BIODIESEL & SVO DISCUSSION FORUMS





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Friends of mine started a distillery. They are accumulating a substantial amount of heads (Initial runnings, the stuff to be thrown away). Is this methanol? The same methanol that I'm currently paying $4.50 a gallon for commercially?

Said another way, can I use these heads to make bio-diesel?
 
Registered: August 18, 2014Reply With QuoteReport This Post
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Foreshots and heads. There is a few compounds, only a small amount of MeOh.
 
Location: New Zealand | Registered: August 15, 2006Reply With QuoteReport This Post
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Hi Bill,

quote:
Originally posted by Bill Burton:
Said another way, can I use these heads to make bio-diesel?
No.






 
Location: ลึก ประเทศอินเดีย | Registered: March 03, 2001Reply With QuoteReport This Post
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Here's an interesting topic! Just to flesh out the answer a bit more... I concur with the "no" response. Paulus is exactly right that there's not that much methanol in the "heads" -- the amount generally depends upon what is being distilled (which is to say, it depends on what was fermented). The potential for methanol is the safety reason for discarding the heads, and the stinky ketones, aldehydes, and other contents are the market reason you don't want them in your bottle of product.

Also, even if the heads were all methanol, the problem is that they are very wet coming out of the still. If the heads ran at an average of 180-proof (itself unlikely), that leaves you with 10% water. That is plenty to wreck the reaction. Whether your friends are running a pot still, or a multi-plate column, or some hybrid setup will largely determine the alcohol content / proof of the heads that are discarded, but in terms of biodiesel production they're going to be "pretty wet" no matter what.

I note all of this because, in my opinion, it's the same reason that making your own ethanol to use for making ethyl ester biodiesel is also impractical -- it's very difficult (or very expensive) to reach the point of anhydrous alcohol. (And if you can reach that point, the product is much more valuable as vodka than as an intermediate fuel ingredient!) Also, at least in the States, the manufacture of distilled spirits is highly regulated -- by both the federal government and the states. Producing fuel alcohol requires more or less the same permitting process as getting licensed to produce booze.

From a cost and labor standpoint, you're miles ahead to produce fuel with commercially sourced methanol and then recover it after you run the biodiesel reaction. You still have to watch out for water content, but it's a substantially smaller problem than it is during ethanol production. With ethanol, you're trying to separate alcohol from water -- and there is basically always some (and at the DIY scale, usually a lot of) water in the output stream. When recovering methanol after a biodiesel reaction, you're more or less trying to separate methanol from oil (with a little bit of water in the mix), which is generally going to result in MUCH less water in your output. That's all old hat to people who have done either of these things or who understand the process, but I thought it was worth putting in the thread in case someone searches it out later on.

As a final note, I would recommend exercising a lot of caution when dabbling in any of this area -- the legal penalties for doing these things wrong or "under the radar" can be pretty stiff. For example, here in Texas, "I was distilling drinking water" or "I was making essential oils" is not a defense to possessing an unlicensed still. From misdemeanors to felonies to federal tax evasion charges, these are authorities you probably don't want after you.

Just curious -- where is your friends' distillery? Lots of those are popping up the last couple of years, and I enjoy trying some of the craft spirits being produced.

Cheers, John
 
Registered: June 17, 2007Reply With QuoteReport This Post
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Excellent comment John and of course the reason why it's difficult to get the last water out of ethanol by distilling is that the two form an azeotrope.
 
Location: New Zealand | Registered: August 15, 2006Reply With QuoteReport This Post
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Distilling ethanol was done in organic chemistry class here. The purest it could normally be distilled as an azeotrope is 95% or 190 proof. I tried to make biodiesel with 95% grain alcohol from a liquor store and got no biodiesel (too much water). I bought 500 milliliters of expensive 99.5% ethanol with 0.5% water in it (for 35 American dollars) and it made ethyl biodiesel using a single base reaction. I used something like 30-35% anhydrous ethanol per litre of new corn oil. An equivalent amount of ethanol compared to methanol is a larger volume. In Texas the law requires an industrial ethanol distiller's permit or license, which was something like 100-150 dollars per year. A license for distilling drinking alcohol costs more, and there are volume taxes collected along the line. Distilling industrial ethanol, not for consumption doesn't have a volume taxation if I recall correctly. Ethanol is in gasoline up to about 10%, so there's a cheap way to produce it for non-consumption purposes. One of my chemistry professors said it's made a lot from natural gas. But to make fairly dry ethanol from the "heads" is to get 190 proof ethanol to start, then add enough calcium oxide to adsorb the water then distill off 199-199.5 proof ethanol to use in making biodiesel. The calcium oxide reacts with water to become calcium di hydroxide, the calcium hydroxide holds the water while the dry ethanol is distilled off. The library reference for that proceedure is given in "A Text-Book of Practical Organic Chemistry" by Arthur I. Vogel. The Texas Alcohol Beverage Commission collects the license fee for an industrial alcohol distilling license. It was something like 100-150 dollars per year.
 
Location: Texas | Registered: April 27, 2011Reply With QuoteReport This Post



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WesleyB is years ahead on me when it comes to the chemistry of it. We're both here in Texas, and I'll chime in that he's also right about the permitting stuff.

Note that either state permit requires you to have the federal permit as well -- either a DSP (distilled spirits plant, for beverage alcohol) or an AFP (alcohol fuel plant, for fuel products). The federal DSP permit is actually free, but involves a ton of paperwork and a months-long wait. I can't speak to the AFP permit, as I've never been through that process.

On the state (Texas-specific) side, a beverage alcohol production permit (here called a Distiller's and Rectifier's Permit) now costs $3,350 every two years. Technically, to manufacture/distill alcohol for fuel purposes, you would need a Local Industrial Alcohol Manufacturer's Permit, which now costs $527 every two years. The oddity is that an Industrial Permit sounds broader but does not allow manufacturing / distilling alcohol (and it's cheaper, at $381 every two years) -- this permit is geared toward people using purchased industrial alcohol as an intermediate or ingredient for food products, chemical products, and so forth. You have to read these regulations with a fine-toothed comb, and they are not always logical!

WesleyB is also correct that fuel alcohol, as long as it is produced in accordance with 27 CFR Part 19 Subpart X, is not federally taxed. Beverage alcohol is generally taxed at $13.50 per proof gallon (federally, states may vary), but the alcohol is not taxed until it is withdrawn from the bonded premises. Basically, you owe tax when it is bottled and released to a distributor for sale, in most cases. Here in Texas, there are some exemptions in the law for universities and state institutions that are making or using alcohol for research purposes, etc., so folks working in those environments are not subject to all of this and do not have to be concerned about criminal prosecution or other enforcement activity.

I don't mean to clutter the thread, as I think the OP's question has been answered -- this is just an area I am personally familiar with and find very interesting, and it can't hurt to have a few data points tossed in for posterity.

Cheers, John
 
Registered: June 17, 2007Reply With QuoteReport This Post
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Absolute ethyl alcohol may be obtained without distillation, thereby avoiding the requirement in USA law for licenses. I figured this out myself. One molecule of Calcium Oxide adsorbs one molecule of water. So figure out on paper how much water is in your head and put in enough calcium oxide to adsorb all the water. Most of the calcium (di) hydroxide product will settle out. Pour off the dried ethanol upper layer to get about 199.5 proof ethanol that you can make biodiesel from. But there's a small amount of calcium hydroxide still in solution. You want to use vegetable oil that's been stripped of free fatty acids to use ethoxide prepared in this manner or you will get some calcium soap, which is hard to remove from biodiesel. Magnesol can strip vegetable oil of most or all of the free fatty acids. Ethyl biodiesel has different properties than methyl biodiesel.
 
Location: Texas | Registered: April 27, 2011Reply With QuoteReport This Post
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Hi Wesley,

quote:
Originally posted by WesleyB:
Absolute ethyl alcohol may be obtained without distillation,thereby avoiding the requirement in USA law for licenses. ... So figure out on paper how much water is in your head and put in enough calcium oxide to adsorb all the water.
The "head" is the initial output of a still so would likely require licensing.






 
Location: ลึก ประเทศอินเดีย | Registered: March 03, 2001Reply With QuoteReport This Post
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quote:
Originally posted by WesleyB:
Absolute ethyl alcohol may be obtained without distillation, thereby avoiding the requirement in USA law for licenses.


All due respect to a fellow Texan, I don't think it's quite so clear as that -- and if you can't tell already, I enjoy getting deep into the weeds on this topic. I certainly won't speak for all fifty states, but thinking about our state and looking at the Texas Alcoholic Beverage Code, I personally wouldn't rely on your loophole. In some places in the code, there are references to distillation. Other places, the law refers only to the "manufacture" of alcohol. Your alternative method is clearly not distillation (and it's really quite creative!), but it's certainly still a process to manufacture of alcohol. The definition of "distilled spirits" explicitly lists "alcohol." (So alcohol is a distilled spirit, even if you didn't use the process of distillation to make the alcohol.)

TABC Section 6.01 says that "a person may manufacture, distill...alcoholic beverages or possess equipment or material designed for or capable of use for manufacturing alcoholic beverages, if the right or privilege of doing so is granted by this code and the person has first obtained a license or permit of the proper type as required by this code." Once again, you see both "manufacture" and "distill," and you also see separate references to "alcohol" and "alcoholic beverages." (And the definition of "alcoholic beverage" also includes "alcohol." The definitions are very broad, and especially so when you start looking at references to equipment "capable of" manufacturing alcohol. It's not hard to reach the point that merely possessing a copper condenser, without a permit, could be criminal! But I digress...)

TABC Section 11.01 puts a sharper edge on it: "No person who has not first obtained a permit...may...do any of the following: manufacture, distill, brew, sell..." So, I think, there you have it -- the law actually closes the loophole of not using a still, because you're still "manufacturing" alcohol.

(If the guys we elect to write this stuff down in Austin were any better, I might have to look for a new line of work...)

Regardless, this illustrates my earlier point that anyone considering getting into this stuff needs to look at the local laws and regulations in extreme detail -- to the point that it's probably wise to identify and hire someone to look at them with you and make sure you understanding is correct. The consequences of getting it wrong can be expensive at best or, from what I hear about jail, quite uncomfortable at worst.

quote:
Originally posted by WesleyB:
I figured this out myself. One molecule of Calcium Oxide adsorbs one molecule of water. So figure out on paper how much water is in your head and put in enough calcium oxide to adsorb all the water. Most of the calcium (di) hydroxide product will settle out. Pour off the dried ethanol upper layer to get about 199.5 proof ethanol that you can make biodiesel from.


Legal stuff aside... This seems like a viable way to reach anhydrous ethanol, particularly once you have distilled to the point of azeotrope and need to get those last few percentage points of water out of the alcohol. But if you were starting just from beer, say at perhaps 8-10% abv, my thought is that it would be cost-prohibitive and quite a mess to use enough calcium oxide to remove such a large volume of water. Maybe not at lab-scale, but I would think that at any production scale it doesn't make sense, or else people would be doing it? Is calcium oxide (lime or quicklime, right?) of an adequate grade something that is readily available in quantity? As I said above, I can't begin to compete with you on the chemistry of it -- high school was the last time I thought about moles and balancing equations and all of that. Beyond my pay grade! The legal aspects are something I actually work with on an occasional basis.

Cheers, John

This message has been edited. Last edited by: dukegrad98,
 
Registered: June 17, 2007Reply With QuoteReport This Post
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There was a forum discussion about making biodiesel with ethanol. I tried making it with liquor store bought 190 proof , 95% with water, grain alcohol. That didn't work. I haven't found my notes but, I dried 190 proof ethanol overnight with calcium oxide, at some point I added potassium hydroxide to act as catalyst. I used new corn oil at room temperature to make biodiesel with the dried ethanol (potassium ethoxide). I did not have to distil the ethanol to dry and use it to make biodiesel. The head fraction , portion is a waste product from a liquor factory if I understand. I suppose it might be considered industrial grade ethanol, and therefore not taxable like whiskey sold at a store. I didn't know about the federal license required for an ethanol still, in addition to the State license.
 
Location: Texas | Registered: April 27, 2011Reply With QuoteReport This Post
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Foreshots and heads from distillation are not ethanol, and nor are they methanol.
 
Location: New Zealand | Registered: August 15, 2006Reply With QuoteReport This Post



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The dried ethanol produced is about 99.5%, 0.5% water, but it has calcium hydroxide dissolved in it and ought not be consumed. I used liquor store bought ethyl alcohol to start that the taxes had been paid on. Manufacturing implies making it. No new ethyl alcohol was produced, a little water is removed. It is not an alcohol beverage with the calcium hydroxide dissolved in it, like denatured ethyl alcohol. The chemistry of drying the 190 proof alcohol is one atom of calcium is double bonded to one atom of oxygen. There are two atoms in the molecule calcium oxide (quick lime) . When it reacts with water with two hydrogens and one oxygen two hydroxide radicals form that are both single bonded to a central calcium atom. The result calcium di hydroxide is not greatly soluble in dried ethyl alcohol, but some does dissolve. It is not a recommended beverage. Probably eat holes in the stomach lining. I'll get another copy of the Texas Alcohol Beverage Code and look at it. Calcium hydroxide is a base like sodium hydroxide or potassium hydroxide, but not as strong a base.
 
Location: Texas | Registered: April 27, 2011Reply With QuoteReport This Post
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Hi Wesley,

quote:
Originally posted by WesleyB:
I dried 190 proof ethanol overnight with calcium oxide, at some point I added potassium hydroxide to act as catalyst.
What reaction did you catalyze when you added the potassium hydroxide?


quote:
The head fraction , portion is a waste product from a liquor factory if I understand.
Not exactly a waste product, it will usually be added back into the next distillation run, but heads will never be sold in a retail store.


quote:
I used liquor store bought ethyl alcohol...
This thread is about heads.






 
Location: ลึก ประเทศอินเดีย | Registered: March 03, 2001Reply With QuoteReport This Post
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quote:
Originally posted by WesleyB:
I used liquor store bought ethyl alcohol to start that the taxes had been paid on. Manufacturing implies making it. No new ethyl alcohol was produced, a little water is removed.


Great point and definitely applicable to your experiment -- I didn't intend to imply that you needed a permit or were doing anything wrong! I was just pondering your method on a larger scale, sort of in conjunction with the idea that it could be a loophole for making potable ethanol from much lower-alcohol starting points. I think the legal loophole is closed for reasons mentioned above. What you did certainly is not manufacturing alcohol -- you simply further purified what you already had. It wouldn't keep me up at night!

When using the calcium oxide as a water adsorbent, you talk about its solubility. Does some small portion of it actually dissolve, or is it just in such suspension that it does not readily settle out? (What I'm getting at is whether a centrifuge would be effective at removing the portion which does not settle -- that works well on suspended solids, but not dissolved materials.)

The entire TABC code is freely available online. https://www.tabc.state.tx.us/l...e/84th/AllTitles.pdf

When perusing it, note that the license fees you might run across do not tell the whole story, and you may have to look at separate TABC fee schedules. In typical government style, almost every Texas permit has a fee, and also a non-statutory surcharge that the TABC can change annually (and which in some cases is as much as or more than the fee). Here's a current table:
https://www.tabc.state.tx.us/l.../files/Fee-Chart.pdf

Thanks for your input -- I always enjoy reading about the science side of biodiesel-related stuff and the experiments you have run. I've made a lot of methyl esters over the years, but I've never even experimented with ethyl esters -- the difficulty of getting anhydrous ethanol being one of the primary barriers.

I wonder how dry the ethanol is that they blend into the E10-E15 gasoline that's at virtually every U.S. pump anymore? Put another way, I wonder how wet our gasoline is?!

Cheers, John
 
Registered: June 17, 2007Reply With QuoteReport This Post
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Hi dukegrade98:

quote:
Originally posted by dukegrad98:
I think the legal loophole is closed for reasons mentioned above. What you did certainly is not manufacturing alcohol -- you simply further purified what you already had.
A still does not manufacture alcohol, it simply purifies what you already have.
It is legal to homebrew beer in the USA but it is illegal to further purify the ethanol in the beer by running it through a still.






 
Location: ลึก ประเทศอินเดีย | Registered: March 03, 2001Reply With QuoteReport This Post
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Alcoholic Beverage Code Title 1. Chapter 1 Section 1.04 Definitions. In this code (1) "Alcoholic beverage" means alcohol or any beverage containing more than 0.5% of alcohol by volume, which is capable of use for beverage purposes, either alone or when diluted. Later the code mentions "Illicit Liquor" which the tax has not been paid on. I think drying 190 proof ethanol that the tax has been paid on , and putting calcium oxide and potassium hydroxide in it to produce potassium ethoxide (poison) makes the ethyl alcohol not a beverage, and therefore legal to use in making biodiesel. The calcium oxide reacts with water to form calcium hydroxide which is at least slightly soluble in 199 proof ethanol. So the heads has alcohols, ketones, aldehydes and water in it. Removing the water from the head might produce a material that could produce a synthetic fuel, and biodiesel. That's a research project I can't do. In other countries such research could be done possibly to advantage.
 
Location: Texas | Registered: April 27, 2011Reply With QuoteReport This Post
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quote:
Originally posted by Tilly:
A still does not manufacture alcohol, it simply purifies what you already have.


Quite right; it's not uncommon to see the scientific or technical (or even "common sense") definition of something diverge from a definition within the law. In this context, it is generally yeast "manufacturing" alcohol from sugar compounds in whatever is being fermented. I know I don't have to tell you this, but if we're stating the obvious... Smile (Personally, I still recall my grade school science lessons about van Leeuwenhoek, and am amused to think of yeast as "wee beasties" doing their work. Yes, perhaps I am easily amused.)

quote:
Originally posted by Tilly:
It is legal to homebrew beer in the USA but it is illegal to further purify the ethanol in the beer by running it through a still.


This is generally true, but it's painting with a very broad brush. Federal law permits homebrewing within certain annual volume limits. (It's proof that Jimmy Carter did manage to get something right during his term...!) However, just like distilling, each state may also regulate homebrewing -- with the result that relying on the federal volume limits might be unwise. In fact, it was only four or five years ago that the last couple of states finally permitted homebrewing. There were a couple of Deep South holdouts, maybe Mississippi and Alabama? I forget. (Texas allows a person to make up to 200 gallons per year of beer, wine, ale, or malt liquor.)

Even with that said, some states still have a local option which gives municipalities the right to prohibit homebrewing. Off-hand, I'm unsure if any cities are exercising that option. As I've made clear here, I don't claim to know the law in all fifty states -- it follows that I certainly wouldn't speak to the law in every single city in the nation.

There is a parallel here in Texas, where whether a geographic area is "wet" or "dry" for alcohol purposes remains a local option issue for voters to decide. It can vary according to city limits, county limits, precincts within a county... Further, an area that votes to go "wet" can do so just for wine and beer, or just for distilled spirits, or both -- it's not an all-or-nothing thing. The result is a confusing patchwork, and the TABC keeps an extremely detailed spreadsheet on what areas are wet (and "how wet") and dry. For instance, I live in a dry precinct of my county. However, I'm about a mile from a city that permits beer and wine sales within its city limits, and five or ten miles from two other cities city that both permit sales of beer, wine, and liquor within their city limits. Those three cities are all within the same dry county precinct, but are "sovereign islands" when it comes to the local option for alcohol regulations. In one sense it's a bit of an inconsistent mess, but on the other hand you can argue that it holds a certain logic or appeal if you believe in local control over "big government."

I would also point out that it is incorrect to say that it is illegal to "further purify" beer through distillation (or perhaps other processes, to tie back in to WesleyB's points). I don't believe I have made that argument here. It's only illegal to do so without first obtaining the proper federal and state permits and then paying applicable taxes when they become due.

I wonder -- are there other countries that allow unregulated home distilling? I realize it likely goes on everywhere as an illicit activity, but I've never researched whether there are jurisdictions that have homebrewing-style exemptions for personal consumption, etc. Seems like I once heard that New Zealand allows it.

Cheers, John
 
Registered: June 17, 2007Reply With QuoteReport This Post



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Hi dukegrad98,

quote:
Originally posted by dukegrad98:

This is generally true, but it's painting with a very broad brush.
It is specifically true.
As of 2013 it has been legal to homebrew beer in all 50 US states.
No doubt there are restrictions on this such as not being able to sell your home brew beer, transporting it from one house to another , how much you can make etc etc. I am sure there are locations within all 50 states where it is illegal to brew beer such as jails, prisons, pre-schools, mental institutions, military barracks, high schools but I do not think this is what this discussion is about.


quote:
Even with that said, some states still have a local option which gives municipalities the right to prohibit homebrewing. Off-hand, I'm unsure if any cities are exercising that option. As I've made clear here, I don't claim to know the law in all fifty states -- it follows that I certainly wouldn't speak to the law in every single city in the nation.
For a person who would not speak to the law of every single state, you seem to be doing a pretty good job of trying to make us think you know the law in every state Wink



quote:
I would also point out that it is incorrect to say that it is illegal to "further purify" beer through distillation (or perhaps other processes, to tie back in to WesleyB's points). I don't believe I have made that argument here. It's only illegal to do so without first obtaining the proper federal and state permits and then paying applicable taxes when they become due.
Again, if you go back and read the thread, you will see that this part of the discussion is concerning the legality of "further purify" the ethanol without a license.

You remind me of a discussion I was having once on another forum about the lubricity of biodiesel compared to kerosine as it pertained to injector pumps. I wrote that biodiesel had very high lubricating qualities.

Some bright spark then replied that if I thought biodiesel had such good lubricating qualities I should use it as engine oil.
You do have to keep in mind what the discussion is actually about.

It would be interesting to know whether any of the 50 US states will license home distilling for your own private consumption.






 
Location: ลึก ประเทศอินเดีย | Registered: March 03, 2001Reply With QuoteReport This Post
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quote:
Originally posted by Tilly:
It is specifically true.
As of 2013 it has been legal to homebrew beer in all 50 US states.


True, but also incomplete -- illustrative of the difference between the truth and the "whole truth," as the oath goes. I already explained the local option above, which can cover entire towns -- not just your hyperbolic list of prohibited areas. A ten-second search reveals that local option prohibition is a somewhat common scenario in our largest state.

quote:
Originally posted by Tilly:
For a person who would not speak to the law of every single state, you seem to be doing a pretty good job of trying to make us think you know the law in every state


For someone lecturing the rest of us about the point of the thread, I shouldn't need to note that my resume is fairly off-topic. It's more than sufficient to note that I'm licensed to practice here in Texas and in a number of federal courts, and have experience with the TTB (federal) and TABC (Texas) both for myself and for a number of my clients. However, I do not represent anyone contributing to this thread, and my posts in this thread should not be construed as legal advice and do not apply to all (or any) individual scenarios. That sort of disclaimer is actually fairly important in my line of work, for reasons not worth explaining. In fact, thinking about the tax aspects inherent to this discussion, I should probably consider including a full Circular 230 disclaimer. (Google it if you actually care.)

quote:
Originally posted by Tilly:
It would be interesting to know whether any of the 50 US states will license home distilling for your own private consumption.


It's a meaningless question. You can go read up on the supremacy clause and the doctrine of federal preemption if you want to understand why.

It turns out I was right in my recollection about New Zealand, though. There's actually an interesting history of how home distilling came to be legal there, and not so long ago.

quote:
Originally posted by Tilly:
You remind me of a discussion I was having once on another forum...


And you've yet again reminded all of us of the many threads on this very forum questioning why conversation here has all but died.

Cheers, John
 
Registered: June 17, 2007Reply With QuoteReport This Post
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