Extraction of beryllium from beryl

Nice plante, I know you will, but please do be very careful with beryllium and its compounds!

Apparently beryl expands very little indeed, ~2.7 ppm/C, on par with borosilicate. It's probably even lower, amorphous. Berylsilicate glassware indeed

Tim

Quote: Originally posted by woelen

I expect molten KF/KHF2 will do the job, but this is really nasty stuff. Not something to try at home in my opinion. Btw, your results, although not very encouraging at the moment, are interesting. They demonstrate that BeO indeed is a dificult material to treat mechanically and chemically. I have finely powdered pure BeO and this has proven to be extremely inert, but as I wrote before, I only tried dissolving in all kinds of hot aqueous concentrated solutions. I did not try any melts.

Quote: Originally posted by plante1999

During the day I found about bicarbonate leaching of beryllium, so I tried it. I added in 3 portion 300 ml of 10% NaHCO3. In the first 100 ml, effervescence was made. in the second part some gelatinous precipitate formed, and the last 100ml made the mixture more fluid. The mixture was filtered and boiled to precipitate the beryllium. .

Quote: Originally posted by Wizzard

I have a broken Argon laser which has an ID'd beryllium ceramic lasing vessel.... Dare I disassemble it?

Quote: Originally posted by plante1999

First I mixed 10.6 g of anhydrous sodium carbonate and 5.5 g of beryl frit. I melted the two together until formation of CO2 stopped, it took about 30 minutes at yellow heat. Then the cooled material was put in 100 ml of cold water and boiled to dissolve a part of it. Then 40 ml of 30% HCl was added and boilled until only a few grams of precipitate on the bottom. It was filtered and boiled down to give very crude beryllium chloride. Theoretical purity is 15% beryllium chloride, the yield was 5g.

Quote: Originally posted by plante1999

Yes, my frit is crush-able, however my mortar broken recently. I just read something very interesting in parson book of beryllium chemistry, and hopefully soon I will have all the reagent I need. Here is the idea: A weight of beryl frit is mixed with it own weight of potassium hydroxide, and melted to a glass. The mix is covered with water, and slightly more than stochiometric amount of conc. sulphuric acid is added, a gelatinous mass is formed. The mix is heated until it is dry and fuming. The dry product is leached, and the potassium alum is precipitated by cooling. The purified beryllium sulphate is purified with other processes, but I would probably only dry the filtrate to get the crude purified beryllium salt. I only need to get potassium hydroxide and I should be ready to try.

A few ml of supernatant liquor from an ammonium alum recrystallisation, saturated at about 2 C, was added to a test tube, then about the same amount of 30 % NH3 solution was added. A little precipitate of Al(OH)3 forms. Both are photos of the same tube, top with flash, bottom without flash:





There’s a bit more precipitate than I had hoped for but then Al(OH)3 is very voluminous. As a first step to get rid of most Al this should work, bar unanticipated interactions.



[Edited on 16-1-2013 by blogfast25]

Quote: Originally posted by Poppy

[...] everyone knows it works better from hot alkali media to neutral than from acid to neutral, because the flakes would no more be gelatinous!

Quote: Originally posted by plante1999

You should try lower the temperature at 0 or lower, like I do.

Quote: Originally posted by woelen

Btw, your results, although not very encouraging at the moment, are interesting. They demonstrate that BeO indeed is a dificult material to treat mechanically and chemically. I have finely powdered pure BeO and this has proven to be extremely inert, but as I wrote before, I only tried dissolving in all kinds of hot aqueous concentrated solutions. I did not try any melts. [Edited on 10-1-13 by woelen]

...powdered BeO? I've seen some RF equipment with beryllium oxide insulators and they were all labeled with big skulls and warnings about BeO, the powder of which was almost considered the devil himself. To be honest I wouldn't dare to handle that stuff at all.

So, here’s my first attempt at walking in the footsteps of French chemist Louis-Nicolas Vauquelin, who discovered beryllium in Beryl in 1798.

The starting material, Beryl:



1. Fritting (not strictly speaking):

Having no access to a heat source than can melt Beryl (> 1600 C), I heated a few small pieces of ore suspended on a tea-strainer in the hottest Bunsen flame I could muster. These hot pieces were then quenched in ice-cold water, recovered and hammered down in a granite mortar and pestle with some water added to it. The coarser material was then separated from the fines using the same tea-strainer and returned to the flame and quenched again. Repeating this process a few times ultimately resulted in very finely crushed wet Beryl, which was dried.



2. Fusing and dissolving:

An earlier attempt using KOH was only half-successful and won’t be fully reported here. Instead about 15 g of crushed beryl was mixed with twice the amount of NaOH prills and fused for an hour in a stainless steel crucible (nickel would be better but I don’t have any) To the cooled mass some deionised water (DIW) was added and the mass then quantitatively transferred into a large beaker and diluted with more DIW to about 500 ml and simmered for about 30 min. The supernatant liquid was a clear green, which must indicate chromium (as chromite), either picked up from the crucible or present in the sample (in the first test, mild steel instead of stainless was used and no chromite was observed, so pick-up is the most likely explanation).




3. Filtering, precipitating and leaching with sat. NaHCO3 solution:

On filtering the green solution turned yellow (as filtrate), which would seem to indicate oxidation to chromate. The filter cake was washed with some 2.9 g of NaOH dissolved in about 200 ml DIW. It looked like a lot of greyish-brown fines with some larger whitish lumps (silica?) as well.




To the above filtrate was added about 25 ml H2SO4 95 % mixed into 30 ml of DIW and the resulting paper pH was about 1 at that point. No silica precipitated, so that must have dropped out at the dilution of the fused mass.

The pH was then adjusted to 7, using small amounts of 12 M NH3(aq). A copious amount of amphoterical, highly flocculent hyroxides precipitated. This was filtered and washed with copious amounts of boiling DIW and the filter cake, which was snow-white and gelatinous, quantitatively transferred to a large beaker and diluted to a total volume of about 250 ml. 25 g of pure NaHCO3 was added and under vigorous stirring this slurry was taken up to about 50 C to help dissolve the NaHCO3.The slurry will now be allowed to stand in a warm place overnight, stirring regularly until I go to bed. This should extract any Be(OH)2 from the precipitated mass.

The leachate will then be precipitated by partial neutralisation and prolonged boiling to drive off all CO2.

Here’s one I did earlier, a little Be(OH)2 from the first test, using KOH:







[Edited on 9-2-2013 by blogfast25]

Quote: Originally posted by zed

Hard to crush? Try cooling it first, with dry ice (solid CO2). This might render your material brittle. Also, Beryl is said to be soluble in certain molten lead salts....Probably the basis of the recrystallized "Chatham" or"Gilson" Emerald. Dissolve Beryl in a molten lead salt mixture, then allow it to cool very slowly and crystallize into a gem quality crystals. Also said to be soluble enough in hot-hot-hot water, to be grown as gem crystals by hydro-thermal means. Beryllium is deadly. Once exposed, there is no real fix, you need a new body. Exercise caution.

Quote: Originally posted by zed

At higher temperatures, Beryl might actually melt. Oxy-hydrogen flame might do the trick. The Vernuiel process can't be used to form Emeralds. The process produces only a glass. But, the strength of such a glass, might be such....That you could easily crush it with a hammer. Or, not.

Quote: Originally posted by Wizzard

Zed - Problem with grinding it down, as I see it, would be getting bits of the grinding material in what was to be ground up!

Finally, a bit of a result. Fusing about 20 g of crushed Beryl with 3 times its weight in KOH, removing the KOH with water (more or less), reacting the fused Beryl with strong H2SO4, filtering, neutralising the filtrate first with NaOH (90 % degree of neutralisation), then with 12 M NH3(aq) to pH about 9, a mixture of Al(OH)3 and Be(OH)2 (and some Fe from crucible pick up) was obtained and isolated as filter cake and washed profusely.

To leach out the Be(OH)2 the filter cake was firstly suspended in sufficient water, then that solvent was saturated with NaHCO3 (10 g/100 ml water) and allowed to stand at about 40 C overnight, stirring occasionally. The volume of suspended material reduced significantly and it was then filtered off and washed with 100 ml of sat. NaHCO3. The filtrate is supposed to contain the Be(OH)2 as a bicarbonate complex.

To break the complex, an equivalent amount (to the NaHCO3) of H2SO4 was added to almost neutral and the CO2 removed by vigorous stirring/beating of the solution. On adding a small amount of strong NH3 the beryllium hydroxide hydrate then dropped out slowly:



It’s a crappy photo because by the time I was ready to take it, a second crop of Be(OH)2, this one even fluffier, had started to precipitate, hence the haziness of the supernatant liquor. The pink hue is due to the dye in my toilet grade 95 % H2SO4 (it will wash out). Tomorrow the Be(OH)2 will be filtered and washed and then refined one more time by dissolving in ammonium bicarbonate (20 %) and precipitating as Be(OH)2 by simply boiling in the solution slowly (the amm. bicar of course evaporates as NH3 and CO2).



[Edited on 20-2-2013 by blogfast25]

It turned out the ammonium bicarbonate food grade was unusable because of all kinds of insoluble crap, mainly anti-caking agents I suspect. I could have filtered it but that wouldn’t have guaranteed purity either. Grrr!

So instead I Buchner filtered the above suspension with my new ‘-20” mercury vacuum’ gizmo (someone get those engineers from out of the steam engine age, please! '-20" mercury' means about 260 mm mercury absolute pressure, so certainly not high vacuum), fresh from eBay. It filtered really well and at the right rate, then washing with several aliquots of mineral water, then DIW, then sucked dry and it came of the filter easily in plates. Here it is drying on a low setting hot plate:



The area of interest is about 10 cm diameter.

This will then be weighed to 0.01 g and hopefully converted to BeSO4.4H2O but I need clean H2SO4 for that.

I've no idea of purity but it's snow white, not a bad sign...



[Edited on 24-2-2013 by blogfast25]

Weighed, the presumed beryllium hydroxide above amounted to about 1.84 g.

An attempt was made to turn this into crystals of BeSO4.4H20. The solubility of BeSO4 (expressed as BeSO4) at 100 C is apparently about 44 w%, from which the amounts of concentrated H2SO4 and water can be calsulated using:

Be(OH)2(s) + H2SO4(l) === > BeSO4(s, aq) + H2O(l)

The calculated amounts of Be(OH)2, water and 96 % H2SO4 were then combined and much neutralisation heat was generated. But also unexpectedly some CO2 bubbles. Either the product contains occluded bicarbonate, is partly basic beryllium carbonate or has absorbed some CO2 during storage.

Also, although most of it dissolved with great gusto, some of it refused to. Minute amounts of extra water and a couple of drops 96 % H2SO4 only partly remedied the problem, all the while keeping the solution on a 100 C water bath.

On cooling overnight white, somewhat non-descript crystals of BeSO4.4H2O did however materialise:



Not too bad for a first attempt with such a small amount of beryllium, really…



[Edited on 13-3-2013 by blogfast25]

Here's some reference Be(SO)4 for you guys

This was made from high-purity 98% sulfuric and high purity Beryllium lump, some fraction of a g of metal, to yeild around 1.5g of the salt.

I did not write down measurements... But it's close. The bottle is 1" and the salt is a bit hygroscopic to the point of deliquiesence.


[Edited on 3-13-2013 by Wizzard]

Quote: Originally posted by Wizzard

Here's some reference Be(SO)4 for you guys This was made from high-purity 98% sulfuric and high purity Beryllium lump, some fraction of a g of metal, to yeild around 1.5g of the salt. I did not write down measurements... But it's close. The bottle is 1" and the salt is a bit hygroscopic to the point of deliquiesence. [Edited on 3-13-2013 by Wizzard]

Nice crystals, Wizz.

@blogfast - Thanks!

@woelen - That may be the case - There was a bit excess sulfuric acid present, and also a bit of undissolved Be! Over the course of about a year in a plastic (barely sealed) container, they became a bit 'slimey', like they had just been taken from water.

One neat thing is they have some dispersion, like a diamond.. It's rather hard to capture. Perhaps I'll grow some larger crystals from my present stock.

If only my hot plate wasn't dead

Quote: Originally posted by AndersHoveland

What about trying to dissolve the beryl in boiling concentrated phosphoric acid ? It can attack glass and fused quartz, though the reaction may take some time.