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blogfast25
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Extracting zirconyl chloride from roll on antiperspirant
After two half-hearted and failed attempts at alkaline cracking of pottery grade Zircon (ZiSiO4) (better attempts to be continued later), I came
across an article that explains the use of Aluminium-Zirconium chloride glycine (Gly) complexes in roll on antiperspirants. With the goal of trying to
extract some small amounts of zirconyl chloride (ZrOCl2 - zirconium oxychloride) from it, I bought 200 ml of 'Mitchum 48 protection - women' (which
includes such a complex in its formula) roll on antiperspirant.
Here's what I did.
I first diluted the stuff, a sticky, thickish liquid, opaque in appearance, to about 400 ml. The pH was just under 3 at that point. I added small
aliquots of NaOH, the pH went up to about 4 and lumps started to form. At about pH = 6 the liquid had turned into a solid mass, unstirrable. By
gradually working more alkali into the mass, the thickness reduced greatly at about pH = 11. Presumably amphoterics like alumina had gone back into
solution.
The liquid proved unfiltrable at least without a Buchner. I diluted the by now about 600 ml to about 3 L, maintaining pH at about 11. Still filtering
was basically impossible but the solids did decant quite easily.
I let them decant completely and siphoned off the supernatant liquid and replaced it with more alkalised tap water (pH = 11), stirring and allowing to
decant once again. I then siphoned off the supernatant liquid again. This should have gotten rid of most of the aluminium as aluminate.
Adjusting the pH of the remaining, decanted slurry to pH = 1 with 20 % HCl, some temperature was developed and the slurry thinned out much noticeably.
Sadly, much of the slurry did not dissolve and that part must be considered the water insoluble part of the complex lipophobic/lipophylic emulsion
these products appear mostly to be made off.
Some attempts at 'breaking' the emulsion have failed so far: adding more acid, adding kerosene and strong alcohol all have no effects on the
unfiltrable emulsion that contains also the zirconyl chloride in the watery phase.
Does anybody here have any ideas on how to 'curdle' or 'cream' this fatty material emulsion and free up the zirconyl chloride containing watery phase?
[Edited on 8-4-2010 by blogfast25]
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zed
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Ummm. Sounds messy, but it might be simple. I'd be tempted to try sticking a wick in it. In other words, I might attempt to burn off all of the
"organic" components.
Thereafter, it might be possible to extract Zirconium compounds from the residual ash.
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blogfast25
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Thanks Zed, but I doubt if that would work: there too much of an aqueous phase present. It'd be a bit like trying to combust milk...
Tonight I'm going to put some of it in a blender to see if I can get the fatty matter to really clump together.
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Sedit
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Quote: Originally posted by blogfast25  | Thanks Zed, but I doubt if that would work: there too much of an aqueous phase present. It'd be a bit like trying to combust milk...
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Then dry it up and torch it.
I think if you are working with this it would be the first order of business to destroy all organics since they in no way are helping your cause. Iv
done plenty of OTC extractions of products since figuring out pathways like this are what im good at.
I don't suppose you have a list of the ingrediants do you because I went looking and can't find a complete list anyware. It appears that burning off
all the organics FIRST would yeild you a much more pleasent starting material to work with by removing any emulsifing agents and more then likely
cutting the bulk of material nearly in half or more.
Odds are your just going to stir it up into a frothed emulsion resembling shaving cream and your never going to get it out then. Can't say for sure
though because im not 100% on what all the material is.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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blogfast25
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Drying the product and burning off the organics is definitely one possibility, albeit more of a last resort, IMHO. Definitely not to be forgotten. One
would end up with very impure zirconia which of course could be purified to required degree.
But at this stage 'emulsion breaking' (e.g. the 'creaming' of milk to obtain butter) would be a neater way to separate the watery, zirconyl chloride
containing phase from the fatty matter.
I do have a list of ingredients and will post it here:
water, Aluminum Zirconium Tetrachlorohydrex Gly, Glyceryl Stearate, Laureth-23, Magnesium Aluminum Silicate (clay), Polysorbate-20, Behentrimonium
Metosulphate, Laureth-4, Cetearyl Alcohol, Lauric Acid, EDTA, Parfum, Alpha Isomethyl Ionone, Linalool, Citronellol, Hexyl Cinnamal, Butylphenyl
Methylproprional, Geraniol.
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Sedit
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LOL well... Theres always a Dildo....
They work very well for breaking emulsions perhaps sonication if you are able could produce a simular effect. It might make it worse though so maybe
test a small amount if your able.
I still will not change my mind that the first thing you should do is take a brand new container and burn off all the organics on the grill or
something. You see that almost everything is organic so all you will be left with is Clay and your good which would cut back your amount of work(and
cost) extremely.
I don't know what the product of heating Aluminum Zirconium tetrachlorohydrex Gly would be but its something to take into consideration before
processing the ash that would be left over. More then likely would result in some oxide would be my guess.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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Ozone
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Now that's a bit of unorthodox apparatus.
How about partitioning against saturated NaCl(aq) or Na2SO4(aq)?
O3
-Anyone who never made a mistake never tried anything new.
--Albert Einstein
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not_important
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Hmmm...
Starting with the original product, oxidise it using chlorine bleach with a Ni salt catalyst. This would chew up the glycerol of the 1st two
ingredients, reducing the total bulk, and convert the PEO end groups and long chain alcohols to carboxylic acids and thus to their salts. I don't
think OCl/Ni will chop PEO chains, but if it does all the better. Then do the further basification, disperse the solids in aqueous alcohol (rubbing
alcohol) and take the pH to around 3 which should be acid enough to give the free carboxylic acids while leaving the Zr hydroxide as such. Dilute with
acetone to get most of the fatty acids and other lipophiles into the alcohol-acetone phase, leaving Zr and Al in the wet solid phase.
Alternatively treat the starting material with concentrated hydrochloric acid to get the metals as aqueous chloride complexes, and extract off the
more hydrophobic stuff with solvents. Go for solvents with as much density difference from water as possible.
Yet another alternative would be to get it slightly alkaline to get all the Ze as hydroxide/hydrated oxide, evaporate off s much water as possible,
disperse in alcohol + some toluene/xylene and azeotrope off the remaining water. Hopefully much of the organics would go into the alcohol phase, the
solids would be disperseed in fresh alcohol, heated, and a less polar solvent such as acetone added to pull off most remaining organics.
A possible problem with burning off the organics would be the formation of Al-Zr oxides that would be rather unreactive to acids or alkali, taking you
back to the problem of starting with ZrO2 or ZrSiO4. ZrOCl2 itself will decompose somewhere between below the boilinh point of water up to 150 C,
giving oxychlorides with lower Cl percentages on up to hydrated ZrO2.
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blogfast25
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@Ozone:
Osmosis, eh? Definitely hadn't thought of that. Suitable OTC membrane?
@not-important:
Certainly I agree that it would have been wiser to pre-treat the product before inducing hydrolysis of the Al/Zr/Cl Glycine complex. Either by
mechanically 'breaking' the emulsion or by chemical treatment.
What about trying to oxidise much of the organics with permanganate or dichromate? Stand well back, I'd say...
Crude burning off of the organics destroys the ZrOCl2, leaving one with a residue of zirconia, alumina (possible aluminates) and some clay. Messy
too...
[Edited on 14-4-2010 by blogfast25]
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blogfast25
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Mechanically breaking ('creaming') the emulsion I simply couldn't get to work.
I then tried chemically breaking it with K2Cr2O7 and separately with commercial bleach.
To 50 ml of the emulsion, 25 ml of saturated dichromate (acidified) were added. Upon boiling no distinct visual changes were noted but the fatty
matter did drop out of the solution very quickly. I may test the supernatant liquid for the presence of Cr [+III] later.
Then 50 ml with 25 ml of commercial bleach (no nickel salt, haven't got any at the ready) were boiled up. Not much to see either but here too the
fatty matter dropped out of the emulsion quickly.
Presumably these oxidisers knock out part of the sophisticated emulsifier system.
The whole of the remaining emulsion has now been 'bleached' and is decanting overnight.
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not_important
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Glyceryl Stearate is the mono-ester of glycerol with technical stearic acid - a mix of saturated fatty acids. Laureth-# are polyethylene-oxide esters
of fatty acids. Polysorbates are polyethylene oxide ethers of sorbatol derivatives, and cetearyl alcohol is long chain primary alcohol made from fatty
acids. All are neutral (no acidic or basic groups) surface active agents. Oxidising them converts terminal HO-CH2 groups into CO2H, in alkaline
solution CO2(-) groups which are not as easy to pull into nonpolar layers; with acid dichromate yu often get chromium complexes of the organic acids
which can be a real bother to "de-chromate". The glycerol may be oxidised fully leaving simple fatty acids, to the same effect.
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UnintentionalChaos
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Am I the only one who's thinking that the zirconium is going to form gelatinous precipitates and refractory oxides if heated, just like the aluminum?
Department of Redundancy Department - Now with paperwork!
'In organic synthesis, we call decomposition products "crap", however this is not a IUPAC approved nomenclature.' -Nicodem
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not_important
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It does, but the texts on extracting Zr from zircon or crude zircronia tell how to get granular type precipitates, and it only goes refractory if
heated considerably hotter that wet processes use. The hydrated oxides formed can be dissolved in mineral acids, halides and nitric preferred as the
sulfates have low solubility.
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densest
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Since you've tried bleach, perhaps something like stronger like TCCA applied carefully might do it, or Ca(OCl)2 as a solid since the desired product
is already chlorinated. Messy and likely to spatter - I'd add the TCCA in 1g quantities in a tall vessel with stirring outdoors. According to Merck
articles, Zr acetate and oxychloride are quite soluble. The acetate is less stable in dilute solutions and more stable if heated past about 65C. So
adding conc. acetic acid, stirring well, heating, and decanting should produce a usable product. Zr sulfate is also soluble. Centrifuging might break
the emulsion as well.
Many zirconium salts form microcrystalline/gelatinous/gummy solids with polymeric structure (also according to Merck) but concentrated solutions are
reasonably stable.
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watson.fawkes
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I was about to mention this myself. It also seems promising
that some chemical additive that's incapable of breaking the emulsion on its own might do so with a bit of added artificial gravity.
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blogfast25
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Centrifuging would really have been the ticket but for that you a, erm... centrifuge! But you still need to break the emulsion first, bar perhaps with
an ultracentrifuge.
I'm relying on good old 9.8 m/s^2. The 'fatty matter' has neatly collected at the bottom, although the supernatant liquid is still slightly turbid and
will need filtering...
Diluted from fairly dilute solution Zr(OH)4.n H2O should be fairly gelatinous but less so than freshly precipitated alumina, at a guess. The aluminium
had been previously separated out.
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densest
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@blogfast - yes, the old G works well given time.  I got a small clinical
centrifuge for under $100 - it has swinging tube holders for 6 15-20ml tubes. One maker sells them under a lot of brand names. My guess is 500xG?
Daigger has similar ones for $250-400 so used ones are not expensive.
I was guessing that a stronger oxidizer might destroy more of the organic emulsifiers since the ones you've tried have made a dent in them.
According to Merck, ZrO dissolves in 66% H2SO4 with heating. The sulfate is moderately soluble in water: 52.5g/100ml @18C. As long as the oxide
doesn't get calcined to utter unreactivity, drying, removing organics with solvents or fire, and redissolving should work. The oxide does seem to be
more reactive than, say, Al2O3. I've seen mention of alkali metal zirconates forming in basic conditions and have no idea of their solubility or
reactivity.
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blogfast25
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The solubility of these oxides really depends a lot on the degree of calcining: e.g. commercially calcined TiO2 only rally dissolves in conc. hot
H2SO4 (and that takes some time too), fused with excess bisulphate and probably in anhydrous HF. I wouldn't really want to take on calcined ZrO2 or
natural ZrO2.
In the mean time I've had the first glimpse of Zr(OH)4. n H2O by alkalising about 20 mL of filtered sample to pH = 13.5 (thus keeping any residual Al
in solution). The sample was about 10 x diluted with respect to original 200 mL roll on antiperspirant product. A small amount of almost opaque
zirconium hydroxide formed and it precipitated neatly to the bottom of the test tube very quickly.
[Edited on 18-4-2010 by blogfast25]
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blogfast25
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The first dilute solution of ZrOCl2 is now in a bottle awaiting crystallisation. All Zr(OH)4 has been precipitated and most will be filtered and
washed tonight. I noticed that a more compact precipitate was obtained at higher pH (13.5) than at lower (11.5).
The current ZrOCl2 was obtained by 'squeezing' the remaining acid 'fatty matter' residue till fairly dry. A couple of hundred mL was obtained and
taken to pH = 13.5, yielding about 50 mL Zr(OH)4 precipitate. This was filtered (it filters reasonably well but a Buchner would be great), once washed
with pH = 10 NaOH, then 5 times with tap water (the filtrate then ran neutral) and once with distilled water.
The Zr(OH)4 didn't dissolve easily in cold 6 M (20 w%) HCl: I used a 100 mL first, then added another 100 mL but dissolution was incomplete still. I
then heated it up, stirring, and at about 90 C the solution was completely clear.
Setting it aside for cooling I then noticed something strange: almost immediately a small amount (definitely less than a gram, at a guess) of
precipitate formed at the bottom: that was definitely not there previously. It looked amorphous. Further cooling didn't increase the amount.
Could this be some reaction product of the 'fatty matter' and the bleach that somehow slipped through the net? A soap-type product that hydrolised in
acid conditions and solidified on cooling? A halogenated fatty acid perhaps? The small amount will be isolated tonight.
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zed
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Seems like a lot of trouble to get a little Zirconium. Might be easier to buy a little piece of cubic zirconia.....Smash it to powder with a hammer,
and then dissolve it in acid, or use some other process to convert it to the salt you desire.
Recently, I have been informed that some ceramic cooking knives, have blades that are composed of Zirconium Oxide.
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Ephoton
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some times its just for the fun of doing it 
the buety (dislexic man never get that one) of amatuer science 
e3500 console login: root
bash-2.05#
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blogfast25
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| Quote: Originally posted by zed | Seems like a lot of trouble to get a little Zirconium. Might be easier to buy a little piece of cubic zirconia.....Smash it to powder with a hammer,
and then dissolve it in acid, or use some other process to convert it to the salt you desire.
Recently, I have been informed that some ceramic cooking knives, have blades that are composed of Zirconium Oxide. |
Well, good luck trying to dissolve annealed Zirconia in anything other than molten alkali or anhydrous HF! Zircon (ZrSiO4) can be 'cracked' by fusing
with NaOH but my limited experience is that that isn't so easy either.
@ ephoton: spot on!
The extraction is now almost complete, after I hit a particular snag. Report to follow.
[Edited on 26-4-2010 by blogfast25]
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not_important
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Following up on blogfast25's reply, not only is it difficult to get ZrO2 to dissolve in something, but cubic zirconia is about the most expensive way
to get it. Both ZrO2 and ZrSiO4 are some in technical grades for use in metal casting and ceramics for much less than gemstone quality zirconia.
Fairly extreme conditions are needed to dissolve those compounds, fusion at 600 C or higher with NaOH or Na2CO3 is used for the production of hydrated
ZrO2, the starting point for many zirconium compounds; hours of fusion is followed by chilling, milling of the solids, and fusion once again. Fusion
with potassium pyrosulfate has been used for analytical purposes.
There's a thesis on the subject at http://upetd.up.ac.za/thesis/available/etd-03062006-161327/ and an overview attached
Attachment: 30123025-Zirconium-and-Zirconium-Compounds.pdf (313kB)
This file has been downloaded 1809 times
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blogfast25
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@not_important:
Is the second link to the wonderful monography by Venables on Zirconium and compounds (or is it a different document?) I'd warmly recommend to
download Venables' book for anyone with an interest in Zr.
The first link is highly interesting and I will now download the various parts and sieve for information, so thanks also for that.
I have a *.pdf on a lab study titled:
High Purity Zirconia and Silica Powders via Wet Process: Alkali Fusion of Zircon Sand
By Chieko Yamagata, João B. Andrade, Valter Ussui, Nelson.B. Limaand José O. A. Paschoal
Presented at the Sixth International Latin-American Conference on Powder Technology, November 07-10, Búzios, Rio de Janeiro, Brazil
It's fairly detailed and the crucial part reads:
"Aqueous caustic soda (NaOH) 50 wt% solution was prepared to using as the decomposition agent of zircon sand. The prepared solution and Brazilian
zircon sand were mixed in wt/wt ratio of 1.0; 1.2 and 1.5 NaOH/ZrSiO4. The moisture was carefully charged into an iron crucible and set in an electric
furnace. The alkaline fusion reaction was conducted following thermal treatment: first heating at rate 20oC/min up to 100oC, remained at this
temperature for 1h and then heating at rate 20oC/min up to 200oC, remained for 1h and finally the temperature was increased to 600oC for 2h, at that
time the alkali fusion reaction takes place and caustic frit is formed, a mixture of sodium zirconate and sodium silicate. This frit was washed with
water, removing the soluble sodium silicate and hydrolyzing the zirconate to an impure hydrous zirconium oxide. The water-leached frit was treated in
cold 8M HCl at 80oC for obtaining an impure zirconyl chloride solution."
Yields of up to 87 % zirconia (+ hafnia) recovery are reported using a high NaOH/zircon (1.5:1) ratio.
A second run on a new batch of 200 mL of roll on antiperspirant ("Mitchum") has now started, this time by attacking the virgin emulsion straight away
with commercial bleach to try and free up the watery phase immediately.
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not_important
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The bleach should destroy the glycine used in the complex, and attack some of the oxidisable stuff too. I'd recommend finishing it by adding some
nickle, even if that means dissolving a copper-nickle alloy coin in acid. Use lots of bleach, you can evaporate off water, cool things down, and add
fresh bleach.
If that seems to give a reasonably behaved mess, then consider evaporating it to near dryness, mushiness, and adding concentrated hydrochloric acid to
make it strongly acidic. That should pull the Zr and Al into solution as chloride complexes, and allow the extraction of some of the organics such as
the fatty acids into a non-polar solvent. After that the strong alkali treatment you used before to remove the Al into solution.
PDF is from Kirk-Othmer Encyclopedia of Chemical Technology. And I knew of that paper you quoted from too, but forgot to mention as the controlled
temperature processing makes it more fussy than just tossing a zircon-soda ash mix into the kiln.
[Edited on 27-4-2010 by not_important]
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