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NNadir

NNadir's Journal
NNadir's Journal
January 19, 2025

It's actually very simple. The 2nd law of thermodynamics states definitively and inviolably that no matter...

...how energy is stored, the act of storing it wastes it. If the stored energy comes from fossil fuels - and let's stop lying to ourselves, roughly 80% of the world energy supply comes from this source - it means that one must burn more fossil fuels than one would do without storing energy. Energy that is put to use, which is always less energy than released in the use of a primary energy source, is called "exergy." Storing energy makes less energy available for use, and thus it destroys exergy.

There's a nice paper covering the whole topic here, giving the thermodynamic efficiency of various forms of energy storage, twelve of them, in fact: Manal AlShafi, Yusuf Bicer, Thermodynamic performance comparison of various energy storage systems from source-to-electricity for renewable energy resources, Energy, Volume 219, 2021, 119626.

The paper refers to the useless concept of so called "renewable energy" in the title, but applies to all forms of energy. The purpose of the useless so called "renewable energy" scheme is to convince a gullible public that energy storage is a good idea, and thus create an increased market for dangerous fossil fuels. The Moss Landing Plant is a dangerous natural gas plant, not a magical so called "renewable energy" plant. When the electricity generated in the plant is used to charge batteries, energy is wasted. Were it applied to the grid directly, without storage, more electricity would be available to provide exergy. Thus to charge the batteries, more natural gas is burned than would otherwise be burned.

Before the energy storage scam became popular because people believed that so called "renewable energy" was both significant and sustainable - it is neither - reliability was managed by running a few extra power plants than needed for immediate demand, to address demand surges. This was called "spinning reserve."

The forms of energy storage described in the paper, which looks pretty damned comprehensive to me, even if it doesn't cover flywheels, where the energy losses are frictional, both mechanical and air based, are shown in the following graphic:



There's a nice table of the ranges of energy losses via storage:



Ranges are given because a thermodynamic system depends sensitively on design, and more importantly, operating conditions, the most important of which is temperature.

Each storage system discussed in the paper has a nice schematic graphic associated with it. Here's the one for the most contemptibly marketed form of energy storage to my mind, one that is almost exclusively dependent on the waste of fossil fuels, hydrogen:



In the graphic, "heat out" represents destroyed exergy.

Here's some text describing the energy losses when the hydrogen is stored and when it is used; there are additional energy losses when hydrogen is produced, which are not discussed here:

2.5. Hydrogen storage
The hydrogen storage system includes a hydrogen storage tank, hydrogen fuel cell, cooler unit, and compressor. The primary input of this system is chemical energy. The main flows of the system are hydrogen and air, with two main outputs, as shown in Fig. 7. The chemical energy is stored in the hydrogen storage, and it leaves as gaseous hydrogen, entering the hydrogen fuel cell. As the air leaves the compressor, it enters the cooler unit to decrease the air temperature, and it enters the hydrogen fuel cell. The reaction of both air and gaseous hydrogen in the fuel cell produces the electrical output along with nitrogen and water.
The hydrogen storage system state point properties are shown in Table 10, and the following assumptions are considered for calculations:

The mass flow rate is calculated by considering 98 kg stored in the hydrogen storage tank (24 h operation considered)

The hydrogen fuel cell has a 30% heat loss.

The isentropic efficiency of the compressor is 85%

7.5% mass loss is assumed for hydrogen storage tank


I hope this helps explain why the popular fantasies about energy storage are pernicious in the extreme.

Enjoy the rest of the weekend as best as you can under the circumstances.
January 18, 2025

The Kiss.



We're going to see this documentary tomorrow if the snow doesn't box us in.

In spite of it all, love persists, as does art.
January 18, 2025

Dissolution Rates of Uranium Dioxide in Used Nuclear Fuel in an H2O2/Carbonate System Are Enhanced by Radiation.

The paper to which I'll refer in this post is this one: Study on the Dissolution Behavior of UO2 in the Na2CO3–H2O2 System Using a Flow-Through Dissolution Device Meng Zhang, Haofan Fang, Mingjian He, Caishan Jiao, Hongtao Zhao, and Chaobo Shang Industrial & Engineering Chemistry Research 2024 63 (50), 21662-21671.

The paper refers to a new, rather mild conditions (compared to the widely used PUREX, and other solvent separation methods depending on nitric acid) for the reprocessing of used nuclear fuel to recover its valuable components. This is the Carbex Process, which reduces the number of organic phase extractions to separate plutonium and uranium as compared to PUREX and the necessity of convoluted oxidation and reduction procedures, and avoids as well, the use of nitric acid to dissolve the used fuel pellets, substituting, hydrogen peroxide, H2O2 and sodium carbonate, Na2CO3.

It is generally employed after a technique called valoxidation, which involves heating the used fuel pellets to high temperatures in the presence of air or oxygen to drive off tritium (as tritiated water), cesium, rubidium, tellurium and under some conditions technetium and other elements with volatile oxides. This process also oxidizes uranium from the +4 valence state in UO2, uranium dioxide to U3O8, potentially either a mixed oxidation state, two U(V) and one U(VI) or a molecular orbital with distributed charge arrayed over three uranium atoms. (cf. Jayangani I. Ranasinghe, Linu Malakkal, Ericmoore Jossou, Barbara Szpunar, Jerzy A. Szpunar, Comprehensive study on the electronic and optical properties of (alpha)-U3O8, Computational Materials Science, Volume 171, 2020, 109264).

Recently in this space, there was an absurd claim, by an advocate of rebranding fossil fuels as "hydrogen," - a very dangerous prospect - that because a minor journal in the Springer Nature family of Scientific Journals (communications earth & environment) published a paper about a putative "hydrogen economy," a line of bullshit that is now 50 years old and still useless and ignorantly embraced, that therefore the following statement is true: "According to Nature.com, hydrogen is considered a crucial element for achieving net-zero greenhouse gas emissions." One hears these things and doesn't want to believe it. One sees these sorts of statements and one painfully understands how we have ended up in this awful political and physical mess. Stupidity rules, but is probably not worth dignifying these sorts of remarks by responding to them.

My point in including the previous paragraph is to remark that because I am discussing this process, I am not necessarily endorsing it. I just think it worthy of discussion. Overall, for the essential process of nuclear fuel reprocessing critical to human survival, but only slowly being recognized as such and quite possibly fitting into the rubric "too little, too late," I'm a fluoride volatilization kind of guy, which can handle the fuels better recovering valuable fission products as well as actinides, with the possible exception of making the recovery of valuable tritium more difficult, and possibly resulting in the release small amounts into the environment. (All nuclear plants do so, in trivial amounts.)

Tritium has the mass psychological property of producing orgies of fear and ignorance, the ever popular employment and celebration of stupidity, even though the amount of tritium in the environment has been falling from a huge peak in 1963, the era of nuclear weapons testing, before the majority of the time that the essential commercial nuclear industry was growing and operating. If you were alive in 1963 or born then or afterwards, you have been living with declining levels of environmental tritium for much of, or all of, your life, and look, tritium hasn't killed you, although something else will eventually. The cost of tritium today is roughly $30,000 per gram, with the main industrial uses being as a tracer, often in medical as well as environmental settings, and providing "glow in dark" watches, displacing the historical use of radium in this setting. It is also potentially useful for fusion reactors if in fact they ever become viable. It is said that one year's use of the experimental ITER reactor will consume the current world supply without providing any exergy (useful work) at all.

All this said, I applaud this paper, even as I don't endorse it, and I concede that the chemistry involved may indeed, under certain circumstances be industrially valuable. I especially admire the statement that used nuclear fuel is not, and should not be regarded as "waste." It's pretty damned valuable, particularly because it can accelerate access to fissionable materials beyond uranium, notably plutonium, but also americium, neptunium, and curium.

From the introduction to the paper:

As of the end of December 20, 2023, the global operational nuclear power capacity was 371.5 GW(e). (1) The large scale of nuclear power has led to a huge amount of spent nuclear fuel (SNF) being produced every year. Managing these SNF has become a limiting factor for the continued development of nuclear power. However, SNF is not a worthless waste, as it contains a large amount of valuable energy materials. By processing SNF, uranium resources can be fully utilized, greatly increasing resource utilization efficiency, ensuring the sustainable development of nuclear energy, and reducing the production of radioactive waste. (2) Currently, most SNF is directly stored in geological disposal repositories, with a small portion undergoing spent fuel reprocessing process. (3)

The only commercially operated spent nuclear fuel reprocessing process now is the PUREX process. The PUREX process has been refined since its proposal, but unresolved issues remain, (4-8) including high costs and significant waste generation; strong oxidizing properties of nitric acid corrode equipment and necessitate extra safety measures. In response to these issues, researchers suggest using a relatively mild carbonate solution as a medium to replace concentrated nitric acid for dissolving SNF and separating uranium, plutonium, and other elements. The CARBEX process proposed in 2008 (CARBonate EXtraction) is one of the representatives. (9) The CARBEX process uses Na2CO3–H2O2 as the dissolution solution and utilizes actinide elements to form stable complexes with carbonate anions for selective extraction of actinide elements. (5,10-12) It is a promising spent fuel reprocessing process, but there is little research on the dissolution stage in the CARBEX process, especially on the dissolution behavior of spent fuel in the Na2CO3–H2O2 system...


The authors note that in proposed and actual "nuclear waste" dumps, a naturally occurring CARBEX type process may take place, not that such a process, to my mind, involves much real risk, but since antinukes - the drivers of the extreme global heating now observed - have shit for brains understanding of risk and rely on paranoia driven by selective attention, worrying that a radioactive atom might show up in their otherwise useless brains.

From the introduction:

As of the end of December 20, 2023, the global operational nuclear power capacity was 371.5 GW(e). (1) The large scale of nuclear power has led to a huge amount of spent nuclear fuel (SNF) being produced every year. Managing these SNF has become a limiting factor for the continued development of nuclear power. However, SNF is not a worthless waste, as it contains a large amount of valuable energy materials. By processing SNF, uranium resources can be fully utilized, greatly increasing resource utilization efficiency, ensuring the sustainable development of nuclear energy, and reducing the production of radioactive waste. (2) Currently, most SNF is directly stored in geological disposal repositories, with a small portion undergoing spent fuel reprocessing process. (3)

The only commercially operated spent nuclear fuel reprocessing process now is the PUREX process. The PUREX process has been refined since its proposal, but unresolved issues remain, (4-8) including high costs and significant waste generation; strong oxidizing properties of nitric acid corrode equipment and necessitate extra safety measures. In response to these issues, researchers suggest using a relatively mild carbonate solution as a medium to replace concentrated nitric acid for dissolving SNF and separating uranium, plutonium, and other elements. The CARBEX process proposed in 2008 (CARBonate EXtraction) is one of the representatives. (9) The CARBEX process uses Na2CO3–H2O2 as the dissolution solution and utilizes actinide elements to form stable complexes with carbonate anions for selective extraction of actinide elements. (5,10-12) It is a promising spent fuel reprocessing process, but there is little research on the dissolution stage in the CARBEX process, especially on the dissolution behavior of spent fuel in the Na2CO3–H2O2 system.


It is probably best to tell the story found in the paper in some equations and graphics:

Water is subject to radiolysis, for good and for bad:



Mechanistically these free radicals interact to make products.



(No, the production of hydrogen is not an industrial route for this much hyped gas, the "G values" which represent the reaction rates per unit of radiation is small.)

In its +6 oxidation state, uranium forms a soluble carbonate complex, which the key to the entire process.



The authors note that this process in a so called "nuclear waste" dump - I oppose all waste dumps as I'm a closed cycle kind of guy - this process may take place, releasing some actinides.

The CARBEX process utilizes the solubility of U+6 to dissolve UO2 by oxidizing it with hydrogen peroxide:

.

Some graphics:

The schematic for the experimental apparatus:



The caption:

Figure 1. Schematic diagram of the flow-through dissolution device in irradiation environment.


The purpose of the paper is to show how radiation effects the hydrogen peroxide/carbonate system, and reaction rates. The authors evaluate the effects of varying parameters in the system as the following graphics will show:




The caption:

Figure 2. Effect of different concentrations of H2O2 on the dissolution rates under the nonirradiation environment of UO2 (25 °C, 4 mL/min flow rate).




Figure 3. Effect of different concentrations of Na2CO3 on the dissolution rates under nonirradiation environment of UO2 (25 °C, 4 mL/min flow rate).


The process takes place in two stages, oxidation followed by dissolution as shown in this cartoon (which also appears in the abstract.)




The caption:

Figure 6. Dissolution mechanism of UO2 in a Na2CO3–H2O2 peroxide system without irradiated conditions.


The reactions associated with dissolution:





Comparison of the effect of concentration of hydrogen peroxide in irradiation and nonirradation conditions:

The caption:

Figure 7. (a) Comparison of the effects of different H2O2 concentrations on UO2 dissolution rates under irradiated and nonirradiated conditions. (b) Dissolution rate when cH2O2 = 0, i.e., the part circled by the red dashed line in (a). (0.5 mol/L Na2CO3, 25 °C, 2 mL/min flow rate, 360 Gy/h).


The Gray is a derived unit of absorbed energy and has units of Joules/kg. It represents the amount of energy deposited in mass by radiation.

The effect of carbonate concentrations under rradiation and nonirradation conditions. (Note that there is a maxima.)



The caption:

Figure 8. Comparison of the effects of different Na2CO3 concentrations on UO2 dissolution rates under irradiated and nonirradiated conditions (1.0 mol/L H2O2 , 25 °C, 2 mL/min flow rate, 360 Gy/h).


The more absorbed radiation, the better:



The caption:

Figure 9. Dissolution rate of UO2 pellets at different radiation dose rates (0.5 mol/L Na2CO3, 1.0 mol/L H2O2 , 25 °C, 2 mL/min flow rate).


Radiation increases the dissolved uranium:



The caption:

Figure 10. Uranium concentration dissolved from UO2 in 0.1 mol/L Na2CO3 solution at different doses (room temperature, radiation dose rate 10,000 Gy/h, solid-to-liquid ratio is 1:100)


The authors note that the experimental conditions are very different than might take place in a putative so called "nuclear waste" dump, if, in a persistent but dubious "dump" mentality continues to exist for used nuclear fuel, particularly in the absence of oxidative peroxide:

...In a (gamma)-irradiated environment without H2O2 present, even after high-intensity irradiation, dissolved uranium remains at low concentrations in solution with [UO2(CO3)3]4- as its main component. Under these conditions, oxidative radiolysis products such as •OH and •HO2 are generated but do not sufficiently contact with solids to significantly promote dissolution processes. This scenario mirrors that found in spent fuel geological disposal repositories...


I enjoyed the paper, especially because it's one in which I learned things I did not know.

Conceivably, a better world is possible, but, under the circumstances, unlikely. Respecting the value of used nuclear fuel, seeing as a gift to future generations rather than another liability in the plethora of other liabilities, far more dire, the worst being the collapse of the planetary atmosphere, would be an honorable idea.

However honor, as a concept, is becoming irrelevant, it seems. History will not forgive us, nor should it.

Have a nice weekend in spite of it all.
January 18, 2025

As Future Generations Will Need to Live on Our Trash: Recovery of Phosphorous and Fluorine from Phosphogypsum.

The paper to which I'll briefly refer in this post is this one: Investigation on the Mechanism of Efficient Removal of Phosphorus and Fluorine Impurities from Phosphogypsum by an In Situ Recrystallization Purification Method Daping Chen, Jinbao Song, Jupei Xia, Binbin He, Qiongbo Zhou, Yidong Hou, Yunxiang Nie, and Yi Mei Industrial & Engineering Chemistry Research 2024 63 (51), 22369-22379.

The world food supply depends on two major contributors to fertilizer, fixed nitrogen, which in theory and in (rather dirty) practice is available via the Haber-Bosch process, now overwhelmingly produced using hydrogen prepared from the steam reforming of dangerous fossil fuels, and phosphorous, which is mined, and thus subject to depletion. The paper refers to the waste products of phosphorous mining, which still contains some industrially inaccessible phosphorous, as well as the industrially important element fluorine.

My interest in the paper was driven by scale, the quantity of waste phosphogypsum, which is reportedly 6 billion tons.

From the introductory text:

Phosphogypsum, whose main component is calcium sulfate dihydrate (CaSO4·2H2O), is an industrial solid waste generated during the production process of wet process phosphoric acid. (1,2) Up to 4–6 tons of phosphogypsum will be produced when 1 ton of phosphoric acid product is obtained. (3,4) The global inventory of phosphogypsum has exceeded 6 billion tons, and it is expanding at a rate of 150 million tons annually. However, due to its high proportion of harmful impurities, the comprehensive utilization rate of phosphogypsum is only about 15%, and most countries still rely mainly on inventory. (5) According to the statistics from the China Phosphate and Compound Fertilizer Industry Association, the production of phosphogypsum in China exceeded 80 million tons in 2021, and the total storage capacity in 2022 has reached 700 million tons, ranking first in the world. (6) The long-term accumulation of a large amount of phosphogypsum has occupied valuable land resources. In addition, the harmful impurities such as phosphorus, fluorine, and metal ions contained in phosphogypsum, once immersed in groundwater, rivers, and lakes, can cause severe water contamination and seriously threaten human life safety. (7,8) At present, phosphogypsum is mainly used to prepare cement retarders, building gypsum powder, soil amendments, roadbed materials, etc., but its comprehensive utilization rate is less than 50%. (9?11) The phosphorus and fluorine impurities from phosphogypsum can affect the performance and quality of subsequent products, seriously restricting their large-scale application. (12) Therefore, to effectively solve the storage and utilization problems of phosphogypsum, it is crucial to eliminate phosphorus and fluorine impurities...


The authors propose a relatively mild procedure for recovering the valuable elements from this waste product.

I will not have time to go into many of the details, but the paper in its conclusions gives the process conditions which involve rather mild conditions accessible from process intensification using heat networks as well as mechanical tools:

In this article, an effective method for removing phosphorus and fluorine impurities from phosphogypsum through in situ recrystallization and washing was investigated. The experimental results show that the optimal impurity purification conditions are as follows: stirring rate of 100 r/min, liquid–solid mass ratio of 3:1, recrystallization time of 40 min, recrystallization temperature of 50 °C, washing temperature of 70 °C, and 3 washing cycles. The removal efficiencies of phosphorus and fluorine are 86.4% and 95.71%, respectively, exhibiting a better purification effect. In addition, the purification mechanism for phosphogypsum is elucidated. During the recrystallization and washing process of FPG, CaSO4·0.5H2O dissolves and then transforms into larger rhombic CaSO4·2H2O particles. In the meantime, the impurities, such as water-soluble phosphorus (H3PO4, H2PO4–, HPO42–, and Ca(H2PO4)2), eutectic phosphorus (CaHPO4·2H2O), and water-soluble fluorine (F–, Na2SiF6, and K2SiF6), carried in FPG are transferred from the solid phase to the liquid phase, thereby achieving purification of phosphogypsum. It is worth noting that some of the eutectic phosphorus entrained in phosphogypsum also dissolves in the liquid phase. The purified phosphogypsum can meet the requirements for producing cement retarders and gypsum blocks.


The paper contains a photograph of a pilot plant attached to an industrial facility in China. It is capable of processing 1.5 million tons per year.

We have screwed future generations royally, and the world is sinking into a vast political garbage heap of proto and actual fascism but perhaps from the ashes of the resulting political and actual fires to come, there will be something left to salvage.

History will not forgive us nor should it.

Have a nice weekend.
January 12, 2025

What Is Not Being Discussed About the LA Fires.

It is well known, and widely reported in the scientific literature, that health risks from wildfires in terms of air pollutants exist and are profound. Since 2021, Google Scholar reports over 21,000 papers on the topic.

Based on the search terms I used, there are far fewer concerning residential fires, and the toxicology of the smoke.

Here's one open sourced paper on the topic I came across: Horn, G.P., Dow, N.W. & Neumann, D.L. Pilot Study on Fire Effluent Condensate from Full Scale Residential Fires. Fire Technol 60, 1–18 (2024)

I don't have any special insight to this topic, but it occurs to me that burning residential (and commercial) buildings in the LA area should generate a set of volatile pollutants very similar to those generated in the World Trade Center Attack and subsequent fires.

Whether we acknowledge it or not, our residences, when combusted, are a toxicological nightmare of polymers, electronics (containing a plethora of potentially volatilizable and highly toxic metals) and (believe it or not) toxic flame retardants, solvents and other chemicals.

The health consequences of these fires will persist for decades.

Things will get worse, not better, as extreme global heating accelerates, an acceleration that will increase (the third derivative) with time given the international (and notably in the suicidal United States) deliberate embrace of ignorance.

January 12, 2025

An Interesting Note on Low Energy Industrial Regeneration of Desiccants with Supercritical CO2

I'll briefly refer to the following paper I came across this morning: Regeneration of Spent Desiccants with Supercritical CO2 Astrid Melissa Rojas Márquez, Iris Beatriz Vega Erramuspe, Brian K. Via, Bhima Sastri, and Sujit Banerjee Industrial & Engineering Chemistry Research 2024 63 (49), 21154-21157.

The paper is open sourced.

It apparently can, in limited circumstances, reduce the energy cost for the removal of water in industrial processes.

Desiccants used in industry are typically dehydrated through temperature swing adsorption. High temperatures of 200–250 °C are required for molecular sieve; (1,2) less aggressive conditions suffice for dessicants such as silica gel (3), where solar dryers can even be used. The energy burden for regeneration is high because the water is removed evaporatively. Supercritical CO2 (sCO2) has recently been used to dewater a wide range of materials ranging from ion exchange resins (4) to sludge. (5) The water is both dissolved and emulsified in the sCO2 (6), which can then be partially expanded to release the water. The energy savings are considerable because the water is removed nonevaporatively at 90 °C. sCO2 has also been used to decontaminate spent sorbents such as activated carbon from compounds such as chlorophenol (7) and xylene. (8) While these spent sorbents are frequently water-laden, especially when they are used to remove dissolved contaminants from water, the focus has been on removing the organic contaminants from the sorbent rather than on dewatering it. This paper describes the removal of water by sCO2 from molecular sieve, activated carbon, graphite and silica gel, and interprets the different conditions that appy to each desiccant. Because use of sCO2 requires a pressure vessel, the approach is especially suitable for high-value low-volume applications, such as the regeneration of desiccants used to capture tritiated water vapor in the nuclear industry. (2,9)


The nuclear plant application is interesting, since the release of tritium generates a lot of public stupidity despite its low risk. This public stupidity has played a role in driving the increasing use of dangerous fossil fuels, causing millions of air pollution deaths each year, destroying ecosystems, and leaving the planet in flames. This form of public stupidity, like many other forms of public stupidity, say like electing a senile moron to the office of President of the United States, kills people.

Tritium levels, which are never zero because tritium forms in the atmosphere from solar radiation albeit at a low level. Levels of tritium in the planetary atmosphere have been falling since 1963, when they peaked as a result of open atmosphere nuclear testing.

Not much isolated tritium exists on Earth, and is chiefly available in Canada, where it is a byproduct of the wonderful CANDU reactors, which utilize deuterium as a moderator. Although the capture cross section of deuterium is very low, accounting for its use as a moderator, it is not zero, and tritium is generated in these reactors by neutron capture.

There is probably not enough isolated tritium on Earth to run a fusion reactor for as long as a year, a subject that is seldom discussed in the magical thinking about fusion energy. However tritium can be generated, as needed, by placing lithium targets in a fission reactor. Tritium in hydrogen bombs is generated using lithium deuteride in situ.

Have a nice Sunday.
January 11, 2025

I hate to inject some reality into this conversation but must do so. I loved President Carter, but...

...despite claiming enthusiasm for human rights, he coddled the Shah of Iran, a very brutal dictator, to have access to oil. This ultimately led to his political downfall.

He funded and hyped "coal to oil" schemes, Fischer-Tropsch chemistry, that had only been industrialized in Nazi Germany and in Apartheid era South Africa. Had this been commercialized in the US; it would have led to a climate disaster at unprecedented levels, although in fairness, although scientists were aware of the issue, it was not publicly and politically prominent until the issue was raised to that level, wisely, by Al Gore.

Carter decided to forego used nuclear fuel reprocessing as a "moral example." (Nations around the world ignored his "example" without a single nuclear war breaking out.) This is something of a mixed bag, since at that time the commercial (and military) route was PUREX processing, and cleaner routes exist now. However, had the United States, the world's largest producer of nuclear energy then and now, used MOX fuels, we would have much higher inventories of fissionable actinides which will be essential to address whatever (increasingly remote) chance to at least ameliorate the extreme global heating we now observe. If he were really a nuclear engineer, rather than a military figure in the nuclear Navy, he would have clearly understood the difference between reactor grade plutonium and weapons grade plutonium. Ideally we could have done away with uranium enrichment, thus lowering the prospect of weapons development.

On Plutonium, Nuclear War, and Nuclear Peace

He proposed the "Carter Doctrine" which was a policy by which the United States claimed the right militarily to seize foreign oil fields, something it did in both Iraq wars under each of the Bushes.

Finally, he hyped so called "renewable energy" which has been an expensive and highly damaging disaster, soaking trillions of dollars and doing nothing other than to accelerate the destruction of the atmosphere - adding the destruction of precious ecosystems, increased mining, and the industrialization of much wilderness to the damage - and entrenching the use of dangerous fossil fuels, on which so called "renewable energy" depends.

President Carter was a good man; his post Presidency was the greatest ever, with the possible exception of that of John Quincy Adams, but his energy policies as President were neither wise nor worthy. The applause for his energy policies strikes me as extremely dubious.

He does not stand as President among the pantheon of great Democratic Presidents since the dawn of the 20th century. Only JFK and Woodrow Wilson stand lower in my estimation, and he does not compare with the greater Presidencies of FDR, Harry Truman, Joe Biden, Lyndon Johnson, Barack Obama, and Bill Clinton.

As a man, he may rank higher than some of these men, but only as a man, not as a President, especially an energy President, as his energy policies were not inspiring at all. They led down the road to disaster.

To answer the question of who is responsible for the extreme global heating we now observe, a mirror would be an extremely useful device to illuminate the answer. Turn the lights on when you use one.

Have a nice weekend.

January 11, 2025

Extraction of Uranium in Supercritical Carbon Dioxide Using Incinerable Reagents

The paper I'll briefly discuss in this post is this one: Direct, Acid-Free Uranium Purification from Solid Analytical Waste by Supercritical Carbon Dioxide Extraction with Incinerable N,N-Dialkyl Amide Adducts, Avinash S. Kanekar, Shiny S. Kumar, Ankita Rao, and Sangita Dhara Industrial & Engineering Chemistry Research 2024 63 (48), 21001-21008.

Recently I remarked in a comment here that the flowback water from fracking operations in Pennsylvania is far more radioactive than seawater outside of the Fukushima reactor, Fukushima fetishes being the focus of antinuke stupidity that has resulted in the ongoing and accelerating destruction of the planetary atmosphere. I remarked that this is because the dangerous mining of dangerous natural gas takes place in a geological formation known as the Reading Prong, which is a fairly rich uranium ore. Fracking operations liberate radium and radon in the uranium decay pathway, these elements being in secular equilibrium with the parent uranium. Further I suggested, that once the fracking operations, which are destroying the atmosphere resulting in the extreme global heating we now experience, the uranium might be extracted using supercritical CO2 (SCCO2) as the solvent. (A current approach to uranium mining without the use of digging equipment is known as ISL (In Situ leaching) which is practiced in Kazakhstan, albeit using water, not SCCO2 as the solvent.

The paper referenced is lab scale, and scale up to industrial level may be problematic, but it's worth considering if not because we need, over the long term, in a sane world as opposed to the one in which we live, to mine uranium - in a fast neutron spectrum, the uranium and thorium already mined might supply all the world's energy needs for many centuries - but as a means of remediating uranium formations through which groundwater used for drinking and irrigation purposes passes.

Note that SCCO2 is an opportunity to put the dangerous fossil fuel waste CO2 to use, and it also notable that in such a case, as opposed to fracking operations, radium would not be extracted but rather rendered insoluble as the carbonate.

Some text from the paper's introduction:

Uranium-based fuels occupy the core of all of the efforts toward net zero attainment by nuclear power generation. (1,2) As a part of the chemical quality control (CQC) operation for matrices relevant to nuclear fuel fabrication, bulk assay of uranium is being carried out by redox titrimetry. (3?5) This results in the generation of a large volume of analytical waste solution containing uranium along with other metal impurities (from the initial matrices as well as redox titrimetric reagents). Precipitation is a conventional route for preconcentration of uranium from such multicomponent systems. (6?8) Two lots of analytical waste solutions were preconcentrated by precipitation with ammonia (W1 and W2) and preserved for further purification. The conventional routes for uranium extraction and purification involve acid digestion followed by solvent extraction with various phosphorus-based extractants, viz. TBP, TOPO, DEHPA. (9) This is then followed by stripping of uranium to the aqueous phase and subsequent precipitation to get a pure solid.

Supercritical carbon dioxide (SC CO2), (10) modified with suitable extractants, is a lucrative option for metal ion extraction owing to its moderate critical constants (Pc = 72.8 atm., and Tc = 304.1 K), radiochemical stability, commercial availability, and nontoxicity. Due to its low viscosity and high diffusivity, SC CO2 extraction finds crucial applications for direct recovery of metal ions from solid matrices, thus limiting the number of process steps and secondary waste generation. Also, under ambient pressure and temperature conditions, CO2 gets converted to gas, leading to collection of a compact, concentrated metal-complex extract. N,N-dialkyl amides, by virtue of being incinerable and having tunable extraction properties with varying alkyl chain, have been investigated widely for solvent extraction studies. (10?15) Few studies on SC CO2 extraction of uranium and thorium, especially from nitric acid medium, using amides have been reported from our group. (16?18) Interestingly, direct extraction studies from crude solid matrices using adducts of extractants, especially tributyl phosphate (TBP), provide a unique opportunity (19) and have been explored by us. (20,21) N,N-dialkyl amides have been demonstrated to have higher selectivity for uranium over TBP. (22,23) However, systematic studies exploring amide adducts for extraction of uranium from crude matrices is lacking.

To the best of our knowledge, this is a first detailed investigation of the usage of adducts of N,N-dialkyl amides, viz. N,N-dibutyl octanamide (DBOA), N,N-dihexyl octanamide (DHOA), and N,N-dibutyl-2-ethyl hexanamide (DBEHA), for direct supercritical carbon dioxide extraction of uranium from actual solid waste matrices (W1 and W2). The physical properties (density and viscosity at different temperatures) and chemical composition (water and nitric acid contents) of the adducts were investigated. Isotherms for SC CO2 extraction of U from UO2 using the DBOA adduct were obtained to optimize the pressure and temperature conditions. The SC CO2 extraction efficiency of uranium from W1 and W2 as well as purification from other impurities was examined. The results were compared with the adduct of TBP. The feasibility of direct precipitation, without stripping, of uranium by ammonia addition was explored from the concentrated SC CO2 extracts for several runs. The precipitates obtained as such and heated to 773 K were characterized...


Some figures from the text:



The caption:

Figure 2. Isotherms for SC CO2 dissolution-extraction of U from uranium oxide employing DBOA adduct (?20 mg UO2; 0.5 mL of DBOA adduct; in situ mode of complexation; 20 min static time + 20 min dynamic time; 2 mL min–1 CO2 flow rate). The results are the average of triplicate runs; average standard deviation = ±4%.





The caption:

Figure 7. Impurity content for the initial waste precipitate and ADU precipitate of the U-DBOA complex in SC CO2 extract for (a) W1, ADU1 and (b) W2, ADU2.


Note: That in SCCO2 mining operations, depending on economics, selectivity toward metals other than uranium may not be a good thing.



The caption:

Figure 8. Uranium content for the initial waste precipitate and ADU precipitate of U-DBOA complex in SC CO2 extract.


In general, with such chemistry being utilized on an industrial scale in ISL settings, this would be an example of CCU, carbon capture and utilization, although it is unlikely that it would make much of a dent in the destruction to the atmosphere wrought by the dangerous fossil fuel waste CO2. Small amounts of the CO2 solvent would be geologically sequestered as carbonates under these condition, but nothing to generate much excitement. It is likely that the operation might also remove some of the fracking chemicals left in the formation by gas extraction. These would need to be treated in some way. The rocks shattered by fracking might perform far better, owing to particle size, in a uranium extraction operation.

From the paper's conclusions:

The properties of SC CO2, viz. favorable transport properties (high diffusivity and low viscosity), allowing penetration through the solid matrix and ability of collection of compact extract, were exploited for two-step conversion of crude solid wastes (less than 30% U content) to purified ADU ( approx stoichiometric U content). Nitric acid adducts of N,N-dialkyl amides were utilized for the dual roles of dissolution and extraction, with DBOA faring best in terms of uranium extraction (88%) and purification (highest separation factors for Fe, Ni, Ti, Cr). The structure of amides and their chemical compositions decided the overall efficiency. The present scheme illustrated a reduction in the process steps and chemical inventory vis-à-vis the conventional route.


Have a nice weekend.


January 11, 2025

Continuous Hydrolysis of CuCl2 in the Copper Based Thermochemical Hydrogen Cycle

The paper to which I will very briefly refer is this one: Continuous CuCl2 Hydrolysis in the Six-Step Cu–Cl Thermochemical Cycle for Green Hydrogen Production Ramdas S. Kadam, Ashwini B. Nirukhe, and Ganapati D. Yadav Industrial & Engineering Chemistry Research 2024 63 (48), 20787-20799.

I have low tolerance for all the bullshit handed out about "green" hydrogen, because usually "green" - a much abused word these days - is connected with so called "renewable energy," a mass and land intensive scheme popularly described as "green," although it is no such thing. The vast sums of money squandered on so called "renewable energy" has been useless, since so called "renewable energy" depends on access to fossil fuels, and thus has had no effect on arresting or slowing the extreme global heating we now observe. In fact things are getting worse faster.

I especially hold in contempt the tiresome, unworkable and frankly dangerous old idea of treating hydrogen as a consumer fuel; this said it is a valuable captive chemical intermediate when handled by highly trained chemical engineers in industrial plants.

There are thousands upon thousands of papers on thermochemical hydrogen production in the literature, across a vast array of hydrogen cycles. The most popular of these is the sulfur iodine cycle, and modifications thereof, which I personally prefer given it uses only liquid and gas phase molecules, and thus, at least in theory is capable of continuous operation in a closed system. The paper here refers another well known cycle the CuCl2 cycle, which also features many permutations (including the change of the halides from chlorine to bromine or iodine). The particular cycle discussed here uses electrolysis to generate chlorine, something I generally do not applaud, although with appropriate heat networks to employ process intensification, it may be possible to continuously produce excess electricity for which no immediate use is available other than electrolysis.

In modern times, perhaps to get grants, thermochemical cycles are often proposed using solar thermal garbage to provide the heat for reactions, since obeisance to the worship of so called "renewable energy" has become an element of quasi-religious faith that is regrettably widely spread throughout the world, despite the fact that it does nothing useful generating far more complacency than energy, complacency that has left the world in flames.

What is notable about this paper is how it defines "green," which is largely consistent with how I define it.

To wit, from the introduction of the paper:

1. Introduction
Hydrogen as a clean energy source has the potential to be a viable replacement for traditional fossil fuels. Hydrogen usage on a large scale will require sustainable, low-cost, and environmentally friendly methods of production. (1,2) If hydrogen is produced using renewable energy sources, it can reduce greenhouse gas emissions (GHG) that contribute to climate change. Cu–Cl cycles represent promising water-splitting techniques that can be integrated, for instance, with nuclear reactors among other green energy sources. These cycles employ thermal processes to decompose water into oxygen and hydrogen, utilizing a series of intermediate reactions. Importantly, these cycles ensure the recycling of all other intermediate chemicals and result in zero emissions being released into the environment. The Cu–Cl cycle is an attractive alternative for hydrogen production by thermochemical water breakdown because it requires lower temperatures and has greater overall efficiency than other thermochemical cycles. (3,4)...


There are several dubious locutions in the introduction, and one should note the genuflection in the direction of "other green energy sources" of which there are effectively none.

Table 1 gives the reaction series for the CuCl2 cycle and the temperatures at which the reactions take place:



A few graphics from the text beginning with a flow diagram:



The caption:

Figure 1. Schematic diagram of the Cu–Cl cycle. (5)


A point relevant to the control of particle size:



The caption:

Figure 2. Schematic of transport processes during hydrolysis of a CuCl2 particle.


A schematic for a reactor for continuous flow of the CuCl2 hydrolysis reaction.



The caption:

Figure 3. Continuous hydrolysis reactor system.


Again, I'm not really a CuCl2 thermochemical cycle kind of guy, but what I appreciate is that the article delineates, in the way I do, what "green" might really be.

Have a nice weekend.
January 11, 2025

Well, as an admirer of his you might have set up a GoFundMe page to cover his legal fees.

Happily, I wouldn't have contributed, but it's worth a shot. There are plenty of assholes who would have funded the asshole.

(Stanford, after appeals paid the legal fees of the scientists he injured with his stupid suit. The money would have been better spent funding scientists to do real research, but a lot of crazy assed shit happens in this burning world.)

Once again, anyone who wishes to utilize an "Appeal to Authority" to support the indefensible, is not going to get a shred of support from me, since I know bad thinking when I see it.

Bad thinking, of course, is very common these days, and is celebrated widely and has become a feature of daily discourse, and drives events like, say, the election of a senile felon to the office of President of the United States, not just once, but twice.

Now, if Mark Z. Jacobson were elected President of the United States, instead of merely being an attendee at a scientific conference on climate, or a member of a panel on climate, he would still be an asshole. We are all clearly aware that being an asshole does not preclude being elected President, nor does it preclude being invited to be on a government panel. Elon Musk is an asshole, and he will be invited to be on Government panels, to be sure. (People here used to worship Musk and his fucking electric car.)

I contend he's an asshole anyway and can offer something called "evidence," to show it:

As a scientist, I frequently access a wonderful web page called "Retraction Watch" which points to fraudulent or suspect science, and sometimes covers other scientific bad behavior.

Here's an article from it concerning the asshole Jacobson: Stanford prof who sued critics loses appeal against $500,000 in legal fees

Some excerpts from the article including quotes of the court case involving rejection of his request to have his legal fees covered, the last one (from the court decision denying him coverage for his legal fees) being particularly delicious.

From the Retraction Watch article:

Mark Jacobson, a Stanford professor who sued a journal and a critic for $10 million before dropping the case, has lost an appeal he filed in 2022 to avoid paying defendants more than $500,000 in legal fees.

As we have previously reported, Jacobson:

…who studies renewable energy at Stanford, sued in September 2017 in the Superior Court of the District of Columbia for defamation over a 2017 paper in the Proceedings of the National Academy of Sciences (PNAS) that critiqued a 2015 article he had written in the same journal. He sued PNAS and the first author of the paper, Christopher Clack, an executive at a firm that analyzes renewable energy.

The fees, based on an anti-SLAPP statute, are “designed to provide for early dismissal of meritless lawsuits filed against people for the exercise of First Amendment rights.” Jacobson tried to argue that, by dropping the suit, he was no longer liable for legal fees because the statute requires that defendants “prevail.”

But the three judges in the District of Columbia Court of Appeals disagreed. Justice Joshua Deahl, writing on behalf of himself and colleagues, held:

..
.under Jacobson’s preferred approach, a plaintiff could engage in harassing and meritless litigation up until the point at which they sense the court might dismiss the case, and then voluntarily dismiss the suit themselves, all the while keeping the threat of refiling hanging over the defendants’ heads and running up their legal bills.

The specter of repeat litigation by Jacobson is not farfetched. In his briefing to this court, Jacobson continues to take issue with “the refusal of Dr. Clack and NAS to correct the false facts to this day, in reckless disregard for the truth.” Much of his brief rehashes his claims that NAS and Clack defamed him and he persists in condemning Clack’s article. In arguing that NAS and Clack have not “prevailed,” Jacobson repeatedly asserts that he retains the ability to refile his defamation suit, “keeping the defendant[s] at risk...”


Another excerpt with the opinion of the court I find "delicious" and albeit from non-scientists (judges) captures entirely what scientific integrity is all about:

In June 2022, Jacobson prevailed on the California Labor Commissioner to order Stanford to pay his own attorneys’ fees because, he argued, bringing the suit was “necessary for my job,” particularly defending his reputation. Stanford’s appeal of that decision, and arguments against paying for the fee awards in the District of Columbia, will be heard at a trial in May.


Commenting more generally on the suit, the judges wrote:

What animates Jacobson’s $10 million defamation suit is nothing more than his indignation at an article critical of his work. Such criticism comes with the territory of academic debate....


For me, this article is supportive of defining Jacobson as an asshole, a thin skinned asshole who can't take criticism.

By the way, here's a response to a criticism launched at the famous climate scientist Jim Hansen and a colleague (P. Kharecha, at Coumbia) to Jacobson's criticism (co-authored by co-asshole Benjamin Sovacool) of Hansen and Kharecha's scientific paper:

Pushker A. Kharecha*James E. Hansen Response to Comment on Prevented Mortality and Greenhouse Gas Emissions from Historical and Projected Nuclear Power Environ. Sci. Technol. 2013, 47, 12, 6718–6719.

The paper is open to the public to read.

Note that neither Dr. Kharecha nor Dr. Hansen sued Jacobson and co-asshole Sovacool; they simply pointed out their bad thinking.

Sovacool, by the way, is the asshole who suggested we tear the shit out of the ocean floor to prove we're "green," and did so in a very important scientific journal, Science:

B. Sovacool. Sustainable minerals and metals for a low-carbon future Science 3 Jan 2020 Vol 367, Issue 6473 pp. 30-33.

The article is not open sourced, but I have full access, and I'll excerpt the particularly disgusting part:

...Although mining in terrestrial areas is likely to continue to meet the demands of low-carbon technologies in the nearer term, we need to carefully consider mineral sources beneath the oceans in the longer term. The International Seabed Authority, set up under the United Nations (UN) Convention on the Law of the Sea, is in the process of issuing regulations related to oceanic mineral extraction. This process is a rare opportunity to be proactive in setting forth science-based environmental safeguards for mineral extraction. For metals such as cobalt and nickel, ocean minerals hold important prospects on the continental shelf within states' exclusive economic zones as well as the outer continental shelf regions. Within international waters, metallic nodules found in the vast Clarion-Clipperton Zone of the Pacific as well as in cobalt and tellurium crusts, which are found in seamounts worldwide, provide some of the richest deposits of metals for green technologies. Difficult extraction and declining reserves of some terrestrial minerals, as well as social resistance against terrestrial mining, may lead to oceanic mineral reserves becoming more plausible sources. Minerals near hydrothermal vents are in more pristine and distinctive ecosystems and should likely remain off-limits for mineral extraction for the foreseeable future...


I can't speak to anyone else's self declared notion of themselves as "environmentalists" - a dubious distinction that poorly educated antinukes, and even well educated antinukes frequently proclaim themselves to be - but in my self declared contention that I am an environmentalist, tearing the shit out of the ocean floor because one thinks "nuclear energy is too expensive" and climate change isn't "too expensive" is appalling in the extreme. Tearing the shit out of the ocean floor will require fossil fuels, just like Dunkelflaute requires fossil fuels.

Sovacool is exactly the kind of absurd asshole I would expect the likes of Jacobson to embrace.

The fucking planet is on fire, and I hold these kinds of people, reactionaries who have not a fucking word to say about fossil fuels but specioously whine about the only sustainable expandable reliable form of carbon free energy available, nuclear energy, responsible for climate change.

By the way, a post of mine that does not rely at all on "Appeal to Authority" arguments, but rather simply reports numbers and the sources for those numbers, including the amount of money squandered on so called "renewable energy" since 2015, as well as the acceleration of additions of the dangerous fossil fuel waste carbon dioxide in the planetary atmosphere is here:

The Disastrous 2024 CO2 Data Recorded at Mauna Loa: Yet Another Update 12/08/2024

I'm entirely comfortable with quoting myself in this context.

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 as of 2024.



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.
.

Note that I praise President Biden in the post for his support for nuclear energy, but this is not an "Appeal to Authority" argument. Nuclear energy is not superior to everything else because President Biden also supports it, nor is so called "renewable energy" sustainable because President Biden supports it. I simply praise the President for holding a reasonable position on nuclear energy, and accept that no one, including the President, is perfect, since I regard his support for so called "renewable energy" as ill advised while respecting, in the extreme, his otherwise outstanding Presidency.

In any case, the value of nuclear energy is independent of who its supporters and detractors are. Nuclear energy is not risk free, but it doesn't have to be risk free to be vastly superior to everything else. All it has to do is to be vastly superior to everything else, which it is, no matter what assholes like Jacobson and Lovins say. Unlike so called "renewable energy" nuclear energy can operate without access to fossil fueled power.

So called "renewable energy" is not sustainable, with or without tearing the shit out of the ocean floor for mines. It has done nothing, absolutely nothing, at a cost of trillions, to reduce the use of fossil fuels. It depends on access to fossil fuels. We are using more fossil fuels than ever.

Breakdown of Carbon Emissions by Source; 2003-2023

This is despite over a decade of bullshit from the likes of Jacobson and his fellow assholes, and half a century of bullshit from other advocates of the reactionary so called "renewable energy" scheme. The planet is burning as a result. It's an experimentally observed result.

To my mind, so much for the "Green New Deal." It's not "green;" it's not "new" and it's not a "deal." Rather it's nothing more than quasi-religious cant.

Have a wonderful weekend. It's been a pleasure to chat.

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