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 Post subject: Re: Lithium-7
PostPosted: Aug 09, 2015 8:47 am 
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Cyril R wrote:
What's the cost difference between 10 ppm Li6 and 50 ppm?


That depends, it probably won't be huge if we are using a longer crown ether extraction stage although we will hit seriously diminishing returns - but using a laser or physical process will put the price through the roof.

Remember this is the opposite problem to normal enrichment - so the normal rule about the price of later stages being almost unimportant no longer holds.


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 Post subject: Re: Lithium-7
PostPosted: Aug 09, 2015 4:37 pm 
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E Ireland wrote:
Cyril R wrote:
What's the cost difference between 10 ppm Li6 and 50 ppm?


That depends, it probably won't be huge if we are using a longer crown ether extraction stage although we will hit seriously diminishing returns - but using a laser or physical process will put the price through the roof.

Remember this is the opposite problem to normal enrichment - so the normal rule about the price of later stages being almost unimportant no longer holds.


What is the difference? Depletion or enrichment, it is both separative work. Unless I misunderstand things, technologically one would expect a SWU to cost the same regardless of enrichment level. Twice the SWU = twice the enrichment cost, right?

The interesting thing is that each atom of Li6 is going to steal 0.x fission event, where x is quite a lot more than 0.l And a fission makes 200 million electron-volts, so that Li6 is expensive to have around. In stead of cost, consider value.


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 Post subject: Re: Lithium-7
PostPosted: Aug 09, 2015 4:53 pm 
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Cyril R wrote:
What is the difference? Depletion or enrichment, it is both separative work. Unless I misunderstand things, technologically one would expect a SWU to cost the same regardless of enrichment level. Twice the SWU = twice the enrichment cost, right?


SWU only really applies to physical processes - chemical processes, like the crown ether extraction or the heavy water processes, do not use the same model.
Cyril R wrote:
The interesting thing is that each atom of Li6 is going to steal 0.x fission event, where x is quite a lot more than 0.l And a fission makes 200 million electron-volts, so that Li6 is expensive to have around. In stead of cost, consider value.


Let's say a reference core DMSR, 30,000kg of lithium, at 50ppm that is 1.5kg of 6Li, as opposed to 0.3kg. Something like 250 moles.
Over 30 years the reference core will produce 22.5GW-years, which is something like 22500kg of fissioned heavy metal, or roughly 95750 moles.

Those 250 moles of neutrons would breed at most 60kg of fissile material - which is only ~550MWh of electricity produced.

Even if every single 6Li atom underwent neutron capture and was burned out - it would not significant reduce the breeding ratio of the core.
There will be a bigger fuel reuse issue because of the 236U contamination in the spent fuel that might require enrichment above the 20% limit.


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 Post subject: Re: Lithium-7
PostPosted: Aug 09, 2015 5:10 pm 
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So if I use a value of half a billion $ per GWe-year, then that is about $117500/mole.

That is a lot of money. Wasting even 200 moles more on captures would forfeit over $23 million.

With the economics of utility powerplants, likely we will go for higher enrichments to get our $23 million, if the added cost is under $5 million or so.

What's the limit of a chemical process like crown ether in max. enrichment terms?


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 Post subject: Re: Lithium-7
PostPosted: Aug 09, 2015 5:19 pm 
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Cyril R wrote:
So if I use a value of half a billion $ per GWe-year, then that is about $117500/mole.

That is a lot of money. Wasting even 200 moles more on captures would forfeit over $23 million.

With the economics of utility powerplants, likely we will go for higher enrichments to get our $23 million, if the added cost is under $5 million or so.

$23,000,000 is only going to provide $750/kg - which isn't really that much to spend on the extra enrichment.
Cyril R wrote:
What's the limit of a chemical process like crown ether in max. enrichment terms?


In theory 100% - just like physical processes.
The problem is that the tails fraction, and more importantly the amount of crown ether required will grow exponentially - so that ~$500/kg price for the 50ppm product will escalate rapidly, I will attempt to calculate how much.


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 Post subject: Re: Lithium-7
PostPosted: May 30, 2016 2:17 pm 
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Hello! This is obviously a crucial topic. A few days ago on May 20, 2016, Jim L started "Article advocating U.S. nuclear power" and I mentioned at one point the HD lithium problem.
Jim L. wrote:
. . . there was a post about a different process that looked promising. That process is titled: "Green and efficient extraction strategy to lithium isotope separation with double ionic liquids as the medium and ionic associated agent" in case you need to search for it, not sure if it was posted in this forum. Feel free to jump into the discussions on it!

The paper is here: Journal of Radioanalytical and Nuclear Chemistry March 2013, Volume 295, Issue 3, pp 2103-2110.
Xu Jingjing, et al. wrote:
The single-stage isotope separation factor of 7Li–6Li was up to 1.023 +/- 0.002, indicating that 7Li was concentrated in organic phase and 6Li was concentrated in aqueous phase. All chemical reagents used can be well recycled. The extraction strategy offers green nature, low product cost, high efficiency and good application prospect to lithium isotope separation.

Another more recent paper is here: Journal of Nuclear Science and Technology Volume 52, Issue 3, 2015. It describes liquid-liquid extraction for lithium isotope separation based on room-temperature ILs containg 2,2'-binaphthyldiyl-17-crown-5.
Received: 4 Mar 2014, Xiao-Li Suna, et al. wrote:
Under optimized conditions, the maximum single-stage separation factor alpha of 6Li/7Li obtained in the present study was 1.046 +/- 0.002, indicating the lighter isotope 6Li was enriched in IL phase while the heavier isotope 7Li was concentrated in the solution phase.

According to the Preface to the text from 2014 Ionic Liquids in Separation Technology, ionic liquids (ILs) are an emerging technology that "has blossomed only within in the last decade." I just received my copy of this text. It looks fascinating.

I read Jingjing, et al. What are the costs of these materials? If commercial implementation of IL techniques is underway for HD lithium, then details will be cloaked under IP. But that would be a good thing. It would indicate that 99.995% 7Li or better can be economically made MUCH safer than COLEX given demand for HD lithium; once the FE LFTR gets licensed for deployment.

I wonder if the B&P Process Equipment and Systems POD Liquid/Liquid Extraction Centrifuge (cheesy video music) would work for IL continuous counter-current 6Li/7Li separation?

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Last edited by Tim Meyer on Jun 08, 2016 6:13 pm, edited 1 time in total.

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 Post subject: Re: Lithium-7
PostPosted: Jun 08, 2016 12:21 pm 
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Journal of Radioanalytical and Nuclear Chemistry March 2013, Volume 295, Issue 3, pp 2103-2110

Attachment:
jingjing2013.pdf [412.64 KiB]
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Received: 21 August 2012, Xu Jingjing • Li Zaijun • Gu Zhiguo • Wang Guangli • Liu Junkang wrote:
Green and efficient extraction strategy to lithium isotope separation with double ionic liquids as the medium and ionic associated agent

Published online: 27 September 2012 / Akade ´miai Kiado ´, Budapest, Hungary 2012

Abstract

The paper reported a green and efficient extraction strategy to lithium isotope separation. A 4-methyl-10-hydroxybenzoquinoline (ROH), hydrophobic ionic liquid — 1,3-di(isooctyl)imidazolium hexafluorophosphate ([D(i-C8)IM][PF6]), and hydrophilic ionic liquid — 1-butyl-3-methylimidazolium chloride (ILCl) were used as the chelating agent, extraction medium and ionic associated agent. Lithium ion (Li?) first reacted with ROH in strong alkali solution to produce a lithium complex anion. It then associated with IL? to form the Li(RO)2IL complex, which was rapidly extracted into the organic phase. Factors for effect on the lithium isotope separation were examined. To obtain high extraction efficiency, a saturated ROH in the [D(i-C8)IM][PF6] (0.3 mol l-1), mixed aqueous solution containing 0.3 mol l-1 lithium chloride, 1.6 mol l-1 sodium hydroxide and 0.8 mol l-1 ILCl and 3:1 were selected as the organic phase, aqueous phase and phase ratio (o/a). Under optimized conditions, the single-stage extraction efficiency was found to be 52 %. The saturated lithium concentration in the organic phase was up to 0.15 mol l-1. The free energy change (DG), enthalpy change (DH) and entropy change (DS) of the extraction process were -0.097 J mol-1, -14.70 J mol K-1 and -48.17 J mol-1 K-1, indicating a exothermic process. The partition coefficients of lithium will enhance with decrease of the temperature. Thus, a 25C of operating temperature was employed for total lithium isotope separation process. Lithium in Li(RO)2IL was stripped by the sodium chloride of 5 mol l-1 with a phase ratio (o/a) of 4. The lithium isotope exchange reaction in the interface between organic phase and aqueous phase reached the equilibrium within 1 min. The single-stage isotope separation factor of 7Li–6Li was up to 1.023 ± 0.002, indicating that 7Li was concentrated in organic phase and 6Li was concentrated in aqueous phase. All chemical reagents used can be well recycled. The extraction strategy offers green nature, low product cost, high efficiency and good application prospect to lithium isotope separation.

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 Post subject: Re: Lithium-7
PostPosted: Jun 08, 2016 6:15 pm 
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From: Re: FLiBe with 99.995% 7Li
Jim L. wrote:
And for the 7Li the Hg amalgamation works - we know it does and we know it has been done in the past (and Russian and China currently use it, AFAIK). Mercury has gotten a bad name in general, and the Hg amalgamation has gotten a bad name in specific due to poor handling by ORNL. However, that just means the method could be used in another country and/or buy off suppliers in other countries. The highly depleted Li supply is not a physics, chemical, or engineering problem, it is a business problem.
Jim, but what if the ionic liquids method works as well or better than COLEX (Hg amalgam)?

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"Those who say it can’t be done are usually interrupted by others doing it."

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 Post subject: Re: Lithium-7
PostPosted: Jun 09, 2016 8:22 am 
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@Tim,

I am optimistic that the ionic fluid method will work, and that several of the "build any kind of MSR RIGHT NOW" companies would use at least 7LiF in a heart beat. And be better off for doing so.


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 Post subject: Re: Lithium-7
PostPosted: Jun 09, 2016 12:17 pm 
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Thanks, Jim. I'm glad you agree with the potential for ILs.
Jim L. wrote:
. . . the "build any kind of MSR RIGHT NOW" companies would use at least 7LiF [from overseas COLEX until IL methods go into commercial production?] in a heart beat. And be better off for doing so.
I believe the U.S. Government will soon be upgrading the DOE and NRC missions to encourage development and deployment of advanced nuclear designs. Once FE LFTR gets going in its licensing plan, the future demand for 7Li will become apparent and drive 7Li production.

I've just begun studying my copy of Ionic Liquids in Separation Technology (2014, Elsevier) that came yesterday. Fascinating!

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Last edited by Tim Meyer on Jun 09, 2016 12:37 pm, edited 1 time in total.

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 Post subject: Re: Lithium-7
PostPosted: Jun 09, 2016 12:35 pm 
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Jim, I'm copying/moving from: Re: FLiBe with 99.995% 7Li to keep all the 7Li discussion here, okay? Thanks!

Jim L. wrote:
@Tim,

I am very optimistic that the ionic method would work, and while I do not have an adequate estimate for cost, I believe there is a lucrative market for the first one to produce highly depleted Li in industrial quantities. Especially if the 6Li tailings can also be sold off to the big money fusion types.

Excellent, Jim, and I agree mostly.

I bought the IL text to also get at the bottom of the costs. Sections talk about the emerging IL industries. The text is from Spain but it's in very good English. I find it interesting that the largest lithium deposits are in South America--Spanish-speaking. Hmmm. Isotopic separation is NOT mentioned anywhere in the text only "industrial processes" as far as I've found so far. The Chinese researchers were publishing around the time of its production and perhaps too new to be included. As the authors say, IL applications are advancing rapidly. They're truly amazing. They'll likely become quite "lucrative" for a great many processes. And it looks like the "traditional" molecular solvents businesses may be losing some customers. Those companies may shift into ILs?

Don't you rather think that the bulk of the 6Li will just get mixed back in with the streams for batteries, pharmaceuticals, and the current "traditional" lithium markets? We all hope for fusion but look at it and ITER. Thorium is readily available NOW!

Green 7Li industrial-scale production by an optimum IL process together with Materion Brush beryllium fluoride production is a crucial part of the FE LFTR licensing plan within a new international regulatory framework for the pure thorium-233U fuel cycle. It's a brand nuclear day, and perfect for fission!

The founder of this topic, Andrew W. Mangold, and fellow members who have been posting in this discussion have yet to evaluate the IL lithium isotopic depletion methods posted here.

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 Post subject: Re: Lithium-7
PostPosted: Jun 09, 2016 1:04 pm 
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October 2009, Kirk Sorensen wrote:
I was thinking about the issues related to lithium enrichment recently and wondered if a market for the "tails" of lithium enrichment might not already exist. Lithium is a lightweight material used to alloy with aluminum in aerospace applications. Using lithium-6 instead of natural lithium (which is mostly lithium-7) could reduce the weight potentially 14%! There might be applications where a 14% weight reduction would be economically justified.
Well? It's been more than six years. Was this ever evaluated?

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 Post subject: Re: Lithium-7
PostPosted: Jun 09, 2016 3:28 pm 
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@Tim,

My comment about 6Li was mostly meant as a slam on the fusion research folks, since I doubt they will ever get there in terms economic large-scale electricity produced by fusion by any method -- yet those folks get an enormous amount of money.

Also, I believe that 6Li is considered a nuclear "special material" by the government, U.N., IAEA, et cetera and would need permits, protections, licenses and all that.


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 Post subject: Re: Lithium-7
PostPosted: Jun 09, 2016 3:34 pm 
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@Jim

Your humor is subtle and thanks for allowing my density but I get your fusion 6Li point now. It is getting huge resources. Very tough.

As it stands, our DOE Y-12 keeps all the 6Li? Correct?

FE LFTR is not just a disruptive technology. It's a 10 on the world energy technology Richter scale.

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 Post subject: Re: Lithium-7
PostPosted: Jul 26, 2016 5:01 pm 
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Remember folks, we are NOT trying to purify Li6 but Li7. If the tails are 50% of each, would it still be a "special material"? What would be considered "Low Enriched Li"?

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