Worried About Methanol And Other Fermenting Hazards

[jtatarin]

Hey guys hows it going. I just found this forum from a google search and I just want to say its truly fantastic! Anyways just for fun I am fermenting about a gallon of sugar/water/yeast mash and another gallon of corn mean/sugar/water/yeast mash. Both have been fermenting since last wednesday so we are coming up on 6 days ( I planned on ending the fermentation on the 10th day). Both batches seem quite active using just common bakers yeast I bought at albertsons. I live in southern california where the weater is in the 80's so it appears to be in an ideal environment.

Anyways when I distill my mixtures Im worried about methanol and other toxins. I have yet to read any articles that seem trustworthy. I know that distilling plain sugar and corn meal produces minimal amounts of methanol anyways but I do plan on fermenting other fruits (even those high in pectins) in the future which I know produce more methanols.

I know that there are several types of alcahols all from which appear in most spirits but they all have different boiling points. Methanol is the lightest molecule so it should evaporate at a lower temperature than the rest of the alcahols. Methanol boils at 64.7 °C so I was thinking about just heating my mash to that temperture so all the methanol would just boil off as vapor and leave. Is this a good way of removing methanols from mash?

I know methanol is found in the foreshot but to me that doesn't make since to DISTILL out the methanol. Why wouldn't people just heat the mash to 64.7 °C and just vaporize off the methanol and be done with it? Thanks

[copperhead]

think you would be better off just tossing the forshots what kind of still are you useing.mabey you should do more reading the mother site.it takes a good bet of methnol to kill you but you don't want to get sick eather.this is a great hobby but please be carful.

[Rebel_Yell]

Welcome to the forum jtatarin.

Have you read the parent site? http://homedistiller.org
You can find the answers to your questions there.

[jtatarin]

Thank you for your reply but I havent found much info on the removal of methanol. I havent found the answer to my question: If I put a half gallon of my fermented mash in to an uncovered container and raise the temperature to 64.7 °C (methanols boiling point) will that remove all the methanol in my mash? Seems to me in would as the methanol would be boiled off. It doesn't make sence to distill out the methanol but contaminating your unit with methanol when you could just heat the mash to 64.7 °C and remove all of it in one fell swoop.

Pot stills vs reflux stills seems interesting to me. I understand the idea of a reflux still but I can't see how a pot still couldn't do the same. I read on the website that a potstill can only make 40% ABV. What would be the other 60% in the distillate? If you closely monitor the temperature of the mash and keep it to 78.4 (ethanols boiling point) how could there be anything else but ethanol in the distillate. Simple science doesn't make sence to me. I cant see how a pot still can't make 95% pure in one pass if you keep the temperature at 78.4 C.

[Enlikil]

For your ABV% question.
Multiple distillations.
lets say you start with a 10% wash Then
1st run through makes 40% product
2nd run through makes 60% product
3rd run through makes 80% or better product

As for your methonal question.
Seperation.. You can't seperate them just by boiling they will hang on to each other for dear life. Same reason its very difficult to make a Alchohol free beer. 0.5% is achievable by boiling off/and or flash freezing. but its still there.

and when yo uare taking about something like methonal, why chance it.. just seperate it and toss it out.

[theholymackerel]

jtatarin, don't get mad but ya obviously don't understand the physics of distillation.

Don't mess around with distillin' 'till ya understand better or ya might hurt yerself or others and possibly do great property damage.

Go to the parent site and read, read, read. (http://homedistiller.org onclick="window.open(this.href);return false;" rel="nofollow)

Once ya understand the basics we here will all be glad to answer questions.

[Longhairedcountryboy]

I think you are missing an important part of the equation here. You can't control the temp of the boil. The chemical makeup of the wash/mash controls the boiling point. The boiling point of methanol is 64.7C, the boiling point of water is 100C. The boiling point of a mixture of the two is somewhere in between, depending on how much of either are present. If there is more methanol than water, the boiling point is closer to methanol's boiling point, if there is more water, the boiling point is closer to water's boiling point. The vapor produced will be a mixture of the components as well. the resulting distillate will be a mixture, just with a higher consentration of the more volitile components. Methanol is just an example. The boiling points of ethanol and everything else produced by fermentation factor into the boiling point of the liquid as well.

The mix doesn't separate easily. It takes many distillations to acheave good separation. A reflux column uses packing and distillate returning as reflux to perform many seperations in one pass. As the vapor loses heat to the packing and condeses on its surface area, some of that heat is absorbed by the more alcohol rich condensation already on it and a the more volitle components are turned back into vapor and the less volitile components stay liquid and fall further down the packing to absorb more heat from the rising vapor, equalling further separation all the way up the column.

A pot still provides very few degrees of separation. You would need to distill the liquid many times to acheave what a reflux column does in one run. My pot still (12" packed column for a little more separation, but not much) starts producing output around 85C on the first run with a wash at ~10%abv or so. The output is around 45 - 50%abv. If I redistill that liquid, it boiles at a lower temp and the output is 70 -80%abv.

At least that is how I understand it. I was hoping someone else would jump in and explain this more clearly. I think if you reread the Theory section of http://homedistiller.org onclick="window.open(this.href);return false;" rel="nofollow and do a search on that site for Height Equivilant of Theoretical Plates (HETP), this will make better sence. After that, do one run through your pot still and redistill the output. Carefully watch the temp and abv of the distillate of both runs. Collect the output in small amounts in seperate containers. Lable them in order of how they came off the still, and at what temp and abv. Smell them in order. Between the two runs, you should see a greater degree of separation between the consentration of smells and it should all become clear to you.

EDIT: I agree with theholymackerel. What you are getting into can be very dangerous. It is important to understand what you are doing and take the proper safty precautions. Just reread the homesite and I know things will start to get clearer for you.

[jtatarin]

I have read many websites over and over and now I understand! When mixing multiple liquids together the actual boiling point varies and this makes a pot still obsolete in making 95% ethanol.

I plan on making a valved reflux still based on these instructions:
moonshinestill.com/page17.htm

At the top of the valve head I want to keep the temp at 78C. to distill out all the ethanol and methanol. But what if I make this reflux still and keep the top at (64.7 C Methanol boiling Point) wouldn't that remove 95% of the methanol just as it would remove 95% ethanol at 78c?

I have read all the articles and i understand it all now Im just worried about methanol. I STILL have not found an article that appears to me to be accurate when removing methanols. Is there a testing kit I can do to my stilled product to test for methanols? I dont have to worry about fusels right if i use a reflux still at 78c?

[Rebel_Yell]

A question for you to ponder, jtatarin...

Isn't Methanol produced in the making of many wines? Even those that are sold commercially?

[Longhairedcountryboy]

OK I hope no one gets upset about this one, but a very quick look at the parent site would be all it would take to find this under safety in the introduction section of the menu...

Will I go Blind ?
A big fear for many new distillers is that they are risking poisoning themselves with methanol - a toxin that can cause blindness. There is little basis for this fear however; if formed, it is only in small amounts, and can be easily discarded with the "heads" collected first (see here) during distillation.

A simple (but effective) rule of thumb for this is to throw away the first 50 mL you collect (per 20 L mash used) for a reflux still. If using a potstill, make it more like 100-200 mL. Do this, and you have removed all the hazardous foreshots, including the methanol. To get a really clean distinction between the foreshots and the rest of the alcohol, increase the reflux ratio to the point where you're taking off this first 50 mL at a very slow rate (eg 1 drop per second). This will give a very stable equilibrium within the column to allow all the methanol to collect at the top of the column and be in this first portion.

If you are doing a double or triple distillation with a pot still, don't worry about removing the heads & tails on the first pass. Wait for the second run, when they are more distinct & easier to seperate. Once you have removed them, they are gone, so much less will need to be discarded from the subsequent runs, other than that dictated by taste, and any improved seperation that may result from running a more pure distillate through the still.

How dangerous are the various fusel oils ? I've got some of them listed below.
The ones with toxicity data listed are ...
Methanol : usual fatal dose 100-250 mL
1-Pentanol : LD50 (rat) 3030 mg/kg
3-Pentanol : LD50 (rat) 1870 mg/kg
Compare this to the amounts present in distilled spirits. The data in Wheeler & Willmotts "Spirits unlimited - a complete guide to home distilling" gives :
Home distilled spirit (untreated): methanol 0.0067%, ethanol 99.632%, fusils 0.361%
Commercial vodka: methanol 0.013%, ethanol 99.507%, fusils 0.48%
Poor quality home distilled spirit : methanol 0.0186%, ethanol 98.453%, and fusils 1.528%
If you're talking about untreated spirits as being dangerous, then to reach the LD50's that are published, you'd need to consume 149 L to be affected by the methanol, or for a 90kg bloke, about 58 L for the pentanol, from the "good" homemade stuff. That would be one hell of a session ! Even on their "poor quality" brew you'd need 11 L for the fusels. Stock standard pissed-as-a-newt high-school-student alcohol poisoning is the greater problem.

Now their "home distilled spirit" was at a time when their best design was only putting out roughly 75% pure ethanol. What's the story from like a Nixon-Stone or Euro doing 95%+ purity ?

Compare that to the levels of methanol etc that you get via other sources ...
Methanol & Other Impurities

Methanol is formed when fermenting beverages high in pectins - eg grapes and berries. Starting with a grain or sugar based wort, in a clean fermentor with a yeast culture from a well aereated source will result in small/none formed.
Carl from Hambletonbard (makers of Alcotec yeasts) details ..
Methanol, you will typically get around 2 or 3 parts per million (or milligrams per litre if you prefer) of methanol produced during fermentation of a standard 6kg type Alcotec - this is extremely low even compared to commercial products. We don't have a great deal of data on methanol because whenever we have tested for it we have got extremely low results.
Mike explains about the pectin ..
The methanol comes from the pectin, which mainly composed of methyl esters of galactose. When pectin breaks down, by enzymes introduced by microorganisms, or deliberately introduced, the methyl esters combine with water to produce methanol, so the aim should be to leave the pectin well alone if you can.

I think Jack would agree that what he means is that fermenting at a high temperature, or adding pectin enzyme, or trying for an abv higher than 12% all increase the risk of methanol being produced, so his advice about low temperature fermentation, adding no exra enzymes, and a target lower than 12%abv is all good stuff.

You are already being exposed to methanol from other sources. Some fruit juices are naturally high in methanol - for example apple juice can have 0.2-0.3% methanol, or if derived from pulp by enzymatic degradation, the levels can be 2 to 3 times higher.

Johan found ..
In http://archive.food.gov.uk/maff/archive ... orange.htm" onclick="window.open(this.href);return false;" rel="nofollow orange juice contains 10 to 50 times as much methanol as sugarmash.

The lethal dose of methanol is at least 100 ml that is equal to about 80000 mg or you need 27000 liters of mash at least to get that amount.

also from the webpage: "Dietary surveys have shown that an extreme consumer of orange juice drinks slightly over 2 litres/day. The estimated maximum intake of methanol based on this consumption would be 455 mg for a 60 kg adult which is below the maximum advisory intake of 600 mg per day for a 60 kg adult, recommended by the Department of Health."

So if we stay under 600 mg per day we are safe, that's the same as 200 liters of mash per day or about 70 liters of 40% alcohol per day if you weight is 60 kg.

total amount of methanol in mash expressed in ml is about 0.1 ml = nothing.

Jack comments ...
The Long Ashton Research Station did some studies that showed that ciders and apple juices clarified with pectic enzymes are higher in methanol due to the demethylation of juice pectins. The methanol content varied from 10 to 400 ppm in the test samples. I don't know which fruits are highest/lowest in pectin content, but apples are commonly considered the highest.

This is why all the old books on cider making refer to a condition called "apple palsey" - it's the massively painfull hangover from the high methanol content. In order to prevent this (I'm sure distilling the pectin turns it into methanol) distillers must fully clarify any fruit wine before cooking it. Rather than use clarifiers, put the wine into 2 or 4 liter plastic jugs (only filled half full) and freeze them solid, then thaw them out, this will result in perfectly clear (and chill- stabilized) wine ready for distilling. After the thawing is complete or maybe as much as a week after, the wine will be crystal clear.
Stephen Alexander reports that commercial spirits contain small levels of methanol. 'Food Chemistry' by Belitz&Grosch list an assay of about 50 different components of about 10 different distilled beverages. The US and Scotch whiskies had methanol levels around 0.2 to 0.3 %. Kevin Brown has scanned in some MeOH chromatograms from a column application guide published by Supelco of Bellefonte, PA. (a vendor for chromatography supplies). Check out http://amlc.uvi.edu/distill/meoh.html" onclick="window.open(this.href);return false;" rel="nofollow for details.

See also "Increasing Direct Marketing for Fruit Farmers by Connecting Producer to Producer through Research and Development of a Value-Added Product" at http://www.ams.usda.gov/tmd/FSMIP/FY2001/MO0341.pdf" onclick="window.open(this.href);return false;" rel="nofollow for quite a detailed report into the compostion & quantities of impurities present etc in fruit brandies, and the factors affecting their production.

The Food and Drug Administration (FDA) advised ATF that 0.1 percent of methanol by volume in wine was a safe level. Any wine containing methanol in excess of this amount is deemed adulterated pursuant to the Federal Food, Drug and Cosmetic Act, 21 U.S.C. 34l(a)(2)(C) and 348.

From http://www.polishvodkas.com/fr_vodka-tech.htm" onclick="window.open(this.href);return false;" rel="nofollow - it reckons that a molasses wash won't have any methanol present !
"....Molasses spirit can also be rectified and then used to produce vodka. In some countries it is even preferred, since it contains no methyl alcohol at all. Crop-sourced spirit contains infinitesimal amounts of methyl alcohol which have no effect on health, but some people, victims of their own overconcern, insist on molasses spirit. I should add that the presence of these tiny amounts of methyl alcohol have no effect whatever on the aroma of even unflavoured vodka. It is simply undetectable. In neutral grain or potato spirit the methyl alcohol has practically disappeared....."

"DBall" asks .. If Methanol is poison and is removed at the beginning of distillation... Question: When/how is methanol removed from wine or beer?

Brad answers ...
It's not tricky at all. Methanol is a by-product of fermentation; more methanol is produced in fruit fermentation than in grains. Brewers do not remove the methanol in beer and wine because methanol is not especially toxic at low concentrations. You are looking at between 0.4%-1% methanol in wines and brandies and smaller amounts in beers. Distillers remove almost all the methanol in most cases. Ever notice how vodka produces clean hangovers and wines (particularly reds) give you very nasty hangovers? Methanol. That, and dehydration!

Methanol is an especially nasty type of alcohol because the body tries to break it down the same way it metabolizes, or breaks down, ethanol, the type of alcohol in beer, wine and other drinks. Metabolizing ethanol produces chemicals less toxic to the body than alcohol. Unfortunately, if the same chemical action is performed on methanol the result is formic acid, lactic acid and formaldehyde.

Formaldehyde attacks nerve cells, especially the optic nerve and can damage the liver and kidneys. Formic acid and lactic acid also attack the kidneys and liver. Most people who have drunk methanol die of severe and sudden kidney and liver failure.

Chronic methanol drinking will cause optical damage. The stories of moonshine causing blindness comes from U.S. prohibition times where some bootleggers used to cut moonshine with methylated spirits to increase profit.
Gregory writes:
It isn't the yeast that controls methanol, it's what you're fermenting. I believe yeast has very limited metabolic pathways around methanol. Quoting from -

"Basically it can be produced biologically in 2 ways; through the oxidation of methane by methane monooxygenase, or by the reduction of formaldehyde, by methanol dehydrogenase (and this reaction normally works in the reverse direction).

It's true that some methanol can be produced during fermentation, but this is not derived from the ethanol or by carbohydrate oxidation. It is produced in small amounts, either by non-enzymatic reactions or through the reduction of formaldehyde."

Methane isn't present in our washes, so the culprit is formaldehyde. I believe the pectins in fruit are methylated and can break down in the wash into formaldehyde. But so long as your wash has only pure fermentable carbohydrates, you can expect essentially zero methanol. There's a bit more in this discussion of methanol here: http://yarchive.net/med/methanol_poisoning.html" onclick="window.open(this.href);return false;" rel="nofollow

Ethyl acetate, OTOH, is produced spontaneously whenever acetate is present with ethanol. There are several possible sources of acetate during fermentation. In general, acetate is formed by oxidation of ethanol. (In fact, acetate is the 'end-product' of our own metabolism of ethanol). In fermentation, oxidation of ethanol into acetate can happen as a result of desperate yeast metabolizing its own ethanol, or by contamination with other yeasts or bacteria.

See http://en.wikipedia.org/wiki/Wine_fault" onclick="window.open(this.href);return false;" rel="nofollow
Methanol Toxicity
Ups advises about methanol toxicity :
The fatal dose of methanol is 60 to 250 mL. Death depends on the size of the individual, their general health and stomach contents. The exposure limit is 200ppm. The highly lethal nature of methanol (compared to ethanol) has not been fully researched, but it is believed to be the result of the byproducts of metabolism, which turn methanol into formic acid and formaldehyde, and formaldehyde has been proven to have selective injurious effects on retal cells- this is the reason for it's ability to cause blindness.

Methanol is metabolized and excreted at a rate about one-fifth that of ethanol, and a single dose may take up to 4 days to leave the body (provided the drinker isn't already dead)

Symptoms fom acute poisoning of a moderate dose- Severe headache, dizziness, nausea and vomiting, and central nervous system depression. Vision may fail temporarily or permanently after 2-6 days. In higher doses the above occurs much faster and turn into rapid shallow breathing, blood pressure falling, dilation of pupils blurring of vision, cyanosis. More than 25% of those who reach this level, even in a hospital, still die.

Chronic poisoning tends to result in visual imparement as the first symptom. The only treatment from chronic poisoning is to halt all exposure.

Treating acute cases must be done within 2 hours of ingestion: give syrup of ipacac. Lavage thoroughly with 2-4L of tap water with sodium bicarbonate (20G/L) added. This is to treat acidosis of the blood)

Antidote: Give ethanol, 50%, 1.5ml per kilo of body weight, orally, diluted to no more than a 5% solution, followed by 0.5-1ml/kg every 2 hours orally for 4 days. ethanol interferes with the absorbtion of methanol by the body and allows it to be excreted with less damaging effects. Also give up to 4 litres of water daily to maintain adequate urine output. Control delirium by giving 10mg valium slowly by injection in order to prevent respiratory depression.

Prognosis:in acute methanol poisoning approx 50% do not recover. Visual imparement will show no improvement after 1 week.

Looking up medical and drug testing labs in the phonebook will help you find someplace to send a sample of the stuff your making (say you found it in a friend's room and your worried about what he's drinking) to see how clean it is.

Isn't this something you have read? All the info you are looking for is in the homedistiller.org site. Take some time and read that site. You will be glad you did.

[Tater]

heh

[duds2u]

Lordy, that should put to rest any further questions on methanol and the safety of our hobby.

[Aidas]

Yet another shining example that Tater's signature will never, ever become obsolete.

Aidas

[muckanic]

The bit about MeOH being formed by the action of heat upon pectin is a tad controversial, I would have thought. It potentially has implications for whether fruit pulp should go into the boiler ...

And the bit about "acetate" being formed by the oxidation of EtOH is just plain confused, although not really relevant to the issue at hand.

[Billy Joe Jim Bob]

Hi LHCB: Thanks, that was a good read...BJJB

[jtatarin]

Thank you for that great read. Methanol is obviously importate for me to understand because I plan on trying to ferment fruit based washes.

Another question: Is methanol REALLY the only BAD bi-product in a fermentation? Is there really ever a need to REMOVE fusels regarldess of what i ferment and distill?

I have already read that entire article but it still doesnt really answer my question.

It says to remove methanol throw away 50ml of the foreshot but doesn't that depend on whats being fermented. What if my wash is simple sugar and water then there is basically no methanol or what if the wash is pure strawberies and sugar? There is just too many factors here... I would rather have a simple cut and dry way of removing toxins that works perfectly on all washes. That article DOES NOT say that.

[Longhairedcountryboy]

The amount of fusels produced in any proper ferment isn't enough to kill you. Might get you good and hung over though. Discard forshots and smell for heads to finish and you will be safe. Tails is where all the fusel oils will be. There boiling point is greater than ethanol. You will smell them, if not, you will definitly taste them. If you are making whiskey, rum, brandy etc., you want some of that flavor. A reflux still strips all the flavor so you are left with vodka. Tails taste bad in neutral spirits (vodka). If you don't cut to tails soon enough, you will know it. You can use activated carbon to remove the oils, or redistill it and make more carefull cuts. It would be very hard to poison yourself if you run your rig properly and make good cuts.

[junkyard dawg]

What the article Does say will make a lot more sense if you just start running your still. Don't drink it for a few batches, till you are sure you have it right. But do smell and taste it the way the site says...

that site may seem vague, but its really just concise. practice running your still a few times and you'll understand. thanks for thinking...

so, got that still built? I have one like that, lots of mods... thats a good design, and you can easily tweak it to do anything. search this forum for some good posts about improvements on the basic design your looking at.