Apple spirit - very sharp heads?

katzgejm · Post by **katzgejm** » Wed Mar 02, 2016 5:20 pm

I work at a commercial winery & cidery, and I thought I'd pass some of our 6.5%abv cider through my home pot still. Cider is made from filtered, pectin-free (supposedly) apple juice. No additives except some tannin and malic acid pre-fermentation, and kms post-fermentation.

20L charge, stripping run, I tossed the 1st 100ml just to be safe.

What's strange is that the heads have gone on for a LONG time (about 2L of collection), 50%abv-40%abv. I have never had something come through my still smelling so SHARP and repulsive. Now that I'm deeper into the strip at about 35%abv, the sharpness is all but gone and the flavour is as expected, rich and appley.

I've read that the heads (and methanol) are elevated in cider, but will they really make up half of the stripping run? I'm very surprised by this as I've distilled apple wines and ciders in the past and never encountered such a quantity or quality of heads.

Post by **Tater** » Wed Mar 02, 2016 9:18 pm

There is more but sounds like you got extra .Can ya talk about recipe for cider and yeast ?

IanD · Post by **IanD** » Thu Mar 03, 2016 2:18 am

It's the sulphite from the kms that's coming through not heads per se. Post fermentation kms is a no no. To fix it you need to add hydrogen peroxide before you do the spirit run otherwise it will be much worse in the spirit run. About 10ml/l 3% solution should do it. Leave it if couple of days and repeat if the bad smell remains.

Incidentally you need to keep a lot of what you might call heads in an apple run and age a year or preferably much longer to make a decent brandy. Just ditch a lot of foreshots and only recycle tails.

Post by **thecroweater** » Thu Mar 03, 2016 6:11 am

I'm going to go out on a limb here and guess your still is stainless steel, a copper still would have removed most of the sulphides in the strip and pretty much what ever is left in the spirit run without any need for chemical amelioration. Assuming my guess is on the money you can try chucking in a good handful off copper off cuts in your boiler and if you can get some copper mesh in the column without causing reflux it may work as a catalyst. Either way this is a stripping run so don' panic and I wouldn't worry about cuts that are going to be further compressed in a slower stripping run

katzgejm · Post by **katzgejm** » Thu Mar 03, 2016 2:41 pm

thecroweater wrote:I'm going to go out on a limb here and guess your still is stainless steel, a copper still would have removed most of the sulphides in the strip and pretty much what ever is left in the spirit run without any need for chemical amelioration. Assuming my guess is on the money you can try chucking in a good handful off copper off cuts in your boiler and if you can get some copper mesh in the column without causing reflux it may work as a catalyst. Either way this is a stripping run so don' panic and I wouldn't worry about cuts that are going to be further compressed in a slower stripping run

you're bang on, i didn't put any copper in the boiler or column because i plan on doing two more distillations.

kms addition was 50ppm about 14 days ago. zero sulphur on the nose of the cider, so i'm surprised it's showing up in the stripped distillate? i also wouldn't call the sharpness sulphurous, but i'll take everybody's word for it.

my next run is going to go through a column packed with copper rings and i'll do a very cautious separation of anything that doesn't smell appley and delicious.

the third and final run is going to be another pot run, with juniper and other botanicals in the boiler. this is meant to be a vaguely appley gin.

Post by **thecroweater** » Thu Mar 03, 2016 5:23 pm

Just re-reading this sulphur might not be the only culprit here and you may have a couple of other nasty compounds at play. apples can have some small amount of cyanide and will very likely have some urea present. Cyanide is a precursor in the formation of ethyl carbonate in fermentation where urea is present and in cider is generally not at levels to cause any major issues. In distilling copper acts as a catalyst for ethyl carbamate so it is non issue with copper, a stainless still with inadequate or no copper in the vapour path will carry this bitter, possibly carcinogenic compound over to the distillate

katzgejm · Post by **katzgejm** » Thu Mar 03, 2016 6:00 pm

thecroweater wrote:Just re-reading this sulphur might not be the only culprit here and you may have a couple of other nasty compounds at play. apples can have some small amount of cyanide and will very likely have some urea present. Cyanide is a precursor in the formation of ethyl carbonate in fermentation where urea is present and in cider is generally not at levels to cause any major issues. In distilling copper acts as a catalyst for ethyl carbamate so it is non issue with copper, a stainless still with inadequate or no copper in the vapour path will carry this bitter, possibly carcinogenic compound over to the distillate

well that's interesting.

i've got the 2nd run going as i type this, through a 30" column packed with a combo of stainless steel scrubbies and about a lb of copper rings (cut from 1/2" pipe). i think the painful, nose-searing smell in the heads is in fact kms. i was surprised because it is completely undetectable in the cider, but over the top after distillation. copper in the column seems to have helped very little.

how do i solve this sulphur problem so my 3rd run is clean? more copper? let the distillate sit on copper for a few days? what's this about hydrogen peroxide?

i should say, i've collected 800ml so far and with each 200ml, the sulphur nose has dropped noticeably.

katzgejm · Post by **katzgejm** » Thu Mar 03, 2016 6:31 pm

IanD wrote:It's the sulphite from the kms that's coming through not heads per se. Post fermentation kms is a no no. To fix it you need to add hydrogen peroxide before you do the spirit run otherwise it will be much worse in the spirit run. About 10ml/l 3% solution should do it. Leave it if couple of days and repeat if the bad smell remains.

Incidentally you need to keep a lot of what you might call heads in an apple run and age a year or preferably much longer to make a decent brandy. Just ditch a lot of foreshots and only recycle tails.

you're right, kms has been magnified on this spirit run i fear. so do i add h2o2 at the same rate to a spirit run at 80%abv? 10ml/L?

IanD · Post by **IanD** » Fri Mar 04, 2016 1:44 am

thecroweater wrote:I'm going to go out on a limb here and guess your still is stainless steel, a copper still would have removed most of the sulphides in the strip and pretty much what ever is left in the spirit run without any need for chemical amelioration. Assuming my guess is on the money you can try chucking in a good handful off copper off cuts in your boiler and if you can get some copper mesh in the column without causing reflux it may work as a catalyst. Either way this is a stripping run so don' panic and I wouldn't worry about cuts that are going to be further compressed in a slower stripping run

Hold on. It's not sulphide it's sulphite that's the problem here. The spelling is important. (The ph vs. f in sulphur isn't important that's just a British Spelling vs. US Spelling thing)

Copper will remove sulphides but will have no effect on sulphites. Nevertheless it's still a good idea to have some copper in the vapour path.

IanD · Post by **IanD** » Fri Mar 04, 2016 1:57 am

katzgejm wrote: you're right, kms has been magnified on this spirit run i fear. so do i add h2o2 at the same rate to a spirit run at 80%abv? 10ml/L?

I think, in your situation, I'd dilute to 40% add h2o2 in slamm increments until I couldn't detect the SO2 smell more over a few days then add a little bit more to make sure it's all gone and then re-run. SO2 + H2O2 -> H2SO4 i.e. sulphuric acid. Not enough to hurt you but I wouldn't want to drink it and running it again will get rid of it. You're going to lose quality and flavour but at this point all you can do is make the best of a bad situation.

Post by **thecroweater** » Fri Mar 04, 2016 2:41 am

Sure about that, reckon ya might find it froms Cu2o3 from sulphite

Copper reacts with sulphur

IanD · Post by **IanD** » Fri Mar 04, 2016 3:50 am

thecroweater wrote:Sure about that, reckon ya might find it froms Cu2o3 from sulphite
Copper reacts with sulphur

My chemistry isn't that good but SO2 gets through in practice copper or no copper. H2S doesn't.

IanD · Post by **IanD** » Fri Mar 04, 2016 4:45 am

thecroweater wrote:Just re-reading this sulphur might not be the only culprit here and you may have a couple of other nasty compounds at play. apples can have some small amount of cyanide and will very likely have some urea present. Cyanide is a precursor in the formation of ethyl carbonate in fermentation where urea is present and in cider is generally not at levels to cause any major issues. In distilling copper acts as a catalyst for ethyl carbamate so it is non issue with copper, a stainless still with inadequate or no copper in the vapour path will carry this bitter, possibly carcinogenic compound over to the distillate

Hmm... a little worrying.

http://www.efsa.europa.eu/sites/default ... ts/551.pdf" onclick="window.open(this.href);return false;" rel="nofollow

katzgejm · Post by **katzgejm** » Fri Mar 04, 2016 2:47 pm

IanD wrote:
katzgejm wrote: you're right, kms has been magnified on this spirit run i fear. so do i add h2o2 at the same rate to a spirit run at 80%abv? 10ml/L?
I think, in your situation, I'd dilute to 40% add h2o2 in slamm increments until I couldn't detect the SO2 smell more over a few days then add a little bit more to make sure it's all gone and then re-run. SO2 + H2O2 -> H2SO4 i.e. sulphuric acid. Not enough to hurt you but I wouldn't want to drink it and running it again will get rid of it. You're going to lose quality and flavour but at this point all you can do is make the best of a bad situation.

i'll try this. i also didn't realize copper doesn't remove sulphites. definitely good to know!

i've got about 1L of distillate at 80%abv (after discarding the very kms heavy heads). i'll cut in half to 2L 40%abv, add 20ml H2O2, and wait a few days. the sulphiric acid that is produced boils at 337C, so in theory i'll have very, very little come over in the third run, correct?

thanks a ton, btw, this has been very helpful.

katzgejm · Post by **katzgejm** » Fri Mar 04, 2016 4:00 pm

come to think of it, is there any reason i shouldn't just add the H2O2 to the 80% distillate? if i should add 10ml/L at 40%abv, then i should add 20ml/L at 80%abv, yes?

also, why not simply go heavy (50ml/L say) with the H2O2 as it too has a higher boiling point than water?

here's my current plan:
add 20ml H2O2 to 1L 80%abv distillate. let sit 48hrs or until SO2 smell is gone. to that i will add botanicals (juniper, rosemary, etc), and let sit 24hrs. i will dilute this to 2L 40%abv, and then run through a final 3rd time with my still in pot mode (no reflux) though i will have some copper rings in the column. collect down to 60%abv or so, and bam, apple gin.

thoughts?

Post by **thecroweater** » Fri Mar 04, 2016 9:10 pm

My thoughts are copper will do its thing, the results you got sound typical of a still with not enough copper running a high sulphur ferment. I tinkers you will find you will not need the chemical additives. You think those chemical won't carry over because of their boiling points but they all change once they form compounds

katzgejm · Post by **katzgejm** » Sat Mar 05, 2016 11:23 am

here's another interesting piece of the puzzle:

"Sulphur dioxide is usually made in the laboratory by heating concentrated sulphuric acid with copper turnings. Cu + 2 H2SO4 ==> CuSO4 + SO2 + 2 H2O" http://www.ucc.ie/academic/chem/dolchem ... p/so2.html" onclick="window.open(this.href);return false;" rel="nofollow

so after my H2O2 addition, if i have any Cu in the boiler, am i simply reacting the H2SO4 right back into SO2??

IanD · Post by **IanD** » Mon Mar 07, 2016 2:22 am

I have been remiss in not providing links to support my claims.

Here are three methods for reducing SO2. If you don't like hydrogen peroxide try one of the others.

http://onlinelibrary.wiley.com/doi/10.1002/jib.100/pdf" onclick="window.open(this.href);return false;" rel="nofollow

There's mention of the peroxide technique here on a professional distillers forum.

http://adiforums.com/index.php?showtopi ... entry10816" onclick="window.open(this.href);return false;" rel="nofollow

Mostly they are as confused as many people here about the difference between sulphites and sulphides.

However you will find confirmation that copper stills don't get rid of SO2. I think the reason is probably that when SO2 is an issue it is present in far greater quantities than when H2S is an issue. Too much for the copper in a still to cope with.

IanD · Post by **IanD** » Mon Mar 07, 2016 2:25 am

katzgejm wrote:here's another interesting piece of the puzzle:

"Sulphur dioxide is usually made in the laboratory by heating concentrated sulphuric acid with copper turnings. Cu + 2 H2SO4 ==> CuSO4 + SO2 + 2 H2O" http://www.ucc.ie/academic/chem/dolchem ... p/so2.html" onclick="window.open(this.href);return false;" rel="nofollow

so after my H2O2 addition, if i have any Cu in the boiler, am i simply reacting the H2SO4 right back into SO2??

The key here is "concentrated" you'll have extremely dilute H2SO4. If you can make SO2 from copper it makes me wonder how copper can also remove it.

IanD · Post by **IanD** » Mon Mar 07, 2016 2:26 am

An incidentally I said 10ml/l of 3% peroxide solution not 10ml/L of pure peroxide.

IanD · Post by **IanD** » Mon Mar 07, 2016 2:32 am

thecroweater wrote:Just re-reading this sulphur might not be the only culprit here and you may have a couple of other nasty compounds at play. apples can have some small amount of cyanide and will very likely have some urea present. Cyanide is a precursor in the formation of ethyl carbonate in fermentation where urea is present and in cider is generally not at levels to cause any major issues. In distilling copper acts as a catalyst for ethyl carbamate so it is non issue with copper, a stainless still with inadequate or no copper in the vapour path will carry this bitter, possibly carcinogenic compound over to the distillate

Ethyl carbamate is only formed in the presence of copper according to this. But it is mostly removed in the spirit run.

http://onlinelibrary.wiley.com/doi/10.1 ... 4618.x/pdf" onclick="window.open(this.href);return false;" rel="nofollow

Post by **thecroweater** » Mon Mar 07, 2016 3:02 am

yes I have read that but it is not a fact in fact it is rubbish. As it has been rehashed many times with many links to refute it I have no intention of going back over it but ethyl carbamate does not need copper it doesn't need a still and it is in many solutions that have not nor ever will be distilled. How it forms can be found on the net, I think from memory there are over 1400 sources mentioning the formation of ethyl carbamate in the absence of copper oh yeah and this wiley one. ethyl carbamate is a problem with some wines where urea is used, not a lot of copper going on there but yes copper is a catalyst for EC and that is a damn good thing

IanD · Post by **IanD** » Mon Mar 07, 2016 5:59 am

thecroweater wrote:yes I have read that but it is not a fact in fact it is rubbish. As it has been rehashed many times with many links to refute it I have no intention of going back over it but ethyl carbamate does not need copper it doesn't need a still and it is in many solutions that have not nor ever will be distilled. How it forms can be found on the net, I think from memory there are over 1400 sources mentioning the formation of ethyl carbamate in the absence of copper oh yeah and this wiley one. ethyl carbamate is a problem with some wines where urea is used, not a lot of copper going on there but yes copper is a catalyst for EC and that is a damn good thing

I don't understand. Catalyst in what reaction involving EC?

Post by **pfshine** » Mon Mar 07, 2016 6:13 am

Not again. Please not again. Dear baby Jesus please not again.

IanD · Post by **IanD** » Mon Mar 07, 2016 6:36 am

Ok, I've got it. Ethyl Carbamate can be formed from both urea and hydrogen cyanate but it normally happens slowly. Copper catalyses these reactions so that the reaction runs to completion quickly and the EC remains in the pot. Without copper the precursors may be present in the distillate and form EC over time.

Thanks, great information to have.

I can't find any articles specifically refuting the findings of Riffkin et. al. Could someone point me at them please?

katzgejm · Post by **katzgejm** » Mon Mar 07, 2016 4:15 pm

IanD wrote:An incidentally I said 10ml/l of 3% peroxide solution not 10ml/L of pure peroxide.

thanks ian, you've been most thorough and helpful.

i've added 20ml of diluted (3%) H2O2 to 1.3L of distillate (71%abv). the SO2 nose has all but disappeared.

i understand that peroxide is a powerful oxidizer, used in bombs, etc. but 20ml of 3% solution, diluted by more than half in the final run (i would add 3L of water to the boiler)--where is the hazard here? not in explosiveness, surely. am i potentially creating dangerous compounds that will come over in my final spirit? i'd like an explanation of how.

TO BE CLEAR, I DO NOT INTEND TO DISTILL THIS BATCH SHOULD ANYBODY RAISE ANY LEGITIMATE CONCERNS

Post by **thecroweater** » Mon Mar 07, 2016 6:16 pm

personally I think the two of you might be better off elsewhere

katzgejm · Post by **katzgejm** » Mon Mar 07, 2016 6:46 pm

thecroweater wrote:personally I think the two of you might be better off elsewhere

i'm a hobbiest distiller, this is a hobbiest distiller's forum. we're discussing a fairly common problem/solution for hobbyist distillers. everything seems to line up.

i appreciate your concerns, truly, but nobody so far has made clear the actual dangers of distilling low wines with a small quantity of diluted hydrogen peroxide in the boiler. if you're so convinced this is a terrible idea, please, enlighten me and the rest of this forum. sharing knowledge is why we're all here, right?

Post by **thecroweater** » Mon Mar 07, 2016 7:46 pm

no it is not a common solution and the common ways to deal with your problem have been addressed, there is a very real chance of you causing an exothermic reaction and i am looking into the likelihood of that. it would seen the amount of peroxide and acetone likely to be present could only cause at best a very small explosion. I'm not trying to be a bastard and what you do is your own business but ppl will read and follow this as sage advise down the track so it damn well needs to be safe to stay here on the boards

Katzgejm wrote
if you're so convinced this is a terrible idea, please, enlighten me and the rest of this forum

Actually you are the one proposing this method and the onus is on you to show why this is a safe method for distilling. You are the one claiming its safe contrary to information available on the net and you really do need to produce some very clear data proving this beyond reasonable doubt to be safe. Somebody suffers lost of property gets maimed of killed because due diligence wasn't shown here and how will you feel about that, I already know how I would feel

IanD · Post by **IanD** » Tue Mar 08, 2016 1:41 am

thecroweater wrote:personally I think the two of you might be better off elsewhere

Ok, I'm away. Please delete my account.

Home Distiller

Apple spirit - very sharp heads?

Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?

Re: Apple spirit - very sharp heads?