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Author: Subject: Extraction of beryllium from beryl
plante1999
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[*] posted on 1-1-2013 at 12:06
Extraction of beryllium from beryl


So I just bought 3 pound of beryl ore, which is not cheap, soon it should be in my mail. Fallowing yield stated by Ullmann's I should get 44-45g of beryllium. When I will get it I will make some test and post the results!



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plante1999
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[*] posted on 9-1-2013 at 13:45


I just go the 3 pounds of beryl ore, in a few hour you should get my first thought and test about it. The beryl is crude, as expected, but do not contain much gange. It is a pale blue/green/gray ore in 3/4 pieces.



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[*] posted on 9-1-2013 at 14:46


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



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[*] posted on 9-1-2013 at 16:51


Well, this rock is the most hard I ever saw! At first I took two piece of total 21.5 g total weight. At first I put the two pieces in 3 plastic bag and smashed with a 16 ounces hammer, the hammer resonated in my hand, but the ore was untouched. Then I took the vise and put a bag under it. Then I put the two pieces in the jaw and crushed them, it took 5 run before a good part of the ore was crushed to frit. 14 g of frit was obtained and 6.6 g pieces. About 0.9 g was lost during crushing. The frit was mixed with equivalent weight of calcium carbonate. It was heated in a S.S 40ml crucible and heated orange red hot and poured while hot in 50ml of cold water. Then 15ml Conc. H2SO4 was added and a lot of effervescence was observed as well as strong sulphuric acid odor and hydrogen sulphide smell.
5 g (NH4)2SO4 was added to a beaker, and the sulphuric acid/beryl mixture was filtered in the ammonium sulphate.

While the mixture filtered and ammonium sulphate dissolved in the filtrate, a 13g piece of beryl was heated to yellow temperature and dropped in 50 ml of cold water. The rock did not flinch so I re heated the ore to yellow temp, and dropped it in 200 ml cold water. The ore didn't seam to bother thermal shock at all. While I heated the ore, I was expecting the ore to explode by air or steam. But it didn't happen. I'm starting to think that berylware would make an awesome glassware!

I looked at the filtrate from the calcium carbonate reaction, and found small crystals starting to form at 20 degree Celsius. I put the beaker in the snow outside, At the moment I wait for the mixture to precipitate most of the ammonium alum.

I had a face shield, and no dust was present during all the experiment.

[Edited on 10-1-2013 by plante1999]




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[*] posted on 9-1-2013 at 18:24


Beryl is hard stuff. Mohs hardness 7.5! I'm glad you could crush some of it for experiments. I hope the rest of the procedure goes well for you.
Happy new year!
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plante1999
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[*] posted on 9-1-2013 at 18:47


Yea, I just experienced its hardness! I just tried to powder 2 gram of frit I made using two steel plate and using pressure and movement to crunch to powder. All I did was making heavy marks on the steel... This experiment will be challenging for me, at least I have 3 pounds of ore to test with! So the precipitate, when at -2, by look was less than I tenth of gram.... For 14g worth of ore. The solution was discarded because of it's very low concentration.

I need more aggressive chemical to dissolve the ore, saddly enough I do not have anymore NaOH left... I will try to find something else.

"I need something stronger"

Happy new year to you, and for every other member!

[Edited on 10-1-2013 by plante1999]




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[*] posted on 9-1-2013 at 23:52


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.

[Edited on 10-1-13 by woelen]




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[*] posted on 10-1-2013 at 04:01


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

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[*] posted on 10-1-2013 at 04:56


I think that you are not hitting it hard enough, fluoride containing fusion mixtures look like the way to go;
http://en.wikipedia.org/wiki/Berylium#Production
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plante1999
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[*] posted on 10-1-2013 at 05:01


I would like a part of the thread to be put in chemistry in general and named extraction of beryllium from beryl. (For the moderators) Thanks!

Tonight I will try to react molten sodium pyrosulphate (made with sodium bisulphate) with the beryl frit. The objective is to solubilise the aluminium and beryllium but not the silica. Then neutralize and leach with sodium bicarbonate solution for the beryllium content. The leach will then be boiled to precipitate the beryllium hydroxide. Calcination and washing should give good purity.

I may also heat a beryl piece to yellow temp and drop cold water onto it while it is heated.

I do not have anymore fluoride, like I already said, it is one of the chemical I use the most. So now I must do without it. 1kg of calcium fluoride would probably be well enough for the 3 pounds of beryl.

I want berylsilicate ware!

--------------------------------------------------------------------

EDIT (woelen): Thread is split and part on beryl ore is moved as requested.

[Edited on 10-1-13 by woelen]




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plante1999
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[*] posted on 10-1-2013 at 09:12


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.


Fluorides, especially complex fluoride such as Na2FeF5 and Na2SiF6 are supposed to eat trough it like a charm. However I am out of stock for fluorides. Some other agresive reagents at high temperature may be efficient too. Beryllium hydroxide leach in sodium bicarbonae solution. And reprecipitate when the bicarbonate is decomposed by heating.

Thank you for splitting the thread.




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[*] posted on 10-1-2013 at 12:57


I have a broken Argon laser which has an ID'd beryllium ceramic lasing vessel.... Dare I disassemble it?
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[*] posted on 10-1-2013 at 14:09


Years ago I found some interesting patents relating to extracting beryllium from Beryl, mostly by fusion with CaCO3. Not for the faint of heart!

This webpage here:

http://www.surechem.org/index.php?Action=document&docId=...

... is fairly wide in it's listing of beryl extraction technologies.

[Edited on 10-1-2013 by blogfast25]




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[*] posted on 10-1-2013 at 16:45


I got my first beryllium hydroxide! I obtained a negligible amount, but still. I used my last 8 g of sodium hydroxide tough. First I took 2 g of beryllium frit and mixed with 8g of sodium hydroxide in a S.S crucible and melted to a glass-like material. Then I dropped 30 ml of cold water onto the glass. I poured the mixture to a beaker and added 20 ml of sulphuric acid, I wanted to use 10 ml but I used the wrong beaker. Then I filtered and added 2 g (NH4)2SO4 and the solution was left in the cold for one day. The second day some crystalline material was precipitated. 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. I got a pinch of white flocculant precipitate, which I assume is beryllium hydroxide. The precipitate may be only a few tenth of mg.

I also tried to grind thermally shocked beryl. It was found to be much easier. This is similar to the statement made in De Re Metallica, he say that when the ore is heated and dropped in water, it greatly help to crunch it to a powder.




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[*] posted on 10-1-2013 at 17:48


There are also some Cu - Be alloys that might make
good starting materials. (probably fairly expensive though).


http://en.wikipedia.org/wiki/Beryllium_copper
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[*] posted on 11-1-2013 at 05:00


So, here my actual plan for the week-end, which start today after school:

Because I found that thermally chocked ore are way easier to grind, I will do this treatment to 60 g ore and grind it. The basic melt seams to be viable, so I will take 55 g of ore powder, and mix it with stochiometrical weight of sodium carbonate. I will heat to melt everything together, and grind it to powder. I will add the powder to 200 ml water and I will boil it to try to dissolve the melt powder. Then I will add 92 ml of H2SO4 and boil the mixture for a few tenth of minutes, to dissolve most of the aluminium and beryllium. I will filter to remove silica and sodium sulphate.

At this point I can do 4 treatment to extract the Be out of the solution. Which one should I use?

1: Precipitate the aluminium as Ammonium alum, filter and boil to get 90% + pure beryllium sulphate.

2: Add a few hundred ml of sodium bicarbonate solution, filter and boil to get 99% beryllium hydroxide/sub carbonate.

3: Add ammonia, filter, wash put it in ammonium chloride solution, and boil it to dissolve the basic beryllium hydroxide to beryllium chloride. Filter and boil down to get 95% + Berryllium chloride

All these are from patents/ Ulmann's.

[Edited on 11-1-2013 by plante1999]




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[*] posted on 11-1-2013 at 13:48


Nice work indeed, plante!

Eliminating most of the aluminium as ammonium alum may be a partial solution to the problem: acc. Wiki, at 0 C, 100 parts of water dissolve only 2.62 parts of ammonium alum. My own observations confirm that more or less: I’ve made ammonium alum many times, also in kg quantities, and get near 100 % actual yield, when chilling the solution to near 0 C.

Of course your supernatant liquor, assuming it still contains all the BeSO4 and there is no co-crystallisation, will still contain some aluminium. Perhaps as final purification, exploit the differing degrees of amphoterism of Al and Be? Using a mild alkali like bicarbonate it may be possible to keep the small amount of remaining Al in solution as aluminate, while 100 % precipitating the Be(OH)2?

Also, could you point to a few of the more interesting patents you’re using?

(It's really this bit I'm interested in:

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. .
)

Check your U2U.


[Edited on 11-1-2013 by blogfast25]




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[*] posted on 11-1-2013 at 15:43


Quote: Originally posted by Wizzard  
I have a broken Argon laser which has an ID'd beryllium ceramic lasing vessel.... Dare I disassemble it?


Wear a dust mask, and avoid creating small particles. In short do not go cutting or grinding away on it. Also best to wear gloves to prevent any tiny particles from getting into any broken areas on your skin (cuts). I like the bag of 50 for 4 bucks Vinyl gloves at Dollar store for stuff like this. So thin you have full feeling and dexterity in your fingers. Not much protection for that reason but just avoid fracturing, cutting, or in general any process which will create dust. In its unbroken, clean, solid form BeO ceramic is not too much to worry about. You can handle clean smooth Be metal without any danger for the most part (within reason, being careful), but I still use gloves for the metal as well. The solid ceramic like the solid metal is reasonably safe. It is when microscopic particles get into cuts or inhaled problems arise. No one desires to turn blue and die AFAIK. When you need to transfer much heat while insulating against high voltages BeO in plate form is amazing stuff and safe when one is careful.However if you do develop a sensitivity to either material it is time to stop playing with it.




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[*] posted on 12-1-2013 at 06:47


If my calculations are correct, at 0 C a saturated solution of ammonium alum in water would contain less than 0.1 % of aluminium (as Al), based on relative mass of alum at 453.33 g/mol and Wiki's stated solubility.

I may run a quick test with that...

[Edited on 12-1-2013 by blogfast25]




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[*] posted on 12-1-2013 at 13:52


So I got a yield, finally!

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.

In industry they use alum precipitation.
For the bicarbonate patent: http://www.google.ca/patents/US2298800?pg=PA4&dq=berylli...





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[*] posted on 12-1-2013 at 14:14


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.



Huh? On this occasion you don't appear to have separated to Be and Al? Your chloride is realyy (Al,Be) chloride? Or am I misunderstanding you?




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[*] posted on 12-1-2013 at 14:46


It is Be, Al, and Na chloride, the Na could be easily removed tough. I keep the crude product until I get a good amount of it, then I will purify it. I may try solvent extraction, or dissolve the Al and Be chloride with methanol, boil it down and react it with H2SO4 and ammonia to precipitate Al, filter and boil down to get the beryllium sulphate.



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[*] posted on 13-1-2013 at 08:29


I see.

Is your frit crushable/grindable? Down to powder? That would increase 'reactivity' enormously...

Another thing that might help with the separation is that AlCl3 is basically insoluble in conc. HCl. I've seen it precipitate with my own eyes: boiled down an AlCl3 solution a lot, cooled, then added excess of 36 % HCl; white AlCl3 hydrated dropped out. But I don't know about BeCl2 behaviour in these circumstances.

Keep it up.




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[*] posted on 14-1-2013 at 16:46


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.




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[*] posted on 15-1-2013 at 05:55


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.


That's a variant on previous, really: 'break' the chemical structure of the beryl first by turning it into silicates/beryllate/aluminates. K alaum is somewhat more soluble in the cold than NH4 alum, IIRW.




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