Esters from Lime salts - using sulfuric acid; process

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Esters from Lime salts - using sulfuric acid; process

Post by distiller_dresden » Wed Sep 05, 2018 10:55 pm

I'm starting this thread to hopefully pull in the various persons I've seen discussing this topic in several different threads. I'm hoping to consolidate the information and see that it's 'nailed down' so that some more people can begin to properly experiment and utilize this technique. The genesis of this was when it was mentioned by der wo, and this lead me to discover this statement on the Hampden distillery website:
Hampden Distillery is the only distillery in Jamaica that specializes exclusively in the making of Heavy Pot Still rums. It prides itself in the Art of making High Ester Rums from knowledge handed down from generation to generation using fermenters made more than a century ago. Although utilizing the latest technology and equipments to ensure product quality, Hampden’s Master Distiller and Wash Masters pride themselves in predicting the outcome of each production run making the process an art as much as a science. It is this, the long history, the retention of skills, the transference of knowledge through the generations, the preserving of tradition, the use of fermenters that allows for the right yeast interaction with the carefully blended wash materials and the unique processing of it’s Lime Salts that makes Hampden paramount in the High Ester universe of rums. Hampden do not use commercial yeast but cultures, suspends and regenerate its own. It is for this reason that Hampden is privileged with having the most loyal of customers that vote their approval via their orders decade after decade. We are proud that some of our current buyers can tell stories of their grandfathers not only buying rums from the distillery many years ago but also supplying equipment for the sugar factory and spending summers at the estate.



Hampden makes a variety of rums ranging from 50 to 1600 Esters. Orders are shipped in Liters Absolute Alcohol (LAA). The higher the ester range, the more intense the bouquet of the rum. Our rums are used extensively in the blending of other rums throughout the world. Our highest ester rums are prized by the food, flavoring and perfume industries. Currently, all rums are manufactured to order, however, Hampden does set aside certain Marks for aging.
So far as I've gathered the process begins with trub (yeast cake at bottom of fermenter) and the application of sulfuric acid and drying to produce a powder that is literally lime salts. If I misunderstood that's okay, it's what this thread is hopefully going to make clear a process to begin to approach making lime salts for funky high ester rums. I have what I believe to be the best yeast for fermenting rums, based on reading and research, the EDV 493, and 55lbs of panela sugar.

I've also prepared a new 7 gallon fermenting bucket with a tap installed 1/3 the way up the bucket side. Then I cut a hole in the middle of the top 4" wide and used silicon sealant to apply a triple layer of cheesecloth over the hole. This will be my infected dunder pit, allowed to breath openly/air, and preventing any bugs from getting at it. The tap allows me to draw off dunder for use in ferments and cooks without disturbing the pellicle. It's the cleanest application I could think up and will make employing dunder much more enjoyable and mess-free.

I know der wo has also spoken of lime-buffered infected dunder, so I am guessing this may also be a source of the lime salts, perhaps the 'drudge' in the bottom of the dunder pit combined with trub and working with sulfuric this will help isolate the lime salts? Letting this thread into the open when I post in hopes our best 'rum scientists' as well as full scientists can stop by to educate on the topic!
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Re: Esters from Lime salts - using sulfuric acid; process

Post by fizzix » Thu Sep 06, 2018 12:14 am

Good idea, 'dresden.
Air this out good because the whole acid thing is both scary and intriguing.

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Re: Esters from Lime salts - using sulfuric acid; process

Post by distiller_dresden » Thu Sep 06, 2018 7:24 am

Hopefully der wo can get to post again to share his experience on the subject too... 'Cause sulfuric is intimidating, but I'm willing to use it if I know how, but without help or a chemistry degree I have no idea what to specifically do.
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Re: Esters from Lime salts - using sulfuric acid; process

Post by Fiddleford » Thu Sep 06, 2018 11:31 am

distiller_dresden wrote:Hopefully der wo can get to post again to share his experience on the subject too... 'Cause sulfuric is intimidating, but I'm willing to use it if I know how, but without help or a chemistry degree I have no idea what to specifically do.
I don't even have a high school degree yet, never took chemistry
These reactions are layed out for us to try
We just gotta inform ourselves of the safety precautions
The ingredients do controls every now and then
Do research on not only the subject but other branches of chemistry
Hell making "shine" was my first step into chemistry
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Re: Esters from Lime salts - using sulfuric acid; process

Post by distiller_dresden » Thu Sep 06, 2018 11:50 am

It is a VERY specific science for emphasizing creation of and accumulating esters in lees/trub/dunder and then further isolating specifically the lime salts and evaporating to obtain them, whilst maintaining the integrity of the salts. If this stuff was stumble-through-and-into or easy to 'figure out' from scratch then everyone would be doing it. Fact is there are a few distilleries that are very good at it, including Hampden as possibly the world's best (making DOK for food and perfume industry the world over) and then Worthy Park. They have been figuring out this science for decades, if not a hundred years.

There's a lot of room between them and us hobbyist distillers being able to post a very specific step-by-step clear checklist directions for anyone to make high ester rums the Hampden way. There are HUNDREDS of threads around here from some of our most knowledgeable members with massive debate and conversation about the production of high ester rums and the processes involved.

Not even to mention that most if not nearly all of us have NO access to the kind of testing equipment to specifically measure the content and count of esters in a spirit. Thus knowing this process and its utilization for producing lime salts then utilizing them properly once obtained is very important and has a lot of room between, "reactions laid out for us to try doing controls every now and then, " and manufacturing then utilizing lime salts to produce a rum with a 250-500gr/la ester count in a home/hobbyist setting.
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Re: Esters from Lime salts - using sulfuric acid; process

Post by Fiddleford » Thu Sep 06, 2018 12:10 pm

Haven't been able to follow der wo and the others to much in rum talk
Read alot of it just haven't been able to think about it
Been dealing with my own issues at home
Point I was making was for newer readers
Know what your dealing with when it comes to acids and such
The other one was der wo did the tests already we should replicate what we know first
You get a better understanding of what they are talking about when you do it for yourself
Never said it was something you could mossie on into
I am excited to see the results from other people
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Re: Esters from Lime salts - using sulfuric acid; process

Post by SaltyStaves » Thu Sep 06, 2018 4:11 pm

I have said it before, but its worth noting, Hampden make essences for the food industry. Therefore, we cannot assume that processes they use for that purpose, are the same for the aged rum distillate they make. It may be a very good way to make a food essence. It may not be a very good way to make a funky tropical rum. That is yet to be determined as far as I'm concerned.

The good thing about the process, is it is relatively risk free and if you end up with a substandard essence, you don't have to waste gallons of perfectly good rum by using it.
You can use low wines, feints, lees/dunder/muck, wash or any combination so long as it has carboxylic acid potential.

Lime is added to the acidic mixture, which causes the acids to form their respective salts. The liquid is then worthless and needs to be separated.
Ethanol is then added to the separated lime, then sulfuric acid. This mixture then needs to be run, either in a retort, or in the still along with fresh wash or low wines. This finished run is then your essence.

This should lay out the order in which things need to happen. I have been intentionally vague because I don't want to make a recipe for anyone to blindly follow. I am not a chemist.
Once you know what needs to occur, then you can decide what quantities are needed for each component.

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Re: Esters from Lime salts - using sulfuric acid; process

Post by Single Malt Yinzer » Thu Sep 06, 2018 5:32 pm

Using a base to cause fatty acids/esters to turn into a salt is called saponification.It's the same process to make soap. It also causes precipitates in finished spirit bottles that look like crystals. Note: I could be wrong on this as I am still kinda new to saponification. Someone with a real understanding of chemistry can correct me.

https://en.wikipedia.org/wiki/Saponification" onclick="window.open(this.href);return false;" rel="nofollow

https://homedistiller.org/wiki/index.php/Saponification" onclick="window.open(this.href);return false;" rel="nofollow

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Re: Esters from Lime salts - using sulfuric acid; process

Post by johnnyv » Thu Sep 06, 2018 8:30 pm

Single Malt Yinzer wrote:Using a base to cause fatty acids/esters to turn into a salt is called saponification.It's the same process to make soap. It also causes precipitates in finished spirit bottles that look like crystals. Note: I could be wrong on this as I am still kinda new to saponification. Someone with a real understanding of chemistry can correct me.

https://en.wikipedia.org/wiki/Saponification" onclick="window.open(this.href);return false;" rel="nofollow

https://homedistiller.org/wiki/index.php/Saponification" onclick="window.open(this.href);return false;" rel="nofollow
Yes, you are forming a salt with free carboxylic acids and calcium.
Esters tend to hydrolyse readily under basic and acidic conditions and as calcium hydroxide is a strong base this happens easily, the liberated carboxylic acids will form salts.
The salts are not volatile and stable as long as they are not brought to their decomposition temperatures.
E.g. Calcium acetate decomposes at 160 C to calcium carbonate + acetone, calcium propionate at 291 C to calcium carbonate + methyl ethyl ketone etc..

The salt is a strong base, weak acid so adding a strong acid like sulfuric will liberate the carboxylic acids to form a more stable salt CaSO4.
You can add ethanol and let the calcium sulphate precipitate settle and decant.

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Re: Esters from Lime salts - using sulfuric acid; process

Post by distiller_dresden » Fri Sep 07, 2018 10:17 am

Okay, now we're getting somewhere! I ordered some scientific/lab quality lime/hydroxide and a 950ml of 98% sulfuric acid yesterday. So I understand bringing an acidic solution up to basic to precipitate the lime salts, where hopefully I'll have esters/ester precursors concentrated in a powder form.
triesters called triglycerides, are mixtures derived from diverse fatty acids. Triglycerides can be converted to soap in either a one- or a two-step process. In the traditional one-step process, the triglyceride is treated with a strong base (e.g., lye), which cleaves the ester bond, releasing fatty acid salts (soaps) and glycerol. This process is also the main industrial method for producing glycerol. In some soap-making, the glycerol is left in the soap. If necessary, soaps may be precipitated by salting it out with sodium chloride.
So should be as easy as letting the salt form and settle, then decanting? Or will I need to boil off the liquid to obtain the lime salts? OR --
johnnyv wrote:You can add ethanol and let the calcium sulphate precipitate settle and decant.
**add ethanol to the solution and the ethanol will cause the powder to fall out of solution?

So, best way to rid of liquid?

Then I understand I'm adding the lime salts to something to be distilled - feints let's say - with a small amount of sulfuric acid, and it will be in the presence of copper as my whole setup is copper.

What do we think the best liquid to treat with lime to obtain salts is? Dunder, infected dunder, plain fermented wash, or?

Also, in der wo's thread Salty and der wo discussed the process, der wo suggested brining the acidic solution up to 7.5 might be sufficient. Is that most likely, or would the chemistry dictate bringing it up to something like 9-10?
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Re: Esters from Lime salts - using sulfuric acid; process

Post by SaltyStaves » Fri Sep 07, 2018 12:27 pm

Before doing the essence run, take a small portion of the salts, ethanol (preferably the rum you intend to use) and a few drops of H2SO4. Gently heat it (test tube in a water bath is good) and then smell the vapour.

If you don't get anything above and beyond the base rum aroma, then you haven't been successful in capturing esters. If you get off-notes that you think wouldn't work in the rum, discard it and start over. This will save you a lot of bother and work.

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Re: Esters from Lime salts - using sulfuric acid; process

Post by johnnyv » Fri Sep 07, 2018 1:44 pm

distiller_dresden wrote:Okay, now we're getting somewhere! I ordered some scientific/lab quality lime/hydroxide and a 950ml of 98% sulfuric acid yesterday. So I understand bringing an acidic solution up to basic to precipitate the lime salts, where hopefully I'll have esters/ester precursors concentrated in a powder form.
triesters called triglycerides, are mixtures derived from diverse fatty acids. Triglycerides can be converted to soap in either a one- or a two-step process. In the traditional one-step process, the triglyceride is treated with a strong base (e.g., lye), which cleaves the ester bond, releasing fatty acid salts (soaps) and glycerol. This process is also the main industrial method for producing glycerol. In some soap-making, the glycerol is left in the soap. If necessary, soaps may be precipitated by salting it out with sodium chloride.
So should be as easy as letting the salt form and settle, then decanting? Or will I need to boil off the liquid to obtain the lime salts?most calcium carboxylic salts have high water solubility so you need to boil off the water OR --
johnnyv wrote:You can add ethanol and let the calcium sulphate precipitate settle and decant.
**add ethanol to the solution and the ethanol will cause the powder to fall out of solution? The free carboxylic acids will be completely soluble in ethanol(the calcium salts of the carboxylics should be insoluble in ethanol), calcium sulphate is not soluble in ethanol and has a high specific gravity so will settle to the bottom of a container allowing easy decant.

So, best way to rid of liquid?

Then I understand I'm adding the lime salts to something to be distilled - feints let's say - with a small amount of sulfuric acid, and it will be in the presence of copper as my whole setup is copper.Copper and sulfuric acid = copper sulfate I would be careful with how much sulphuric you added

What do we think the best liquid to treat with lime to obtain salts is? Dunder, infected dunder, plain fermented wash, or? Pot still backseat from a second distillation or thumper backseat from a continuous distillation, as it won't contain molasses solids and yeast cells

Also, in der wo's thread Salty and der wo discussed the process, der wo suggested brining the acidic solution up to 7.5 might be sufficient. Is that most likely, or would the chemistry dictate bringing it up to something like 9-10? By acid solution you mean the carboxylic acids before forming the calcium salt? If so 7.5 would get the free acid but would not be good for hydrolysis of any existing esters (if any).

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Re: Esters from Lime salts - using sulfuric acid; process

Post by johnnyv » Fri Sep 07, 2018 1:57 pm

SaltyStaves wrote:Before doing the essence run, take a small portion of the salts, ethanol (preferably the rum you intend to use) and a few drops of H2SO4. Gently heat it (test tube in a water bath is good) and then smell the vapour.

If you don't get anything above and beyond the base rum aroma, then you haven't been successful in capturing esters. If you get off-notes that you think wouldn't work in the rum, discard it and start over. This will save you a lot of bother and work.
Yes, this process seems like a lot of work!
I would definitely only do this on a small scale to see if viable before trying to make a large quantity.

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Re: Esters from Lime salts - using sulfuric acid; process

Post by distiller_dresden » Fri Sep 07, 2018 2:46 pm

Okay, drilling down to it now. So my adjusted understanding is:

Using lees/contents of my thumper -- digression:
I normally place 32oz of fermented wash, or fresh unfermented wash without yeast and feints, into my thumper for a 'charge' and to flavor the distillate. For this process to obtain lime salts it would be best to start a run with an empty thumper and let it fill as it will, then this will be the best possible starting point for my acidic solution? Or would the charge, which usually doubles to 64oz, be fine to use that result if using 'fresh' wash so no yeast cells?

Continued, using lees -- take this liquid and add to it my lime until achieving a PH of 9-10 for hydrolysis of present esters into lime salts. (seems the comment RE 7.5 and acids indicated higher basic PH was necessary for getting what I'm after, the existing esters?)

Once I have that done, next step is to boil the solution until I have a powder. OR am I going to see a powder drop out of solution when I bring PH to 9-10? The middle part of response to my comments about this seemed confusing, probably my fault... Coming from the thumper this solution will definitely already have ethanol in it. Once I've added lime to a PH of 9-10, if anything does settle out is that discardable, then I boil off liquid until I have a powder?

Once I've gotten the lime salts isolated in powder form, now I can begin experimenting with them. Using a small amount to test with only a drop or very small amounts of sulfuric acid and an amount of ethanol, heat and see what I get -- nothing or something I don't enjoy or something I do enjoy, then proceed to a larger batch. Question here, Salty, when you say with off-notes discard and start over - discard the lime salts, or discard the sample and do another? Not sure if the formation here is 'random' and in the small sample I'm making a 'super' ester ethanol to blend, or if I am testing the batch of lime salts I've made and if they make off-notes I need to discard the whole batch because that's all I'll get out of that batch ester-wise...

Thanks VERY much Salty and Johnny for stopping by and assisting with this procedure. Once I have nailed down a decent understanding start to finish, and of course I have my acid and lime delivered, I will bust out my Dexter's Lab DVD's, then report back here in perpetuity with results and procedure as I perform it and subsequent performances. Hopefully others interested in this will gravitate and report as well!
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Re: Esters from Lime salts - using sulfuric acid; process

Post by NZChris » Fri Sep 07, 2018 3:16 pm

The thumper should be used to simulate the 'high wines' retort of a Jamaican style still, (they use an abv well over 40%).

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Re: Esters from Lime salts - using sulfuric acid; process

Post by SaltyStaves » Fri Sep 07, 2018 3:25 pm

distiller_dresden wrote:Question here, Salty, when you say with off-notes discard and start over - discard the lime salts, or discard the sample and do another?
Discard the lime salts. Anything 'off' about them in an aroma test, will indicate the same aroma will carry over to a bigger batch.

I made a single essence from multiple rums. It was a gamble to do it that way, because I could have ended up discarding all of it. By doing batches of salts, you get more options if one batch isn't to your liking, but the above still applies. If it smells wrong, don't include it.

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Re: Esters from Lime salts - using sulfuric acid; process

Post by distiller_dresden » Mon Sep 10, 2018 1:09 pm

Getting deeper into this, had a brainstorm that may or may not be valid, and another that is valid based on studies and papers.

First, the worker - studies have shown doing an acetic acid 'wash' of your barrels (or dominoes/staves, obviously) prior to filling will encourage the production of pineapple esters. Taking this further, it seems valid and rationally deductive, that a wash of any carboxylic acid of the wood would produce esters associated with those acids. To such an end, and involved with part/idea two...

Found on Amazon liquid heptanoic, propionic, and benzoic acids, pure. Planning to order these Friday, apply them via idea one. Now, onto idea two, intertwined with idea one. I also found pure powder salt forms of butyric acid (Calcium magnesium butyrate), caprylic acid (sodium caprylate), benzoic acid (sodium benzoate) -- as these are salts, would they work in powder form just like the lime salts? Add a small bit of powder, a drop or two sulfuric, and ethanal (small sample size), then heat and smell for results? Also, would I just add water to these to make liquids of the acids in order to use as wash for wood?
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Re: Esters from Lime salts - using sulfuric acid; process

Post by distiller_dresden » Tue Sep 11, 2018 12:05 pm

Okay chemists; I have my lab quality lime and 98% sulfuric acid.

I assume it can be safely placed/mixed in glass. My question (besides the above post questions, not related) is what kind of dropper can I use for the sulfuric? I've been reading and it will over time vulcanize and harden rubber bulbs (if I get the acid all the way to the top of a glass dropper/pipette). I've also seen silicon bulbs, and read it can damage silicon.

What's the safest dropper top for dosing my sulfuric when I begin?

Would these work?
https://www.amazon.com/Teenitor-Capacit ... Src=detail" onclick="window.open(this.href);return false;" rel="nofollow
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Re: Esters from Lime salts - using sulfuric acid; process

Post by SaltyStaves » Tue Sep 11, 2018 12:34 pm

distiller_dresden wrote: Would these work?
https://www.amazon.com/Teenitor-Capacit ... Src=detail" onclick="window.open(this.href);return false;" rel="nofollow
Those are fine.

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Re: Esters from Lime salts - using sulfuric acid; process

Post by distiller_dresden » Tue Sep 11, 2018 12:40 pm

Thanks Salty! I have a 50/100/250 beaker set in my cart as well, getting that and the .2ml pipettes Friday along with the liquid carboxylic acids --

Do you know with the powders I listed, if I add water do they become a liquid form of those acids? Seems maybe a dumb question but I don't know specifically how chemical reactions all work.

Also, would the powder forms as salts, even though they aren't lime salts, work with sulfuric and ethanol just the same as the lime salts do?

As an aside, I have 2 gallons feed molasses with propionic acid as a preservative in it, which the same brand I've read others as 'cleaning' first and also just using with no effect on the ferment finishing -- however, would this propionic acid remain through fermentation and work during distillation as an ester precursor if I add a few drops of sulfuric to the wash? Furthermore, I know that dunder would have at least the propionic carboxylic acid in it, if it remains through fermentation...

Not long now before I'll be posting trials and results!
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Re: Esters from Lime salts - using sulfuric acid; process

Post by SaltyStaves » Tue Sep 11, 2018 2:56 pm

I can't answer those questions unfortunately.
I cultured my bacteria in a molasses based medium, because that is the environment they need to be adapted to. The bacteria that aren't, will perish and not contribute to what ends up in my glass.

There is no accounting for the suitability of what you have ordered.

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Re: Esters from Lime salts - using sulfuric acid; process

Post by distiller_dresden » Tue Sep 11, 2018 6:54 pm

Yeah, see via dunder pits and bacteria we are getting bacteria to produce butyric acid, etc.

So I am seeing if it is possible to 'craft' the other side of the process, as the end result of lime salts, there are no bacteria left living in there. But ideally there are carboxylic acids, which are ester precursors when introduced to ethanol and a small amount of sulfuric acid and heat. So my reasoning is for the liquids, I have read studies of doing acetic acid wash on the insides of barrels and that causing pineapple/tropical esters to arise through aging rum distillate in the barrels. The logic stands to reason that any carboxylic acid (as acetic is) which are ester precursors would work the same as the acetic, so I'm testing on these liquid acids the same way, but with dominoes.

Then the process with lime salts, they are chemically salts and the things in them that are making esters are the trapped carboxylic acids dried and salted from whatever the bacteria produced. So I thought, why not obtain these CA's directly and then attempt the lime salt process that way with powder CA salts. If it works I can customize flavors/flavored rum. I'm hoping a chemist will stop by, but if not that's what I'll be trying, and reporting on.

Then I also have a dunder pit began as well, for the traditional means.
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Re: Esters from Lime salts - using sulfuric acid; process

Post by distiller_dresden » Sat Sep 15, 2018 12:50 pm

So begins the first experiment; I acquired some pure heptanoic acid. My current ferment is now cooking - panela, maple syrup, and date syrup, at 48 hours I introduced infected dunder, all using 493 EDV at 92F. It's gone for about 17 days, just completely finished yesterday.

Wash in the pot, fresh wash unfermented in the thump, as well as feints, and .5ml of heptanoic acid.

This chart is pertinent to these experiments:
table-of-esters-and-their-smells2.jpg
Will see how this works out, am cooking/heating up slowly to allow the formation of esters from the heptanoic as well as the waxes naturally occuring in panela sugar, not to mention whatever shall come from the infection via the added dunder, and esters created from the EDV and high ferment temp.
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Re: Esters from Lime salts - using sulfuric acid; process

Post by distiller_dresden » Tue Sep 18, 2018 9:15 pm

So the cook went great! Early heads had lots of peach and plum, like over ripened peach. Then it tapered into a light tropical fruit throughout the run, and the distillate had a distinct rummy flavor as well. This all remained after 48 hours airing. When I made cuts I did decide to include a few ounces of the heads because I couldn't not include that wonderful ripe peachy and red plum esters I had developed in the distillate. Overall it immediately had the sweet/rummy flavor that a molasses distillate develops after some time on oak, but I couldn't pick out the maple/date/panela qualities and they almost had melded into one whole flavor, and it had a perfumey quality that was pleasant like a bouquet of rum flowers. It's aging now on high vanillan french oak dominoes from Still Dragon, Japanese Maple, yellow birch, and soft maple (both the latter from Black Swan cooperage - check their sticks out I absolutely love them, whatever they do they PUNCH flavor they claim into your distillate)

I have some butyric acid and caprylic (octanoic) now, can't wait to experiment with this further and the hope is to start crafting customized, controlled, flavored rums!

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Re: Esters from Lime salts - using sulfuric acid; process

Post by distiller_dresden » Wed Sep 19, 2018 9:18 am

Well community I am SUPER FREAKING EXCITED to report on the results of some experimental trials I've run this morning!

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Firstly, for purpose of expediency these are the carboxylic acids I've been referring too so far and will be in this post that I've acquired to date. As you can see two are salt form, one is liquid. For reference if you add water to the salts, they will convert to the acid form; I've yet to research how to mix and properly create a 98% solution acid from these salts, but that's for a near-future project.

For today's experiment I had on hand the following:
Sulfuric acid 98%
Feints (heads and tails)
.2 ml disposable plastic droppers
Set of 3 500/250/100 glass flasks
Squares of tin foil
Handheld torch
Steel cooling rack
The three carboxylic acids (octanoic, butyric, heptanoic)

Procedure was as follows:
Place the cooling rack 1/4 over the sink, creating a platform to heat on. Wrap a square of foil around the base of the 100ml flask, protecting it from scorching/black. For salts, place 1/4 a capsule into the 100ml flask, for liquid, place .6ml of acid into 100ml flask. (Flask was rinsed in between and washed)

Following the introduction of the carboxylic acids, I then add .2ml of sulfuric acid into the 100ml flask. Then I add .75oz of feints, or fill the 100ml flask to about 40%. Then I place the full 100ml flask atop the cooling rack over the sink, and apply the torch until the liquid begins to steam and bubble. I let the steam subside, then I smell the flask carefully.

Results:
Heptanoic- berries, over-ripened peach, and lightly a hint of tropical fruit/exotic fruit smells, but mainly this is a 'mixed berry' punch, like mixed berry yogurt smells
Octanoic- citrus and apple juice, not orange but tang, it smells like freaking tang mixed into apple juice; I was hoping for butter notes, but at least this one worked too
Butyric- pineapple and maybe pear, it was a lot of pineapple, but maybe a bit sweet for pineapple which is where I think pear may have come in, the pineapple was overwhelming

So - SUCCESS!! The next step is making solutions for the two salts I have so that I have liquid versions of all 3 acids that are as pure as the heptanoic I have. Then I intend to run trials to figure out consistently the dosing for scaling purposes. It would be a lot easier and less frustrating to do it this way than via my thump and cooks! I will try and figure out via this flask and heat method how much acid equals how many esters/ester density. I'm not sure how I'll do this without a way to calculate/measure esters in gr/laa... But the end goal is to be able to craft custom, intentionally made and flavored rums (or ANY spirits) based on controlled introduction of specific amounts of various carboxylic acids into my thumper prior to the cook so that the esters are strong and present throughout the run, not just in the heads.

Even that Jamaican 'funk' is simply an ester coming from a carboxylic acid, so if I'm able to procure more of these acids in their pure or salt forms, eventually I'd even have no need for infected dunder unless I was making purposeful infections to obtain the top part of the chain of the ester charts via bacterial activity in my wash to prepare for the combination with my carboxylic acids. But this line of scientific distillation inquiry has me deeply excited!
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Re: Esters from Lime salts - using sulfuric acid; process

Post by Single Malt Yinzer » Wed Sep 19, 2018 11:42 am

Great find with those acids. One thing though doping with singular acids may yield a different or not as strong as a funk as you're changing the mixture of chemicals in the mix. I do think though you'll be able to dial in the flavor you want better than with dunder/muck. With dunder/muck you're at the whims of what bacteria/yeast/etc sets up camp there. With your method you can better target a flavor profile. It removes any terroir but I don't think that's a huge deal.

I think you're on to something awesome. Keep it up.

---------
Another experiment to try: Add those acids at the beginning of your ferment. Ester formation also happens during yeast growth phases. During that phase it's easier to create longer chain esters.

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Re: Esters from Lime salts - using sulfuric acid; process

Post by SaltyStaves » Wed Sep 19, 2018 12:17 pm

Esters and water are non-polar. The ester sits on top of the water. Ideally you'll need to extract it either with a pipette or a separatory funnel.

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Re: Esters from Lime salts - using sulfuric acid; process

Post by NZChris » Thu Sep 20, 2018 12:06 am

I'm not keen on the idea of putting hard won esters into the last retort/thumper/pot/whatever before the heads are gone. If you don't already have the ability to shoot the thumper, you should be thinking about it.

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Re: Esters from Lime salts - using sulfuric acid; process

Post by Simpo » Thu Apr 04, 2019 2:10 pm

Hi, as there been any progress since? Did this work progress into a different thread by any chance?

I'm so excited someone tried this and had success!

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Re: Esters from Lime salts - using sulfuric acid; process

Post by distiller_dresden » Tue Apr 23, 2019 9:51 am

Hi Simpo - I've had better results with dosing washes lately at the beginning with 750mg each of several of the acids, or picking one and going in on it, like benzoic to get those vanilla notes. I like the blend of benzoic and heptanoic, which ethyl heptanoate makes peachy and cognac aromas, real complimentary. Where these methods shine is when it hits wood, and the esters I've gained in the fresh distillate have an opportunity to form into long chain, more complex esters.

I've had a HELL of a time trying to source formic acid without paying through the nose, which makes literal just 'rum' aromas and flavor. It's most common in bees, ants, the shell of these insects is my understanding. These things are a rabbit hole because something like that being cost prohibitive, if only I had access to a bio-bank and could just get hold of a bacteria that made formic acid like clostridium butyricum (obtained from Amazon). I've also been working the other side of the formula, the dunder/bacteria, and using the typical lacto et al. spread in my dunder pit, but exploring last couple washes complimentary infections like streptococcus thermophilus and lactobacillus delbrueckii bulgaricus due to their synergy and ability to produce formic acid.

I've also gotten more into that rabbit hole, utilizing bacteria in certain yogurts, lactococcus lactis-biovar diacetylactis which under anaerobic conditions can produce enzymes to work lactic acid into diacetyl, and have in mind after some more work and my different dunders aging, to create a wash with a dosed start, not only with these bacteria but also the fatty acids, and get a full bodied heavy rum that retains a buttery note, to then age off and get mature.

In as far as anyone working just with lime and sulfuric, use 'slaked' lime or calcium hydroxide, as it's mostly readily soluble, and is also a great alkaline PH for wash chemistry. This is the same lime I use on my thumper contents to 'save' the esters/fatty acids I worked to get there for the distillation, so they can then be recycled in future washes. In as far as hard science and measuring amounts dosed or captured, I don't have the hardware and lab to do such, but am just going by nose and taste, which takes longer and is obviously less exacting.
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