A moonshiner question

krd

I'm not shining the moon. But my chemistry is really terrible.

A really big problem in making any kind of spirit for human consumption is Methanol. (The Czech government have enacted a moratorium over the sale of any liquor above 20% volume - as they've had a rash of methanol adulteration related deaths - many Czechs are displeased - Pivo just ain't the same thing.)

Typically in moon shine production, to avoid killing your clientèle, you distil off and dump the methanol from your mash. This is a real pain in the ass thing to do. As, in the context of a still, the boiling point of methanol is not far from ethanol. You will lose ethanol product, in the process of distilling the methanol. Some shiners, skip this part of the process - occasionally resulting in liver failure, brain damage, blindness and death.

Anyway. I did know a moonshiner. And he said - though the conversation was in a noisy pub, that he added some calcium compound to his mash. And then the reaction precipitated the MeOH, as I believe, Calcium Carbonate.


What was that calcium compound my Moonshiner friend threw in his mix?

He said it was something readily available.

Tigger

krd wrote: »

I'm not shining the moon. But my chemistry is really terrible.

A really big problem in making any kind of spirit for human consumption is Methanol. (The Czech government have enacted a moratorium over the sale of any liquor above 20% volume - as they've had a rash of methanol adulteration related deaths - many Czechs are displeased - Pivo just ain't the same thing.)

Typically in moon shine production, to avoid killing your clientèle, you distil off and dump the methanol from your mash. This is a real pain in the ass thing to do. As, in the context of a still, the boiling point of methanol is not far from ethanol. You will lose ethanol product, in the process of distilling the methanol. Some shiners, skip this part of the process - occasionally resulting in liver failure, brain damage, blindness and death.

Anyway. I did know a moonshiner. And he said - though the conversation was in a noisy pub, that he added some calcium compound to his mash. And then the reaction precipitated the MeOH, as I believe, Calcium Carbonate.


What was that calcium compound my Moonshiner friend threw in his mix?

He said it was something readily available.

Calcium chloride I'd assume
He's making calcium oxalate as we tho and that stuff is bad for you so make sure it's filtered well

Personally I'd prefer triple distilled temperature controlled ethanol than some half arsed lazy stuff

krd

Tigger wrote: »

Calcium chloride I'd assume
He's making calcium oxalate as we tho and that stuff is bad for you so make sure it's filtered well

Methyl alcohol is far worse for you. I suppose you could do a filtration but it's really about getting the mash ready for ethanol distillation.

I've looked up Calcium Chloride and I don't think it's the thing. I think it turns your ethanol to ethylene. You're looking to lose your methyl while keeping the ethyl.

Personally I'd prefer triple distilled temperature controlled ethanol than some half arsed lazy stuff

If you've ever tasted Irish potín - the vast majority of it is really awful. What makes it really awful is fusel oil.

Liquids will vaporise before their boiling points. Which is why, even if you're controlling the temperature you will get fusel oil coming through your distillation - fusel oil should have a very high boiling point. In a triple still, the job is to condense the fusel oil out.

If you want to get the methanol out, you have to lower the temperature and wait. But you will lose ethanol product in the process. And you may lose a lot. I saw a comment on a home distilling website, where they were discussing temperatures, apparatus etc. And one poster said, they were all wrong, and what they should do is set up their still at a low temperature (below ethanol's boiling point), and leave it over night. I believe what he said is correct. Spirits have been made for a long time. They're are traditional methods all over the world where it's basically a barrel, a wood fire, and an air cooled condenser - no thermometer. I've had Romanian homemade brandy made this way, and it's not nasty at all.

If you're brewing your alcohol, the amount of Methyl is dependent on what you feed your yeast. If it's grain, the yeast will produce mostly ethanol. If it's wood chips, you'll get a lot of methanol. So these traditional recipes like plum brandies, where it's brewed plums, there generally isn't enough methanol to be worried about. In the Czech Republic - the recent deaths could have been due to a counterfeiter being cheap and using saw dust instead of sugar. Or, they may have not removed the adulterants from industrial alcohol.

Commercial alcohol/drinks producers may be using a chemical process to remove methyl from their mixes. I have heard that they actually buy industrial alcohol by the barrel and treat it - then add the flavourings - that way they get a consistent product without the headaches. And that the old copper stills are just for show.

Capt'n Midnight

krd wrote: »

Commercial alcohol/drinks producers may be using a chemical process to remove methyl from their mixes. I have heard that they actually buy industrial alcohol by the barrel and treat it - then add the flavourings - that way they get a consistent product without the headaches. And that the old copper stills are just for show.

Just to note - that's food grade alcohol. IIRC Baileys is made from the alcohol got by fermenting whey.


Most of the reactions listed about converting methanol to something else only happen at very very high temperatures and will also affect the ethanol too. Things like Methanol dehydrogenase that turn methanol into formaldehyde probably aren't the way to go because while formaldehyde might possibly be easier to remove, it's also a lot more toxic. (same goes for formic acid and to a lesser extent lactic acid )

So the golden rule is to avoid production of methanol in the first place.


Even then you need more than one distillation and throw away the first and last portions even though they will contain ethanol because you are also throwing away some of the nasties too.

Note: the cure for methanol poisoning is lots of ethanol and that's more or less just to dilute it. Ethanol binds to the enzyme Alcohol Dehydrogenase better than methanol does so your body don't turn as much methanol into nasty things as it would otherwise.

krd

Capt'n Midnight wrote: »

Just to note - that's food grade alcohol. IIRC Baileys is made from the alcohol got by fermenting whey.

Are you sure they're fermenting whey? Most of it would be casein protein. I understood it, that yeast preferred sugar for making alcohol. Bacteria loves casein - and the smell is rotten milk.

Something like Baileys is very tricky to make. The cream and alcohol has to emulsify. I've heard it doesn't always happen, and they have to dump an entire batch. Maybe Baileys have figured it out. I heard there was a company in Waterford making a similar liquor years ago. The emulsification failed about half the time. As the story goes, as they were dumping a failed batch - staff members would wait at the drains with receptacles - it would be still good to drink for a few days.

Most of the reactions listed about converting methanol to something else only happen at very very high temperatures and will also affect the ethanol too.

I think this reaction is a low energy one. My chemistry is pretty awful so I can't figure it out myself. In solution the ions are dissociated. Whatever the addition is, it just precipitates the methanol (well if it's CaCO3, I'm not sure but I think the only byproduct of the reaction will be water).

The person who told me about this reaction was a chemical engineer - and in their factory, the chemical engineers used to run stills all the time. As a hobby, and it made them look busy. One thing they told me they did, was add the calcium to denatured industrial alcohol, and once the methanol was gone, they'd distil what was left.

So the golden rule is to avoid production of methanol in the first place.

Yes, which I think is why homemade plum brandy tastes fine, and Potín tastes like the famine. There's something nasty about fermenting potatoes.

Yeast is funny as well. Depending what the feed is, it can make undesirable products. This is why I've heard apples are terrible for making spirits - the lunatic compounds in lunatic soup end up going through the distillation.

Even then you need more than one distillation and throw away the first and last portions even though they will contain ethanol because you are also throwing away some of the nasties too.

I'm not running my own still by the way. Just curious. I think it depends on what kind of still you're using. The throw away the early portion, and then the last, is a kind of rule of thumb. If you have a very controlled distillation you might sit and wait out getting rid of your methanol. When you're getting down to the dregs, is where you have your fusel oil - but you'll have your fusel oil from the beginning too. There's one kind of still I've seen that uses two condenser stages - the first condenser stage is made up of children's marbles - the fusel oil tends to condense and stick to the marbles - so it's mostly ethanol going to the next condenser stage.

Note: the cure for methanol poisoning is lots of ethanol and that's more or less just to dilute it. Ethanol binds to the enzyme Alcohol Dehydrogenase better than methanol does so your body don't turn as much methanol into nasty things as it would otherwise.

The problem in Czech is they don't know what is and isn't contaminated spirit. The spirit containing methanol is in counterfeit labelled bottles.

Capt'n Midnight

In the UK the crooks had a bottling plant on the back of forty foot trailer including labeller. But that has nothing to do with popular science.

Tests for methanol would be more science.

epicmoe

Dispelling a few myths posted above...
To get rid of the methanol, You just start your still up as normal, to get to the desired heat, it has to go through the temperature for distilling ethanol anyway, to get there. Just throw away the first bit that comes out the still, which will also contain other unwanted compounds like acetone, and various esters and aldehydes, and other volatiles.
Also, '

So the golden rule is to avoid production of methanol in the first place.

ALL beers, ciders, mashes, and washes contain methanol. with beer etc, it is not a concern as it is at such a diluted ratio, but when distilled it becomes a problem, and must be taken out.

... and Potín tastes like the famine. There's something nasty about fermenting potatoes.

Although it is possible to make poitin from potatoes, it is traditionally and more usually made from an all grain mash, it is essentially just an un-aged whiskey. Sometimes it is made from a sugar wash.

Also, in answer to the OP's Question, What the man Your moonshiner friend may have put in his mix ix Epsom Salts. Not a sign of a good distiller. Not exactly frowned upon, but seen as a 'quick fix', instead of doing it properly.

OcocO

epicmoe wrote: »

Dispelling a few myths posted above...
To get rid of the methanol, You just start your still up as normal, to get to the desired heat, it has to go through the temperature for distilling ethanol anyway, to get there. Just throw away the first bit that comes out the still, which will also contain other unwanted compounds like acetone, and various esters and aldehydes, and other volatiles.
Also, '
ALL beers, ciders, mashes, and washes contain methanol. with beer etc, it is not a concern as it is at such a diluted ratio, but when distilled it becomes a problem, and must be taken out.

Although it is possible to make poitin from potatoes, it is traditionally and more usually made from an all grain mash, it is essentially just an un-aged whiskey. Sometimes it is made from a sugar wash.

Also, in answer to the OP's Question, What the man Your moonshiner friend may have put in his mix ix Epsom Salts. Not a sign of a good distiller. Not exactly frowned upon, but seen as a 'quick fix', instead of doing it properly.

Interesting.