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Atarijedi

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Posts posted by Atarijedi

  1. If you live somewhere that gets a lot of sun, and depending on the size of your equipment, you can use Evacuated Solar Tubes (ESTs) to completely heat, or at least pre-heat water, or oil, for heating everything else. There is a distillery in Richland, Washington, called Solar Spirits, and they heat everything with solar thermal. 

    https://www.solarspirits.com/

    https://www.rackhousewhiskeyclub.com/blogs/blog/solar-spirits-a-sustainable-solar-powered-approach-to-distilling
    https://1889mag.com/think/solar-spirits-a-sustainably-focused-distillery-brings-together-tech-and-craft/
    https://wineandcraftbeveragenews.com/solar-powered-distillery-approaches-craft-from-tech-perspective/
    https://www.techbriefs.com/component/content/article/tb/stories/blog/31986

    There is also a lot of research in the industrial ethanol world, to make things more efficient, and they have come up with a lot of interesting things.

  2. Okay so, the most basic and technically correct definition of a saponification (base hydrolysis) reaction, is when you turn an ester of any kind, into a carboxylic acid salt, aka a carboxylate. So turning ethyl acetate (aka ethyl ethanoate), a simple ester, into ethanol and sodium acetate, using sodium hydroxide as the base reactant, is technically a saponification reaction. But realistically, and over time, the world sorta shrunk the definition down to only fatty acid esters being turned into a soap of some kind.

    So not all saponification reactions are the same. Wikipedia might like to tell you that they are almost irreversible, but that is quite untrue. What is true though is that it is very difficult to take a fatty acid salt (a soap), that was the result of reacting a base with a mono/di/tri-glyceride based ester in the presence of the right alcohol, and then reversing the process so you recreate that exact ester. It's even more difficult if you had multiple esters, formed multiple soaps, and then want to put everything back the way it was (just watch NileRed on youtube attempt it, doesn't go well).

    The Cousins Process does work, and I will layout why it works. I'll break down the process and what is happening. I'm going to use ethyl caprylate (ethyl octanoate) as the example fatty acid ester, calcium hydroxide is the strong base used (aka milk of lime) in the process, and sulfuric acid is the strong acid used. 

    But first, before I get into that, it seems like a huge hassle to do the process. You can literally buy all the ester precursor acids, both simple and fatty acids, for not huge amounts of money. Acetic acid, butyric acid, lactic acid, oleic acid, caproic acid, caprylic acid, linoleic acid, etc... You could add them to some rum was, or feints, that you add into the still when you do a run, or you could put small amounts of them into a chemistry reflux setup, along with some ethanol, and create the esters themselves. Then just add them after distillation, or before distillation, to taste. Or you could just buy the esters themselves. Sure none of these are as romantic a notion, but it would create a more "known" and reproducible product, especially if you are adding esters (made or purchased) to the new make.

    For the process itself, I'm not going to get into amounts, because that's more than I want to do right now to be honest, lol. I'll note that H.H. Cousins was pretty flippant with his terminology use, like ethers for esters, and lees for thumper-backset, the liquid you start with is the "waste liquor" from the thumpers, of which they would use between 1 and 3 (usually 2), I will refer to it as backset, since I don't want to conflate it with dunder(stillage) or muck. Finally, he mentions "high wines", which seem to be talking about the tails fraction. Specifically, the 2 thumpers at the end of the run would have "low wines" or low alcohol tails in first thumper, and "high wines" or high alcohol tails in the second thumper. So high alcohol tails is the "high wines", although I imagine in most of our cases, it would just be tails period, since I doubt many have 2 thumpers.

    Okay, so now onto the process. It's a pretty simple process, but I made it sound more complicated than it is by explaining the chemistry that is happening.

    1.  First thing is to create the fatty acid salts from an alkaline substance (alkalines are bases that are water soluble), and a fatty acid ester. They do this by mixing the calcium hydroxide into the thumper backset (from all thumpers), which disassociates (separates) into 1 calcium ion (Ca2+) and 2 hydroxide ions (-OH). One hydroxide ion will tear an ethyl group (CH3CH2) away from that ethyl caprylate and bond with it, creating ethanol (CH3CH2OH). So that turns the ethyl caprylate into caprylic acid. Immediately after that happens, the second hydroxide will attack the caprylic acid, tearing a hydrogen off the OH group on the end of the molecule creating a caprylate ion, leaving a free negatively charged oxygen ready for something positively charged to attach itself, and that positively charged thing is the calcium ion, at the same time as that calcium is attaching itself, the hydroxide bonds with that torn hydrogen and is turned into water. Technically speaking, since the calcium ion has a charge of 2+, and the oxygen is only 1-, than 2 caprylate ions will join with that 1 calcium. It looks like the following image (courtesy of PubChem).

    ZuohSyJ.png

    2. So now you have your fatty acid salt. These long chain fatty acid salts aren't all that water soluble, so it precipitates out of solution. You are supposed to collect them up by evaporating almost all of the liquid, and then remove it from the container and dry it out with gentle heat, or just in the air.

    3. You are then supposed to mix your high wines (high alcohol tails), the fatty acid salts from step 2, and the sulfuric acid together. So what happens here. The sulfuric acid (H2SO4) will disassociate in the rum wash, you'll have 2 free hydrogen (2H) ions and 1 free sulfate (SO4) ion floating around (for every molecule of sulfuric acid). The 2 hydrogen ions will break the bonds between the caprylate and the calcium, and replace the calcium while freeing it, turning the caprylates back into 2 individual caprylic acid molecules. That free calcium ion will then bond to the free sulfate ion from the sulfuric acid, creating calcium sulfate which isn't very soluble in water or ethanol and should mostly precipitate out. You end up with the fatty acid caprylic acid, and calcium sulfate, if everything went perfectly. That fatty acid is intended to react with ethanol when distilling to make more ethyl caprylate. The process also performs a calcium chloride titration test to determine if the right amount of sulfuric acid was used, and tells you what to do if you are over or under.

    This is what I believe is happening chemically, especially with the longer carbon chained fatty acid salts (6 carbons and up), since they aren't super soluble in water. The chemistry for the shorter ones might be a bit different, only insofar as they are more ionically bonded and less covalently bonded, so when they dissolve they naturally disassociate (e.g. calcium acetate is a short chain fatty acid salt, the calcium and acetate would separate on its own when put in water) so the acid doesn't need to tear the carboxylate away from the alkali ion. The outcome is the same though, so it doesn't really matter, but I thought I'd mention it.

    I hope people understand what I just wrote, lol. I tried to simplify it as much as I could.

    But it does work, sulfuric acid is strong enough to break that alkali-carboxylate bond in the fatty acid salt. I haven't done this specific Cousins process before, but I have done everything that happens in this process in other ways, including turning fatty acid salts back into fatty acids.

    Both homedistiller, and reddit, have accounts of people attempting this process, links at the end of my comment. Not very many people in those threads seem to know much about chemistry either, so it's kinda a crap shoot going through it. It isn't a complex process, I mean it's only 3 steps, but it's more complex than it needs to be in this day and age. To do it properly, you would need to know a bit of chemistry, so you could choose the right compounds and calculate the correct amounts of those compounds, but the math is pretty easy. 

    The point of this process seems to be to make a super high ester rum-adjunct, that is to be used as an additive to add estery flavours to your new make rum. Personally, I think just adding the organic acids themselves to the still itself either during the stripping run, during the spirit run, or in a thumper during either runs would be vastly easier. 

    If you have any questions about what I wrote, fire away!

     

    https://www.reddit.com/r/firewater/comments/kxk5ow/home_cousins_process_rum/

    https://www.reddit.com/r/firewater/comments/kytqta/cousins_process_rum_tasting/

    https://homedistiller.org/forum/viewtopic.php?f=101&t=81272&p=7649404

    https://homedistiller.org/forum/viewtopic.php?f=101&t=70947

     

     

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  3. On 3/2/2021 at 12:13 AM, Alex_Sor said:

    The middle esters are formed at elevated (more than 40 ° C) temperatures and when acidic esters are heated.

    The middle esters are insoluble in water, but readily soluble in hydrocarbons and organic solvents. Under the action of water or an alkali solution, the middle esters can hydrolyze to form first alcohol and alkyl sulfuric acid, and then alcohol and sulfuric acid

    🙂

    Esters of wines and cognacs are mainly represented by esters - products of substitution of hydrogen atoms of OH groups in mineral or carboxylic acids by hydrocarbon radicals.

    They (esters) are involved in the formation of the aroma and taste of wines and cognacs. Certain high molecular weight esters are also involved in the formation of haze in beverages. Esters of lower and middle representatives of aliphatic acids and alcohols are colorless volatile liquids, often with a pleasant odor. Esters with the smallest number of carbon atoms are poorly soluble in water, but well in organic solvents. High molecular weight ethers are insoluble in water.

    Esters can undergo saponification (hydrolysis) to form the corresponding alcohol and acid. They are capable of transesterification (alcoholysis) in an acidic environment in the presence of a large amount of alcohol. When interacting with ammonia and its derivatives (ammonolysis reaction), they form amides.

    For example, with the action of ammonia on ethyl acetate, acetamide is formed, which gives the wine a "mouse" tone. The esters that make up the essential oils of raw materials for winemaking have little effect on the aroma of the resulting wines and cognacs, with the exception of methyl and ethyl esters of anthranilic acid, which have an odor that determines the aroma of Vitis labrusca grapes, as well as wines made from it.

    Esters that affect the aroma of wines and cognacs are formed mainly as a result of alcoholic fermentation. They are mainly represented by ethyl esters of aliphatic acids with the number of carbon atoms from 1 to 12, as well as acetates of aliphatic alcohols from 1 to 12 (with an even number of carbon atoms) and cyclic (3-phenylethyl alcohol.

    The variety of esters of wines and cognacs is due to the large number of possible combinations between alcohols and acids. Their number is several dozen, and the concentration of ether is from fractions of a milligram to several milligrams per cubic decimeter (1 dm3 = 1 liter). Ethyl acetate is formed in the greatest amount. In wines there are also acid and medium esters of hydroxy acids and polybasic acids, such as , for example, lactic, succinic, malic, tartaric, etc. Their content in young wine is about 50mg/dm3, and after aging - up to 100-400mg/dm3.

    Acetates of furancarboxylic and terpenic acids have also been found. involving the use of yeast, you can achieve an increased content of some esters. egg wine materials in the presence of yeast forms 50-100mg/dm3 of ethyl esters of nylon, caprylic, capric and lauric acids, which determine the "soapy" tone characteristic of some types of cognac. The same esters, as well as ethyl linoleate, etc., are released from yeast during autolysis and are characteristic of champagne.

    Esters of higher fatty acids and alcohols with carbon atoms up to 32, as well as esters of glycerol and sterols, which are part of grape waxes, yeast lipids and oak wood, can participate in the formation of turbidity in wines and cognacs due to poor solubility in water alcoholic environment, especially when cooling. Gas-liquid chromatography and other methods are used to study the composition of ethers.

    🙂

    There is a chemistry error in your explanation. When esters undergo saponification (base hydrolysis), the products produced are an alcohol and a salt of the ester, not an alcohol and an acid like in an acid hydrolysis. Like if you mixed sodium hydroxide with oleic acid in water, you'd end up with glycerol and sodium oleate (a soap), or sodium hydroxide and ethyl acetate gives you sodium acetate (technically a soap, but not really, since it doesn't have any hydrophobicity). Just thought you should know.

    Also, I saw you talking about copper, and I figured you might like to read this study done by some fellows at the Scotch Whisky Research Institute, and published in the Journal of the Institute of Brewing. It's free to read, and pretty enlightening on why one would want to have copper in their still.

    https://onlinelibrary.wiley.com/doi/pdf/10.1002/j.2050-0416.2011.tb00450.x

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  4. On 6/18/2020 at 9:55 AM, bconley said:

    You know, the guy at Smoke Wagon made an interesting comment the other day regarding proofed whiskey...he tried a sample of something he said had just been proofed, so the "chemical reaction was still happening" and it needed to cool down. What exactly is that reaction? We have been bottling right after final proof and now I'm wondering if we are doing it all wrong....

    The main reaction is the destruction and formation of hydrogen bonds. Water molecules are hydrogen bonded to each other, when that bond breaks, energy is consumed to break the bond. Then the water and ethanol forms a hydrogen bond, and when that happens energy is released when the bond is created. There is more released energy than consumed energy, so the solution heats up.

    More specifically about the bonding, hydrogen bonding is when a hydrogen molecule that is covalently bound to an electronegative atom (e.g. hydrogen bound to oxygen as in water) is attracted to another atom that is electronegative (another oxygen, or a fluorine, or a nitrogen, and some others).

    In this specific instance, the hydrogen atoms from water, will create a bond to the oxygen atoms of the OH group on the ethanol molecule. The hydrogen from the OH group on the ethanol molecule will also make bonds with the oxygen atom of a water molecule. So you get this network of H-O bonds across the entire solution.

    You'll get the greatest amount of heat when you add equal amounts of water and ethanol, as you'll get the highest number of bond breaks and bond creations, and you'll get the greatest increase in heat if you add large volumes/masses of water to ethanol in one go.

    How, or why, this affects the qualities of the spirit, I can't say. Chemical reaction kinetics(speeds) will increase with an increase of heat energy. There will be more hydrolysis reactions with the greater presence of water. I have some ideas on how adding water might trigger saponification, but I don't think the speed at which you add it matters, I think that if saponification is going to happen, it is going to happen, regardless of the speed at which you add it.

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  5. I've been looking into making some Shochu, and I just thought I'd note for anyone else that stumbles into this thread, that there are some regionally protected terms that come along with Shochu, like with Bourbon Whiskey or Cognac Brandy.

    They are "Iki Shochu", "Kuma Shochu", "Satsuma Shochu", and "Okinawa Awamori". If you aren't making them in those regions of Japan, you can't use those terms on your bottle. That said, afaik, "Shochu" and "Awamori" themselves are okay to use. This applies to any country that falls under WTO protected geographic indication (PGI), which is most countries.

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