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Author: Subject: Obtaining rare earths from around the house
eidolonicaurum
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Obtaining rare earths from around the house

As an element collector, I thought it would be a good idea to start a thread on obtaining the rare earth elements from household/common/readily available materials, and possibly then separating them. There are quite a few threads on specific rare earths, but I cannot find any specifically for all of them.

For sources, I have found the following:

For separation of the NiMH batteries, I dissolved the innards (minus the metal sheets) in sulphuric acid, and allowed much of the nickel sulphate to crystallise out. The next step will be to add H2O2 to the solution to oxidise the manganese ions present to MnO2, then filter this out. Cerium will stay in solution because the liquid is still quite acidic. Then add bromine water to selectively precipitate Co2O3.H2O. Maybe evaporate further to crystallise out more nickel sulphate. Then add an excess of ammonia to form complexes with the nickel, and an aluminate with aluminium. The rare earths precipitate out as hydroxides because they do not form complexes with ammonia. Calcine this precipitate to from the oxide, then add nitric acid. CeO2 is not soluble in nitric acid, so it can be separated. Then add ammonium nitrate to form double salts. The double salt with lanthanum is not particularly soluble, so this can be separated out. Then its the joys of fractional crystallisation toseparate praseodymium and neodymium.
I plan to make a video of this at some point, but I have about 10ml of acid left, so it will have to be when I get around to ordering some more.

For the separation of fluorescent light bulb phosphors, I will dissolve the phosphor in acid, crystallise out the salts and manually separate under UV by harnessing their fluorescent properties. Europium fluoresces red, while terbium fluoresces green. Recrystallise to purify.

Any ideas on the rest (besides buying them)?

[Edited on 9-4-2014 by eidolonicaurum]
Edit: new yttrium source

[Edited on 10-4-2014 by eidolonicaurum]

deltaH
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I have always been fascinated by scandium, it appears almost to be a forgotten element by chemists today. Its production is very limited and it is exceedingly hard to obtain, not because it is essentially that rare per say, but simply because it appears to hardly have practical applications and so few refiners of rare earths bother isolating it in large quantities?

That said, apparently the Russian military have used it to prepare speciality ?aluminium alloys for fighter jets and indeed, it seems that if you live in Russia and perchance had legal access to a military junkyard and could pull some alloy off the correct fighter models' skeletal remains (with the right 'remuneration' exchanging hands?), you may have some hope in separating out a small amount of scandium. However, I don't know which parts were made of scandium containing alloy, nor how much is present.

As a testament to how ludicrous the scandium situation is, I quote the Sigma price for dendritic Scandium pieces: about $300/g; also the price for ScI3! According to tables of natural abundance of elements in the earth's crust, scandium's abundance is comparable to cobalt Meanwhile, tellurium, with an abundance similar to gold, trades around$110/kg

Supply and demand

I would be very intrigued to hear from members here who may know of other places scandium alloys may be lurking...

[Edited on 9-4-2014 by deltaH]

Zyklon-A
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Wow! Very nice procedure, I have been collecting NiMh batteries for this reason, and will definitely give this procedure a go.

While on this subject, what about cerium from ferrocerium flints? Certainly getting the flints out of lighters is an enormous waist of time, but magnesium fire starters have a big ferrocerium flint, which I have weighed to be about 3.4 grams. I have already bought three of said fire starters for the Mg, but I think I have at least two flints left somewhere. I would like to experiment with them a little, and try to extract cerium and/or other rare-earths from them.

I've got a big book on the elements which may give some more clues and ideas on extracting other metals.
BTW, The relative amount of gold in the earth includes seawater and far below the earths crust, so it's mostly impossible to get. There's about as much gold in the earth as titanium!

[Edited on 9-4-2014 by Zyklonb]

deltaH
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 Quote: ...There's about as much gold in the earth as titanium!

?!

Not according to this:

http://en.wikipedia.org/wiki/Abundance_of_elements_in_Earth%...

[Edited on 9-4-2014 by deltaH]

blogfast25
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 Quote: Originally posted by deltaH I have always been fascinated by scandium, it appears almost to be a forgotten element by chemists today. Its production is very limited and it is exceedingly hard to obtain, not because it is essentially that rare per say, [...] [Edited on 9-4-2014 by deltaH]

The main problem is that very few worthwhile deposits have been found. It's not that rare but that it's scattered all over the place in low content ores.

There's a quite famous British trader from whom you can buy it. I've had offers from a Hong Kong metals house but the price (for the oxide) was prohibitive.

deltaH
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 Quote: Originally posted by blogfast25 The main problem is that very few worthwhile deposits have been found. It's not that rare but that it's scattered all over the place in low content ores. There's a quite famous British trader from whom you can buy it. I've had offers from a Hong Kong metals house but the price (for the oxide) was prohibitive.

Pulled this off Wikipedia...
 Quote: Madagascar and Iveland-Evje region in Norway have the only deposits of minerals with high scandium content, thortveitite (Sc,Y)2(Si2O7) and kolbeckite ScPO4·2H2O, but these are not being exploited.[12]

... I always wanted to go to Norway, wanna come? Pack a pick axe, on second thought, as the mineral is called thortveitite... pack a hammer
[12] is a market report about scandium, I've done the courtesy of attaching it here for those interested in scandium in general.

Attachment: Scandium report.pdf (82kB)

[Edited on 9-4-2014 by deltaH]

Zyklon-A
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Oh, I guess I was wrong. I remember hearing that approximation of gold-titanium, I don't remember where.
There is surprisingly little, information on scandium in the book.
I'm hand typing this so bare with me:

 Quote: Scandium heads a list of 10 metals called the first row transition elements, which occupy the center of the periodic table. As the number protons in the transition elements increases across the row of these elements, electrons are added to an incomplete inner shell, rather than the outer valence shell. Consequently, the number of valence electrons is virtually the same for all of these elements. Scandium is a scarce element that makes up approximately 0.0025% of the earth's crust. Scandium is a very lightweight metal with a fairly high melting point, and a good resistance to corrosion. These property's have made it of great interest to the aerospace industry in the production of aircraft. The pure metal was not available until 1937, and some of the first samples of the silvery-white metal were produced for the US air force. Pure scandium is usually prepared by electrolysis of ScCl2. It has a tendency to develop a yellowish color when exposed to air. Scandium has few useful compounds. The metal itself has found some use in electric devices, such as high-intensity lamps that produce light with a color close to that of natural sunlight. Lamps of this kind are often used to illuminate football and baseball stadiums.

Sorry, it looks like it took away all my paragraph breaks, and margins. Which makes it harder to read, I took the time to hand type this, so at least take a few seconds and read it.

[Edited on 9-4-2014 by Zyklonb]

eidolonicaurum
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If anyone can find/work out/discover/stumble up a method of separating praseodymium and neodymium without having to fractionally crystallise or use ion-exchange columns, that would be both a huge relief anr a massive breakthrough! On the other hand, if cheap/readily available ion-exchange resin is available, that too would be very useful. However, I expect it will be rather expensive (I havent looked, but it just seems to be).

Zyklon-A
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It wont be easy, but maybe possible. But even if we can't get praseodymium and neodymium, the rest would be great!

eidolonicaurum
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 Quote: Originally posted by Zyklonb what about cerium from ferrocerium flints? [Edited on 9-4-2014 by Zyklonb]

I've investigated these too, only theoretically for the time being because I don't have any yet, but that procedure is very similar. According to wikipedia, they contain:

 Quote: Element Iron Cerium Lanthanum Neodymium Praseodymium Magnesium Percentage 19% 38% 22% 4% 4% 4%

The iron is present as the oxide. My theory was to use this fact to avoid dissolving the iron, since I have had difficulty deliberately dissolving ferric oxide before, so this should separate it out. An identical method to the NiMH batteries could then used to separate the remaining elements.

blogfast25
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Praseodymium/neodymium separation should be one of the easier ones because Pr shows a IV oxidation state that Nd doesn't. There are plenty of threads here relating to Nd from neomagnets by the resident RE nutters, 'Brain&Force', 'Mr Home Scientist' and myself.

Setting up a resin exchange column needn't be expensive at the hobby level. But detecting the various fractions isn't so easy.

RE prices have come tumbling down in recent years: simply buying the elements or some of their compounds has become within reach of the hobbyist. It will often be cheaper than to extract them from stuff, no matter how much fun that can be.

[Edited on 9-4-2014 by blogfast25]

MrHomeScientist
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I see you included my blog under neodymium! The source of that procedure (and the results of my attempts at it) are here on the forum, in The trouble with neodymium... thread. There's a ton of information there, way more than on my blog.
Spoiler alert: I was never able to get much of anything out of that method. Just a few tiny flakes of what might be the metal. Work in progress!
eidolonicaurum
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It certainly does appear that extracting the metal from a rare earth compound is extremely difficult, but half the procedure is separating and purifying the different compounds. Even if the metal cannot be obtained, I expect a lot of fun can be had with just the compounds alone.

With regards to detecting the various different fractions in a resin exchange column, could the colour not be used, or is there a glaring error with this idea? I have never seen one of these columns, so I have no idea. I understand the principle though. Alternatively, the fluorescence of some of the compounds, along with other unique properties could possibly be used? eg different colour in different lights etc

Bert

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 Quote: Originally posted by deltaH I would be very intrigued to hear from members here who may know of other places scandium alloys may be lurking...

In the USA, ask a gunsmith?

The revolvers in particular seem to have a durability problem, should be some scrapped frames out there.

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Brain&Force
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And I shall complete the trio of rare-earth nutters!

The more distant the lanthanides are on the periodic table, the more likely you are to separate them. Seperating, say, neodymium and ytterbium is easier than erbium and holmium. Note that many RE salts are colorless, but the colored ones can be identified quite easily. These would be cerium, praseodymium, neodymium, samarium(II), europium(II), holmium and erbium.

Some glasses contain praseodymium, neodymium, and erbium as colorants. Green laser pointers contain neodymium yttrium orthovanadate. Ytterbium is used in some forms of stainless steel. The SoundBug gadget contains Terfenol-D, which is an alloy of iron, terbium, and dysprosium. Gadolinium is used in contrast agents, and some high quality magnets may use dysprosium and holmium as polepieces.

If you want to seperate cerium, praseodymium, europium, and terbium, you can oxidize them to a higher state (or reduce it in the case of europium, which I have started a thread on). I have some information on terbium and how to seperate it from iron if it's an impurity, but I don't know about seperating it from other

Scandium is actually less abundant in earth's crust than it should be, but most of the problem arises from the fact that scandium has a very small atomic radius and doesn't deposit with the lanthanides. The uses of scandium are also pretty few and far between, though it can be used to strengthen aluminum.

As far as I can tell, lanthanides don't fluoresce in solution, so this may present a problem for tracking them in mixtures.

Raney nickel can't hydrogenate dank memes.
elementcollector1
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And then there's me, attempting to be a rare-earth nutter on the side but not really succeeding.
I wish there were better sources for more of the RE's, but I had no clue about the NiMH batteries. Is this a similar composition to mischmetal?

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For your list: you can get tungsten welding electrodes with lanthanum or cerium (usually around 1 to 2%) as an alternative to thorium-containing electrodes.
Also, some gas mantles may contain rare earth oxides these days (also replacing thorium), but I recall most use zirconia.

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deltaH
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Excellent suggestion Bert and nice link, thanks.

aga
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Wonderful.

Absolutely wonderful.
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I've been looking at working with praseodymium and I would be using the chloride route as per a modified procedure of J. Inorg. Nuc. Chem 1962, Vol. 24, pp. 387-391.
Dan Vizine
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 Quote: Originally posted by deltaH I have always been fascinated by scandium, .... but simply because it appears to hardly have practical applications ... According to tables of natural abundance of elements in the earth's crust, scandium's abundance is comparable to cobalt Meanwhile, tellurium, with an abundance similar to gold, trades around $110/kg Supply and demand Actually, if Scandium were cheaper you'd see it everywhere. It has excellent structural properties. Verry high end bicycle frames (and other parts) were made of scandium or (more likely) scandium with alloying additions. Abundance is not in any way to be confused with ease of isolation from nature. The paramount factor is beneficiation (concentration). That is, if nature gathers it together, it's cheap (generally). Think Monazite sands, ore veins, etc. Some elements (Rb for example) simply don't have ores. They are "widely dispersed" and thus costly. High processing costs (isolation & purification) are secondary. [Edited on 9-4-2014 by Dan Vizine] Subcomputer Harmless Posts: 15 Registered: 23-3-2013 Member Is Offline Mood: No Mood elementcollector: for what it's worth, the wikipedia article looks like it says that NiMH batteries using high lanthanum mischmetal or lanthanum improved mischmetal have been on the market, but that doesn't mean much as to whether the batteries you get will be of a certain purity. Especially with mischmetal industrially meaning essentially "the lanthanum-cerium and whatever RE else that's left over after it's no longer economically viable to separate out the good stuff", and that was before the survival kit companies decided to redefine terms to include ferrocerium, added magnesium, etc. Speaking of dropping prices, I bought 10g each of ampouled "cerium" for ~$12 and "neodymium" for ~\$16 from ebay seller yaolihong2013 . Can't wait to see what I actually get.
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 Quote: Originally posted by eidolonicaurum With regards to detecting the various different fractions in a resin exchange column, could the colour not be used, or is there a glaring error with this idea?

Many of these compounds are colourless, and the colourful ones often are only that in quite concentrated solutions (something ion exchange resins don't 'do' well)

Even Classic XRF apparently isn't capable of telling them apart: the techniques has to be combined with XRD to separate the emissions, which are very close together in terms of eV.

I'm not sure but I think detection of REs in an ion exchange eluate would be by means of UV/VIS spectrometry.

Dan Vizine
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The first chromatography I ever did in my life was the separation of 6 RE compounds on ion exchange resin in a freshman chemistry class. Each RE compound was visually detected in the eluate. They were all different colors. Unfortunately the identities of the compounds are lost in the mists of time.

That being said, I think chromatography is your best bet. Fractional crystallization is generally a horribly lossy and labor intensive process.

Is your goal to experiment or attain samples? It will be cheaper to buy RE materials than separate them (probably). If this is a learning exercise, have at it. Good luck!
blogfast25
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 Quote: Originally posted by Dan Vizine The first chromatography I ever did in my life was the separation of 6 RE compounds on ion exchange resin in a freshman chemistry class. Each RE compound was visually detected in the eluate. They were all different colors. Unfortunately the identities of the compounds are lost in the mists of time.

Visually as in 'by the naked eye'? No photometric detection?

[Edited on 10-4-2014 by blogfast25]

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 Sciencemadness Discussion Board » Fundamentals » Chemistry in General » Obtaining rare earths from around the house Select A Forum Fundamentals   » Chemistry in General   » Organic Chemistry   » Reagents and Apparatus Acquisition   » Beginnings   » Responsible Practices   » Miscellaneous   » The Wiki Special topics   » Technochemistry   » Energetic Materials   » Biochemistry   » Radiochemistry   » Computational Models and Techniques   » Prepublication Non-chemistry   » Forum Matters   » Legal and Societal Issues