimposed on a roughly quadratic axis:
Monthly Average Mauna Loa CO2
The maxima of the sine wave usually occurs later in the spring. In 2024, the then highest value ever recorded 427.94 ppm took place in the week beginning April 21, 2024, and fell thereafter. In 2023, the then highest value ever recorded 424.64 ppm took place in the week beginning May 28, 2023, and fell thereafter. In 2022, the then highest value ever recorded 421.63 ppm took place in the week beginning May 29, 2022, and fell thereafter and so on.
We may end up in 2025 seeing readings slightly lower, at, or even higher than 430 ppm in 2025. We'll probably see it by late May, assuming that the Observatory is not shut by the anti-science bigots who have seized control of our government and canceled our Constitution. The consequences, irrespective of whether the numbers are available and honestly reported, will not be subject to lies or misrepresentations by potentially thuggish liars; the planet will continue to burn, the weather will become more extreme and out of control. Oh and assholes will still carry on about how nuclear energy is "too dangerous," and the destruction of the planetary atmosphere isn't "too dangerous." These people will tell us, in a delusional counterfactual statement that so called "renewable energy" will save us.
This week, by the way, saw the highest daily reading ever recorded at the Mauna Loa Observatory:
March 08: 428.44 ppm
March 07: 430.60 ppm
March 06: 427.57 ppm
March 05: 428.00 ppm
March 04: 428.02 ppm
Last Updated: March 9, 2025
Recent Daily Average Mauna Loa CO2
March 7, 2025 is the first such reading to exceed 430 ppm.
The people who chant that "renewable energy" will save us and that nuclear energy is "too dangerous," will continue to so chant despite the observable fact that "renewable energy" has not saved us, isn't saving us, and I assert won't save us.
The reactionary impulse to make our energy supplies dependent on the weather, this precisely at the time we have destabilized the weather by lying to ourselves about our continuous and rising use of dangerous fossil fuels, was always an ignorant attack on nuclear energy. It was never about preventing the extreme global heating we now observe, never about the environment (you don't tear the shit out of wilderness to make industrial parks and declare yourself "green" ) and never about costs, since the required redundancy - while kept off the books dishonestly - is expensive, and, as it is almost always fossil fuel based, dirty.
We still have people here at DU, this late into the disaster prattling on about how so called "renewable energy" is beating out nuclear energy, even though the combined solar and wind industry combined has never, in an atmosphere of sybaritic bourgeois saturnalian enthusiasm, not once, produced as energy as nuclear energy produces routinely in an atmosphere of malign (and ignorant) criticism.
It is interesting and notable that the same people who still carry on with stupid reference to "costs" - they couldn't give a fuck about the cost of the extreme global heating we are now experiencing - and attack nuclear energy on this basis are completely and totally disinterested in attacking the unimaginable external costs of dangerous fossil fuels, costs recorded in millions of deaths each year, the destruction of vast ecosystems by fire and alternately inundation or just plain heat.
Irrespective of their inane anti-science rhetoric about batteries and hydrogen, as it disregards the laws of thermodynamics, an apologetic orgy of wishful thinking designed to make the failed solar and wind industries appear to be reliable, which they will never be, all the money spent on solar and wind is clearly wasted and ineffective. The impulse is reactionary, to make our energy supplies depend on the weather, precisely at the time we have destabilized the weather because the reactionary fantasy is not working.
How much money is it?
The amount of money spent on so called "renewable energy" since 2015 is 4.9 trillion dollars, compared to 524 billion dollars spent on nuclear energy (including a vague term the IEA calls "other clean energy" ), much of the latter to prevent the willful and deadly destruction of existing nuclear infrastructure. Presumably "other clean energy" includes fusion, which has provided zero useable energy for any purpose
IEA overview, Energy Investments.
The graphic is interactive at the link; one can calculate overall expenditures on what the IEA dubiously calls "clean energy," ignoring the fact that the expenditure on so called "renewable energy" is basically a front for maintaining the growing use of fossil fuels. One may also download a *.csv file with the data.
The Biden administration has rightly described itself as promoting "the largest sustained push to accelerate civil nuclear deployment in the United States in nearly five decades."
It is sad that we are now entering a very dark age, one in which propaganda and lies will obscure real knowledge. President did what he could do to save us; it proved to not be enough to overcome our collective ignorance.
White House holds summit on US nuclear energy deployment
My strong opinion that nuclear energy is the last best hope of the planet is not subject to change by appeals to clap trap about so called "nuclear waste," the big bogeymen at Fukushima, Chernobyl (and even more silly) Three Mile Island, blah, blah, blah...
I suggest finding someone more credulous than I to whom to chant endlessly about these points. Take a drive in your swell car out to a "no nukes" concert and convincing yourself that rock stars know more about energy than engineers and scientists. You deserve it. Whether future generations suffer in extreme poverty because of your smug pleasures and appalling selective attention is not your concern.
Oh, and of course, be sure self identify as an "environmentalist." As one who gives a shit about extreme global heating, I won't credit this self identification anymore than I credit Donold Trump's descriptions of himself as a "very stable genius" and all that, but who cares what I think? The "...but her emails..." and "...sane washed Donold Trump..." media describes antinukes as "environmentalists" after all, even if I find that absurd and delusional, so there's that.
Be sure to prattle on about your complete and total indifference to the laws of thermodynamics, laws of physics that are not subject to repeal by appeals to wishful thinking, by carrying on about energy storage, lots of battery bullshit, hydrogen bullshit, etc. as if there was enough so called “renewable energy” to store for months at a time. There hasn’t been any such "renewable energy" surfeits, to justify this junk, there aren't any and there won’t be any, but none of this should prevent you from the ruined landscapes and mining pits you leave for future generations as piles of ruins. Screw future generations. If they need resources, they can sort through our landfills and ruins.
Do all these things. Don't worry. Be happy.
Our media will declare you an “environmentalist.” Good for you.
As for me, I'm far more concerned with the collapse of the planetary atmosphere than I am with the fear that someone somewhere at sometime may die from an industrial accident involving radiation. Let me repeat: I am far more concerned with the vast death toll, extreme environmental destruction, and the global heating associated with the normal use of dangerous fossil fuels than I am about carrying on insipidly about Fukushima.
Nuclear energy is not risk free, nor will it ever be. It is simply vastly superior to all other options, which in a rational world, as opposed to the one in which we live, would be enough to embrace it.
In any case I am certainly prone to thank our last Constitutional President, Joe Biden, for his hard work to press for the expansion of nuclear energy, since very clearly we are out of time.
When our country, as precious as it has been to us, is an ancient memory, the rot we left behind in the planetary atmosphere will still persist.
History, should history exist, will not forgive us, nor should it.
Have a pleasant Sunday afternoon.
According to Open Secrets, Brown Forman, (Jack Daniels) donated largely to Democrats.
This may not be as much of a case as Leopards and faces as we think.
Neil DeGrasse Tyson Interviews Nuclear Engineer Kathryn Huff: Our Future Energy
Kathryn Huff served as Under Secretary of Energy for Nuclear Energy in the Biden Administration.
Talk show format with jokes and seriousness
Canada's Bruce 4 Nuclear Reactor Defuelled in Record Time.
The world won't collapse under His Maggotcy King Musk and his Ventriloquist's dummy, just the United States.
Bruce 4 defuelled in record time
Bruce unit 4 began its Major Component Replacement - or MCR - outage earlier this month. It is the third of six units at the Bruce site in Ontario to undergo MCR, which involves removing and replacing key reactor components including steam generators, pressure tubes, calandria tubes and feeder tubes, adding 30-35 years to the reactor's operating life.
The first unit to undergo MCR, Bruce unit 6, took 46 days to complete defueling, and the second - Bruce unit 3 - took 29 days. Each successive MCR has leveraged innovation and lessons learned from the previous projects, said Bruce A Plant Manager Lucas Van Wieringen. "Our private investments in state-of-the-art innovative modifications to improve safety and efficiency of our defuel campaign set our teams up for success," he said. "Our continued focus on proficiency of our workforce and a high-quality schedule through planning and preparation will enable us to continue to build momentum in our Life-Extension Program."
The next major milestone for the Bruce 4 MCR project is the chemical decontamination of the Primary Heat Transport (PHT) system prior to the start of construction activity, which begins with major component disassembly. Lessons learned from the first MCR outage at Bruce 6 led to the development of an innovative approach, with chemical decontamination of the PHT system at low level drain state, before the start of work at Bruce 3...
Despite the delusional complaint by antinukes, including "I'm not an antinuke" antinukes is that building nuclear plants is "too slow," these complex efforts can be built and operated in a timely fashion with experience and training.
These people - who I personally hold responsible for extreme global heating - have no sense of history, and no sense of how complex industrial processes are streamlined. The key to making nuclear operations go fast is something called "experience."
Oh Canada...!!!!!
Cabinet moves to reverse Italy's anti-nuclear stance.
The world won't collapse under His Maggotcy King Musk and his Ventriloquist's dummy, just the United States.
Cabinet moves to reverse Italy's anti-nuclear stance
On 28 February, on the proposal of President Giorgia Meloni and the Minister of the Environment and Energy Security Gilberto Pichetto Fratin, the Council of Ministers (the Italian cabinet) approved the draft delegation law on 'sustainable nuclear energy'.
The government said the text is aimed at "the inclusion of sustainable nuclear and fusion in the so-called 'Italian energy mix' and intervenes organically from an economic, social and environmental perspective, within the framework of European decarbonisation policies with a time horizon of 2050, consistently with the objectives of carbon neutrality and security of supply".
It added that the intervention aims to: ensure continuity of energy supply in the presence of a constant increase in demand and promote the achievement of energy independence; contribute to the decarbonisation objectives necessary to tackle climate change; and ensure the sustainability of costs borne by end users and the competitiveness of the national industrial system...
Canadian Company Validates the Molten Salt Reprocessing of Used Nuclear Fuels for Recovery of Materials.
The world won't collapse under His Maggotcy King Musk and his Ventriloquist's dummy, just the United States.
Pivotal moment for Moltex recycling process
Excerpts:
The innovative process - short for Waste to Stable Salt - extracts valuable materials and radioactive byproducts from used nuclear fuels in oxide form, including Candu, light water reactor and certain fast reactor fuels, such as mixed oxide (MOX) fuels. It does this in a single, streamlined 24-hour chemical process, with a versatile pretreatment step that the company says can accommodate exotic, experimental, or advanced reactor fuels.
The extracted transuranic elements are concentrated to produce molten salt fuel, while fission products are removed. This reduces waste volumes dramatically but also transforms nuclear waste into clean, dispatchable energy, permanently eliminating long-lived transuranic elements like plutonium, the company says. Coupled with Moltex's Stable Salt Reactor-Wasteburner - or SSR-W - reactor technology, the process enables the creation of a closed fuel cycle.
The WATSS process has now been validated on used fuel bundles from a "commercial reactor in Canada" through hot cell experiments carried out by Canadian Nuclear Laboratories, which has the only facilities in Canada equipped to handle used nuclear fuel. The experiments demonstrated that the process can extract 90% of the transuranic material from used fuel in 24 hours, with greater efficiency over longer periods of time, the company said...
This a very big deal, very big. I had no idea this process was being explored in Canada. It further enables them to close the border and move on.
After three years as a contract worker, my son was officially hired full time with benefits at his University.
He's been the gallery director in the art department since the University from which he graduated recruited him to work on a contract basis. He had no benefits and had to cover his own medical insurance. He worked long hours, did hard work, and was, as a result of one of his curatorial efforts, invited to go to China for several months to study a Chinese artist.
He lived with us for free during much of the time, and was able to put away a decent amount of money while planning the rest of his life. He finally left home a few months ago, just after a painful breakup with his first real love.
Finally, after a significant donation, the department - which has struggled financially - was able to create a permanent position. He's been moody and depressed in recent years, because of the uncertainty of with his future, and of course, most recently the intellectual, political, cultural, and moral collapse (and coming economic collapse) of the United States.
He had to go through the bureaucratic process of interviewing for the job he's been doing for years, did so, and was hired. He now has medical coverage - and what most excites him, dental coverage, paid vacation and what really, really, really thrills him, union membership.
It's been hard for me to speak with him in recent years because of his stress induced anger.
I had to call him on a technical issue yesterday, and he was a new man, his joy ringing through the conversation.
Today - this has never happened - he called me up, just to talk about his art, his work, the books he's reading, his thoughts on our country's struggle, his coming first date with a woman he met. In turn, it filled me with a happiness such as I have not known recently in these very stressful and frightening and in many ways appalling times, that my son is happy.
My sister-in-law visited, came with us to one of the best scientific lectures outside of my field I've ever attended, joined my wife and I for lunch with a good friend, saw people in the streets demonstrating for Ukraine, and then we spent two nights, Friday and Saturday having very nice wines before the fireplace, talked about my nephew's recovery from severe organic depression and how he kicked his pot habit, and my niece's thrill at her adventures in Italy.
It's a bad time, I know, and we had a few family downers on the periphery but this weekend for me, was personally, one worth living.
I wish you weekends as good as this one was for me.
Canada's Bruce Power Sets a Record for the Production of Cobalt 60 for Medical Use.
The Bruce Power Plant in Ontario, Canada features 8 CANDU (Pressurized Heavy Water) Nuclear Reactors built over a 10 year period from 1977 to 1987. The reactors have been undergoing a series of stepwise planned refurbishments to extend their lives for another 40 years or so.
The following article focuses on the refurbishment now underway on the Bruce 3, but also mentions the record production of the important medical isotope 60Co:
Milestones for Canada's Bruce Power units
Separately, Bruce Power announced it had completed its celebrated its largest-ever harvest of cobalt-60 during a planned outage at Bruce unit 5 during which upgrades will also be carried out to allow an increase in the production of cobalt -60 and High Specific Activity (HSA) cobalt-60. Cobalt-60 is used to sterilise around 40% of the world's single-use medical devices, including syringes, catheters, IV sets, surgical gloves and gauze used in a wide range of health care applications. HSA cobalt-60 is a medical-grade radioisotope used in the treatment of brain tumours and breast cancer through non-invasive procedures.
"The production of these potentially life-saving medical isotopes is a beacon of hope that is provided by our nuclear industry," Bruce Power Chief Operating Officer and Executive Vice-President and Chair of the Canadian Nuclear Isotope Council James Scongack said.
Civilization persists outside our borders despite our loss of it here.
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