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plante1999
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Yea, when I read about beryl, it was very often said that the idea is to break the crystalline structure of beryl. Even if K alum is more soluble, I
still have trick to purify it. I may try Di-(2-ethylhexyl)phosphoric acid from 2-ethyl hexanol from PVC gloves and phosphoric acid, using the compound
in kerosene.
I just found that my 15% BeCl2 took water... It was in a beaker, and when I looked today, it was in a solution. I do think the aluminium chloride took
water, but it may be the beryllium chloride.
I never asked for this.
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blogfast25
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2-ethyl hexanol (the alcohol of DOP) is a pain to extract from PVC gloves but there are a few threads on it in the organic section. I did it once and
it was fun but never again!
Personally I think partial elimination of Al as alum (NH4 or K), followed by extraction of Be(OH)2 with NaHCO3 solution as the most promising for home
chemistry. And it should be possible to use NH4 alum a 'precipitant', even when digesting with KOH: neutralise with H2SO4, then add small excess (on
stoichiom.) of NH4 sulphate. Cool and ice overnight.
I'm running a small recrystallisation test with NH4 alum to visualise the amount of Al left in a 0 C sat. solution of this alum. Photo later on...
[Edited on 16-1-2013 by blogfast25]
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blogfast25
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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]
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plante1999
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You should try lower the temperature at 0 or lower, like I do. I process that the process is viable to make crude purified beryllium salt. Now I wait
to get the potassium hydroxide, but when I will I will test the process I posted yesterday. There is other mean of refining tough. The bicarbonate way
seams promising for the amateur.
I never asked for this.
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Poppy
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Pardon my compliance, this garage extractions seems promissing etc.. lol
But just a cleanising on the Al(OH)3 precipitation, everyone knows it works better from hot alkali media to neutral than from acid to neutral, because
the flakes would no more be gelatinous!
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blogfast25
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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!
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It's not the volume that matters here but the degree of separation obtained. Just neutralising would also precipitate all the Be(OH)2.
[Edited on 17-1-2013 by blogfast25]
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blogfast25
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I'm fairly sure it reached 0 C during the night, then went up a little after the ice bath had melted.
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tubelectric
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| 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. 
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plante1999
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Well, yes it is the same stuff. But when we work with something, e try to take the protectons associated with its use. If one take care there is not
much difference from it then working with an heavy metal solution.
I never asked for this.
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blogfast25
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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]
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zed
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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.
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blogfast25
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| 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. |
Any references re. the first two points, Zed? I've just finished reading an admittedly old monography on Be and only lead salts as a means of
digesting Beryl was mentioned.
The toxicity is well known.
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blogfast25
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Dissapointingly, no beryllium hydroxide was to be found in the bicarbonate leachate of the second run (NaOH).
It seems the NaOH wasn't able to 'break' the SiO2/BeO solid solution, in my specific conditions.
A third run will now be made, returning to KOH (1 part Beryl/3 parts KOH).
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zed
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The Chatham and Gilson methods are proprietary. They ain't talking.
http://www.minsocam.org/ammin/AM52/AM52_744.pdf
An older reference paper to synthetic emerald growth. Nobody mentions molten lead salts in relation to emeralds.
Perhaps, sometime in the foggy past, I saw such a reference. Perhaps not. Might have been Sapphires or Rubies.
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.
[Edited on 10-2-2013 by zed]
[Edited on 10-2-2013 by zed]
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blogfast25
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| 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.
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Heat treatment, including melting and quenching to cause vitrification (and thus separation of the phases) is part of several industrial processes for
the extraction of BeO from Beryl. Induction heating is caused to get above 1600 C. Hyperfast cooling causes the molten Beryl to turn to glass,
grindable and soluble in very hot, concentrated H2SO4 (except for the silica phase, of course).
The more wasteful alkali fusion method (essentially scaled up 'wet' analysis) used by me doesn't really require vitrification.
[Edited on 11-2-2013 by blogfast25]
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Wizzard
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@Zed - You are thinking aluminum oxides + analogous impurities in molten molybdenum trioxide. Used to make small, gem-quality red ruby (Al2O3 and
Chromium oxide impurities) natural crystals.
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zed
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If you have standard lapidary gear, the easiest method to "break-up" your material, might be to grind it to a fine slurry, via a diamond rough cutting
lap lubricated with water.
Diamond is a lot cheaper than it used to be. Such a lap is now manufactured by pressing diamond into a metal disk, and then electroplating it into
place.
Alternately, a water cooled/lubricated carbide grinding wheel might suffice. Just grind away the Beryl, and collect the remains. Provided, your
grinding wheel is hard enough to cut Beryl.
Yup! Just checked. Beryl is hard, but not exceedingly hard.
[Edited on 13-2-2013 by zed]
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Wizzard
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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!
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blogfast25
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| 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! |
There's no question that the beryl abrades off some of the granite from my mortar and pestle but that just cannot be avoided as I'm unabe to properly
'frit' this ore.
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blogfast25
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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]
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plante1999
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Glad you got some yield. I would have boiled the bicarbonate leach instead of adding an acid and then a base, for purity concern. I'm taking a break
on my side, due to the lack of certain reagents at the moment, but in a few week I will continue my work.
I never asked for this.
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blogfast25
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There can't be much difference precipitating it from a sodium carbonate solution (by boiling) or from a sodium sulphate solution (like I do). It's
different if you use ammonium bicarbonate, which evaporates completely.
Look forward to seeing your results!
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blogfast25
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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]
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blogfast25
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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]
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Wizzard
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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]
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