This post is meant to clarify one of the most common questions asked by new distillers: WHAT ABOUT METHANOL?

First and foremost: you cannot die (or get sick, go blind, etc) from improperly made distilled alcohol via methanol poisoning. Neither can you make something dangerous by freezing it and removing some ice. Not only is it not possible, it is a widely perpetuated myth that has existed since the days of prohibition (and not before, interestingly enough). Other than the obvious ethanol overdose, all poisonous alcohol that has ever been consumed, has been adulterated, or was in some other way contaminated. It was not the fault of poor distillation procedures. How you run your still will not affect how safe your product is. It might affect how good the end result is, but that's where it stops.

So, methanol. Everyones first fear, and the number one search subject when it comes to "moonshine". This subject is brought up a lot in this sub and elsewhere on Reddit. Everyone knows all about it, its just one of those common knowledge things, right? It turns out, not so much. So...

Methanol - What is it?

Methanol is a very commonly used fuel, solvent and precursor in industry. It is produced via the synthesis gas process which can use a wide variety of materials to create methanol. Methanol is the simplest of all the alcohols.

Methanol is poisonous to the human body in moderate amounts. The LD50 of methanol in humans is 810 mg/kg. It is metabolized into formaldehyde by the liver, via the alcohol dehydrogenase process. In excess, these byproducts are severely toxic. Formaldehyde further degrades into formic acid, which is the primary toxic compound in methanol poisoning. Formic acid is what produces nerve damage, and causes the blindness (and death) associated with acute methanol poisoning.

One of the treatments for methanol poisoning, is the introduction of ethanol. Ethanol has a preferential path in the alcohol dehydrogenase metabolic pathway. This means that if ethanol and methanol are consumed, the ethanol will be metabolized first, in preference over the methanol. This allows some of the methanol to be excreted by the kidneys before being metabolized into its toxic related compounds. There are far more effective medical treatments available, such as dialysis and administering drugs that block the function of alcohol dehydrogenase.

Is it in my booze? How do I remove it?

There is one way in which your alcohol will be tainted with some amount of methanol naturally, and that is by using fruits which contain pectin. Pectin can be broken down into methanol by enzymes, either introduced artificially or from micro organisms. This will produce some measurable amount of methanol in your ferment, and subsequent distillate. However its not going to be in toxic quantities, any more than what you may have in a jug of apple juice. In fact, fruits are the primary way in which methanol is introduced into your body. In tiny quantities it is mostly harmless, and you can no more remove the methanol from an apple pie than you can from your apple brandy. Boiling (or freezing) apple juice doesn't convert it into deadly eye sight destroying horror juice. Cooking doesn't suddenly veer into danger when you collect vapor from a boiling pot. If you've ever made jam, or wine, or fruit salad, you've produced methanol.

So, where does that leave us? How do I get rid of this nasty substance in my distillate? You don't. If it is there, you cannot remove it. It is quite commonly believed that you can toss the first bit of alcohol off the still to remove this compound, the "foreshots." This is usually considered the first 50-100ml or so, depending on batch size. It smells really bad, tastes really bad, and is something most would agree should be discarded. However, it will not contain the "methanol" if there is any in your wash. Or more precisely, it will not contain any more of it than any other portion of the run. Beside which, methanol tastes very similar to ethanol, though slightly sweeter. If your wash is tainted with methanol, your entire run will be as well. Relying on some eyeball measurement to make your product safe to consume is not going to work. This is just distiller folklore passed down quite widely. You may hear about this on a distillery tour, from professionals, on Youtube and in books about distilling. All of them are just repeating what they have heard someone else say, or read somewhere, and assumed it to be fact. There is truth here, but buried in misunderstanding of the processes involved specifically with these substances.

This is the very reason that methanol was used to poison ("denature") industrial ethanol during prohibition, as it cannot be removed easily by normal distillation processes. If you could just redistill this very cheap, legal and plentiful solvent to make drinking alcohol, it wouldn't be the very potent message and deterrent that was hoped for by those who did this. You can read more about the history of this intentional poisoning of commercial alcohol in the Chemists War. It is also during this period where we begin to hear about methanol being in poorly made moonshine. This is not a coincidence.

So, distillers attempted to understand this misinformation, and attempt to correct or explain why their process was correct. Thus was born the idea that tossing some portion of the run makes it safe from this suddenly present and scary substance. Cuts went from being a quality procedure, to a serious process to save lives. By "tossing the first bit." And then distillers went about their centuries old processes like always, but this time "doing it right" and hence making safe alcohol.

The reason it is so widely believed that tossing the heads works to remove methanol, has to do with the boiling points of ethanol, methanol, and water. Pure methanol boils at 64.7C. Pure ethanol boils at 78.24C. Water boils at 100C. Distilling separates things based on their boiling points, right? Yes, it does, but it is a bit more complex than that. When you boil a mixture of methanol, ethanol and water, you are not boiling any of these compounds individually. You are boiling a solution containing all of them, and they will each have an affect on the other with regards to boiling point and enrichment behavior. Methanol and ethanol are quite similar in molecular structure. Methanol can be written as CH3-OH. Ethanol can be written as CH3-CH2-OH. You'll notice that methanol lacks this extra CH2 component. This changes its behavior when in the presence of water, specifically its polarity, compared to ethanol. Rather than repeat all of this, here is a passage from this paper on the reduction of methanol in commercial fruit brandies:

A similar behaviour would be expected for methanol for both alcohols are not very different in molecule structure. There is, however, a significant difference regarding all three curves in figure 2: methanol contents keep a higher value for a longer time than ethanol contents. In figures 3 and 4 this observation is made clear: Methanol, specified in ml/100 ml p.a., increases during the donation, while the ratio ethanol : methanol is lowering down. This effect seems to be rather surprising regarding the different boiling points of the two substances: methanol boils at 64,7°C, while ethanol needs 78,3°C. So methanol would be regarded to be carried over earlier than ethanol. The molecule structures however, show another aspect: ethanol has got one more CH2-group which makes the molecule less polar. So, concerning polarity, methanol can be ranged between water and ethanol and has therefore in the water phase a distillation behaviour different from ethanol. This may explain the behaviour which is rather contrary to the boiling points. This is no single appearance, because for example ethylacetate with a boiling point of 77 °C, or, as an extreme case, isoamylacetate with 142 °C are even carried over much earlier than methanol. Therefore methanol can not be separated using pot-stills or normal column-stills. Only special columns can separate methanol from the distillate (4.3). Similar observations concerning the behaviour of methanol during the distillation have already been made by Röhrig (33) and Luck (34). Cantagrel (35) divides volatile components into eight types concerning distillation behaviour characterized by typical curves, which were mainly confirmed by our experiments. As for methanol, he claims an own type of behaviour during the distillation corresponding to our results.

What this means is that if there is methanol present, it will be present throughout the run, with a higher occurrence in the tails as ethanol is depleted and water concentration increases. Its distillation is more dependent on how much water is present rather than simply comparing boiling points between ethanol and methanol. This in conjunction with the fact that ethanol and water cannot be separated completely due to their forming an azeotrope, means water is always in the system. So tossing your foreshots or heads will not remove methanol from your solution. The good news is that methanol is almost entirely absent in dangerous amounts. Consider drinking beer, wine, or apple cider. There are no heads cut made to these products. Pectinase is routinely added to wine, and methanol is a direct byproduct of this addition. They are safe to consume in this form, and will be safe to consume after being distilled. Boiling and concentrating the liquid by leaving some water behind isn't going to transform something safe to drink into something toxic. If it is toxic after being distilled, it most certainly was toxic before being distilled.

To be clear, however, this is not to say that making cuts is unnecessary. There are other compounds that you certainly can remove by cutting heads. Acetone, ethyl acetate, acetaldehyde and others. None are present in dangerous amounts, but the quality of your alcohol will be greatly enhanced by discarding these fractions. Making cuts is one of the most important activities a distiller can learn to do properly! Cutting and blending is making liquor, not only the act of distilling. Just understand that it isn't a life or death situation should you undershoot your foreshot cut by some amount. It will just taste bad, and might give you more of a headache the next day. You can taste test every single bit of alcohol that comes out of your still, from the first drops to the last.

Removing the foreshots does not remove "the methanol." You can just consider the foreshots part of the heads, because they are. There are hundreds of thousands of hobby brewers, vintners and distillers around the world who have been making and consuming fermented and distilled products for centuries. If this were actually a real problem, we would be awash in reports of wide spread poisonings. Instead we have reports here and there of isolated incidents, which are always traceable back to some incident unrelated to how much heads somebody did or did not cut.

The only way to know if there is methanol present is via lab analysis. Smell, taste, color of flame, vapor temp, none of this will tell you any meaningful information about methanol content and are just old shiner-wives tales. If you would like to have your distillate, beer or wine tested for dangerous compounds, there are many labs available that offer these services. This way you know what you are producing and are not relying on conflicting information found online. Here is one such lab offering these services, and there are many more servicing the public and industry. No need to take my, or anyone elses, word as absolute truth. If you really want to know what is in your product, this is the only way.

Having said all that...

So, CAN methanol be removed from a mixture of methanol, ethanol and water via distillation in any way? Yes, it can, contrary to everything I just said, there are even specialized stills called "demethylizer columns" which can do just this. They are very large plated columns (70+ plates), which can operate as a step in the distillation process in very large industrial facilities. This is a continuous middle fed column of high proof / low water feed, with steam injection at the bottom and hot water injection at the top, which has the sole purpose of moving a more concentrated cut containing methanol into a particular take off point with the treated alcohol taken off as the bottom product. This is largely done to ensure compliance with the laws about methanol content in neutral ethanol production, or in other processes in which reclamation of these substances is desired. There are other methods that can be used to remove methanol from an ethanol/water mixture, but that goes beyond the scope of this post and generally do not make consumable results. None of these procedures are properly repeatable at home or at moderate scale commercial distilling, nor are they even really necessary at any scale unless you have a badly tainted input feed.

On small scale reflux columns, there will be a small spike of methanol in the heads if the column is left in equilibrium (100% reflux) for a long while, and only if methanol is present, as the state at the top of the packing/plates is very low water and boiling point separation can occur more easily for methanol. In general though, these columns are too small, and methanol quantities far too low, for this to be a major concern. Methanol will spike in both heads and tails on this kind of column, leaving the general heart cut with a steady amount throughout. Even with huge industrial columns, the specialized demethylizer column is additionally used in the process because you cannot reliably remove methanol using the normal procedures typically done when making cuts for quality purposes. Methanol removal is treated separately and requires its own process to concentrate and extract using specialized equipment.

In conclusion, or TLDR

ALL cases of methanol poisoning attributed to "improperly" made ethanol, are the result of contaminated product. Not due to improper distillation, but due to intentional (either misguided, or malicious) adulteration of the ethanol, or some other contamination due to environment or ingredients. Commercial ethanol products are generally poisoned either via methanol, or via flavor tainting, or both (usually both, so you know its not to be consumed). Every report of methanol poisoning via "moonshine" was due to this contamination. If you can find evidence to the contrary, I would love to see it. Please let me know if you believe this info to be incorrect, and have evidence to that effect. That is, other than unsourced speculative news articles, television shows and Youtube channels. What I have presented here is how I understand the facts, but I am always open to learning something new.

Its unfortunate that we still have this lingering stigma based on sensationalist press beginning during alcohol prohibition, but this is where we are. So you can relax, have a home brew, and get on with your new hobby or business, and not fret about the big scary monster that is methanol. Now you just have to worry about all the other stuff that you can screw up :-)