Pure acids and ester production

[RedwoodHillBilly]

That was my guess from the reading that I did. Adding acids to low wines should allow them to create esters with alcohols that wouldn't be present in any appreciable amount in a finished spirit.

Yes. But following this theory, adding the acids to the finished washes before stripping would be the best way. Perhaps you have to add more acids this way, but those acids are cheap.

True. This more closely replicates the process of an infected wash.

[der wo]

40ml Rum feints (mostly tails) + 20ml infected dunder,
divided on 2 jars,
one with 5 drops sulphuric acid, the other without:

The flavor is different immediately. The jar with the sulphuric acid is fruity, bright and clean, the one without of course better and more fruity than the pure dunder but less than the jar with the sulfuric acid and still a bit musty.
After 24h no further changes.

I think with sulphuric acid we have the chance either to make spirits with a much higher ester count or to get a decent amount of esters without using much acids (or heavy infections).
Those 5 drops sulphuric acid are around 4ml per liter. 5-10 times more than what is used for acidifying mashes in the spirits industry. And perhaps 1/5-1/10 of this dosage would have given the same result in my experiment. Perhaps other acids work too. Citric acid doesn't work (or much less), I tested it out a month ago and recognized no change.
I am convinced to use sulphuric acid in future exclusively for acidifying mashes. No citric acid anymore. Also for fruit mashes probably I will add it together with calcium carbonate.

[der wo]

10 days since I mixed my ester solutions. I stored them in small glass jars with plastic lined lids. Here a picture how they look now:

left acetic ester, middle lactic ester, right butyric ester

The lids looked like new before. The liquids never touched them. You see how nasty their fumes are. Be careful when you experiment with concentrated esters!

Captain RedwoodHillBilly, we are waiting for your experiments.

[LWTCS]

I bet you fellers could reach out to Brian Davis and he would give some pretty good feed back.
Maybe keep you from going down too many rabbit holes?

[RedwoodHillBilly]

I bet you fellers could reach out to Brian Davis and he would give some pretty good feed back.
Maybe keep you from going down too many rabbit holes?

I've thought about that. I live about 40 Miles from Lost Spirits. Maybe when I have time I'll reach out to him. Who knows, the worst he can do is say is no.

[der wo]

I bet you fellers could reach out to Brian Davis and he would give some pretty good feed back.
Maybe keep you from going down too many rabbit holes?

The guy who claims that he can make 20yo Rum in 6 days? Ok, he has a distillery and does experiments. But probably only legal experiments he can use commercially. I don't think what we do would be legal for him.

I am very happy with my experiments. I learned a lot.

[RedwoodHillBilly]

I bet you fellers could reach out to Brian Davis and he would give some pretty good feed back.
Maybe keep you from going down too many rabbit holes?

The guy who claims that he can make 20yo Rum in 6 days? Ok, he has a distillery and does experiments. But probably only legal experiments he can use commercially. I don't think what we do would be legal for him.

I am very happy with my experiments. I learned a lot.

I don't disagree with you. He had a problem with chlorine generating TCA from a swimming pool that leached into the ground contaminating his wooden fermenters. But, he is experimenting with esters in rum production. There may be some knowledge to be gained here.

[LWTCS]

He like so many others was a hobby distiller too.
He is a smart guy that does have an unorthodox approach,,,,like so many hobby distillers.

I have a bottle of his rum. It's very good.

Have you read his paper?

[kiwi Bruce]

Here is the only problem I have with this "Out-side of the ferment" ester making...There are noticeable differences between the same acids that are made by different organisms. Example...acetic acid made by Brettanomyces...(in beer brewing called Brett) and acetic acid made by Acetobacter aceti...(known as vinegar mother) Brett is a yeast and is used to sour Belgian Beers...Mother is a bacteria and turns ethanol into vinegar...they are both making acetic acid but Brett is bring "more to the dance" as it were.

[RedwoodHillBilly]

That is kinda the whole idea that I was thinking about. To identify the esters created by the various acids that different micro organisms produce. And to make it reproduceable. Each organism will produce more than a single byproduct, just as yeast doesn't produce just ethanol and CO2. They will also metabolize different parts of the feedstock as well. The logical endpoint of the experiments would be to identify a combination of acids that produce a combination of esters that would enhance the particular product being made.

This could be a very large rabbit hole. Large enough to produce multiple doctorate thesis. But, the journey of many miles starts with the first step. My big problem is that I haven't found a way to make my days 40 hours long.

[der wo]

He like so many others was a hobby distiller too.
He is a smart guy that does have an unorthodox approach,,,,like so many hobby distillers.

I have a bottle of his rum. It's very good.

Have you read his paper?

No. But thanks for the hint. I only clicked through the homepage of his distillery, and things like "Lost Spirits invented a new technique capable of recreating the angels share. The last missing link to recreating 30 year plus spirits in the laboratory." destroyed my interest. But now I have found many pdfs here:
https://www.stilldragon.org/discussion/ ... -thread/p9" onclick="window.open(this.href);return false;" rel="nofollow
Thanks LWTCS, I will read them the next days.

[der wo]

I read through the stilldragon-link. Great thread.
And what I found there from Bryan Davies. Mostly about his fast aging, but there is also mentioned, he buys specific bacterias and adds them to his Rum washes or dunders (together with banana pels). Nothing new generally, also the names of the bacterias are well known from Arroyo. But of course the details would be interesting. Also the thread is more about adding bacterias than adding acids like our thread. Or like adding things which contain probably the right bacterias (what I do mainly).

And I found this...
https://www.stilldragon.org/uploads/Fil ... 26a727.pdf" onclick="window.open(this.href);return false;" rel="nofollow
...a study about lowering the pH of grape wine for brandy with sulphuric acid and measuring the esters and aldehydes of the distillate:
Page 8:
In order to obtain a side varlation in pH in the base wine, six gallons were prepared for each of the following pH's: 2.5, 3.0, 3.5, 4.0, 4.5. The pH of the original wine was raised or lowered by means of calcium carbonate and sulphuric acid respectively.
Page 10-14: The results are simple. The lower the pH the more esters and aldehydes. Bingo.

[Single Malt Yinzer]

Page 10-14: The results are simple. The lower the pH the more esters and aldehydes. Bingo.

Thanks for that! Good nugget of info right there! Keep going guys!

[kiwi Bruce]

I read through the stilldragon-link. Great thread.
The pH of the original wine was raised or lowered by means of calcium carbonate and sulphuric acid respectively.[/i]
Page 10-14: The results are simple. The lower the pH the more esters and aldehydes. Bingo.

You are right this is a great thread...what caught my attention was the detail that the amount of sulfuric acid was so small that it has no affect on the copper in the still.

[der wo]

Yes. He writes, it has less effect than tartaric acid (at the amount you need for the same pH).

[Single Malt Yinzer]

So to Der Wo's use of Sulfuric acid - Fisher Esterification uses two acids and an alcohol molecule to create an ester. One of those acids acts as a catalyst. And Sulfuric acid is a great acid to use as a catalyst. Der Wo for the win!

Fisher Esterification - https://www.khanacademy.org/science/org ... rification" onclick="window.open(this.href);return false;" rel="nofollow

[der wo]

So to Der Wo's use of Sulfuric acid - Fisher Esterification uses two acids and an alcohol molecule to create an ester. One of those acids acts as a catalyst. And Sulfuric acid is a great acid to use as a catalyst. Der Wo for the win!

Fisher Esterification - https://www.khanacademy.org/science/org ... rification" onclick="window.open(this.href);return false;" rel="nofollow

I know
I wrote the same today in one of the other dunder threads.

[RedwoodHillBilly]

Der Wo, have you found an optimum molar ratio of H2SO4 to carboxylic acid ratio. I've seen 5% to 10% but I was wondering if you have any data. I suppose that it wouldn't hurt to use an excess of H2SO4 since it is a catalyst. Thoughts?

[der wo]

Sorry, I don't have experimented in this direction. It's a catalyst, so it should be not so important how much you use. It will affect the needed time, that's all. At least with butyric acid you will smell very good, how long it needs, because the difference between the smell of the acid and the flavor of the ester is huge. With lactic acid it's more an increase of the flavor. You can calculate the amounts I used (20drops = 1ml) and probably use much less, if you don't need a result in 2h.
If you want first produce esters in a jar like I did (and not add acids to a wash, what's the final experiment probably), it's important, that you use more ethanol than acid. You don't want, that there remain acids unesterificated.

[RedwoodHillBilly]

Thanks. I know that you need an excess of alcohol for the esterification. I wasn't sure of any side reactions that would deplete the H2SO4 as a catalyst. So I guess I'll just use an excess. It's pretty easy to calculate molar ratios assuming that all of the H2SO4 is consumed in the reaction (which it shouldn't be). I would add heat to drive the reaction faster in any case.

I've got 6 set of experiments to try.
1) carboxylic acid and H2SO4addition to (relatively pure) ethanol
2) carboxylic acid and H2SO4 addition to low wines
3) carboxylic acid and H2SO4 addition to wash
4) H2SO4 addition to wash to promote additional esterification
5) H2SO4 addition to low wines promote additional esterification.
6) H2SO4 addition to feints promote additional esterification.

The most common esters would be of a short chain (carboxylic) acid and ethanol, but I'm curious about esterification of short chain acids and some of the higher alcohols (fusel alcohols).

I really need to build a small lab still (2L or so) to try and isolate the end products.

edit: I also need to add a 7th experiment: H2SO4 addition to backset promote additional esterification for use in a sour mash.

[RedwoodHillBilly]

The more that I think about it, I believe that Fischer esterification is being used without knowing the chemistry behind it. Ian Smiley in his book "pure corn whiskey" recommends using H2SO4 for ph control in a mash. I believe that this would tend to promote esterification. Much more so than using backset or as is common practice in the industry using phosphoric acid to control ph.

[der wo]

Yes. All pros use sulphuric acid (or nothing). Because it's cheap. That's why their spirits taste so much better than our crap. But now everything will change...

Great experiments!
I wouldn't use heat. I would let work time instead. But it's up to you of course.

[RedwoodHillBilly]

Yes. All pros use sulphuric acid (or nothing). Because it's cheap. That's why their spirits taste so much better than our crap. But now everything will change...

Great experiments!
I wouldn't use heat. I would let work time instead. But it's up to you of course.

From reading the ADI (American Distilling Institute) forums, I see that most of the craft distillers here use either backset or phosphoric acid for ph control during the mash. I guess that the gallon of 85% phosphoric acid that I have will be relegated to rust removal or as an electrolyte for electro polishing. I think that I'm going to convert to sulfuric acid for ph control if I don't use backset. Glad to have some confirmation.

As to using heat to drive the reaction, the thought is that it was an expedient so that my experiments wouldn't take as long. But when I "deesterify" my crap likker using a base (generally Ca(OH)2) to make a neutral in my CCVM, I usually let it set for a week or so before running it.

[der wo]

From reading the ADI (American Distilling Institute) forums, I see that most of the craft distillers here use either backset or phosphoric acid for ph control during the mash.

This is different in my country. In my country we have mainly fruit brandies and "Korn" (something between white dog and vodka). The pros use sulfuric acid, the hobbyists buy expensive "Biogen M" (a liquid mixture of fruit acids and buffers).
Probably this is why the crap from ADI craft distillers doesn't taste better than our crap.

[RedwoodHillBilly]

Probably this is why the crap from ADI craft distillers doesn't taste better than our crap.

Let's put the "craft distillers" to shame. "Those damn hobbyists in their basement make better stuff than we do "

[RedwoodHillBilly]

Der Wo, I don't know if you can get it there, but have you tried the "Wild Turkey 101". It has a pretty standard rye bourbon grain bill i.e. 75% corn, 13% rye, 12% barley. This about the same grain bill that I use. It has floral/fruity notes that I can't replicate. I wonder if this is due to a lactic infection and a sulfuric acid ph control that allows for higher esterification. The floral/fruity notes are something that I would love to get in my bourbon. As a matter of fact, this is in part why I started this thread.

[kiwi Bruce]

Der Wo, I don't know if you can get it there, but have you tried the "Wild Turkey 101". It has a pretty standard rye bourbon grain bill i.e. 75% corn, 13% rye, 12% barley. This about the same grain bill that I use. It has floral/fruity notes that I can't replicate. I wonder if this is due to a lactic infection and a sulfuric acid ph control that allows for higher esterification. The floral/fruity notes are something that I would love to get in my bourbon. As a matter of fact, this is in part why I started this thread.

Red, you may be able to get a lot of the floral/fruity esters with a change to a high ester forming yeast. I'm about to try safbrew WB06 in a single malt wash. It's a Bavarian brewers yeast specifically made to produce high esters and phenols in wheat beer. It's not cheep at $9.00 a pack, but if it will produce the end result I'm looking for it will be worth every penny. The other thing I've been reading about, but have not tried yet, is to ferment at a temperature that's way higher than normal. This stresses the yeast and can make it produce esters. I haven't tried this yet because I don't know if the results would be constantly reproducible. I will post my results with the WB06...it's just a thought, it may help you too.

[RedwoodHillBilly]

Der Wo, I don't know if you can get it there, but have you tried the "Wild Turkey 101". It has a pretty standard rye bourbon grain bill i.e. 75% corn, 13% rye, 12% barley. This about the same grain bill that I use. It has floral/fruity notes that I can't replicate. I wonder if this is due to a lactic infection and a sulfuric acid ph control that allows for higher esterification. The floral/fruity notes are something that I would love to get in my bourbon. As a matter of fact, this is in part why I started this thread.

Red, you may be able to get a lot of the floral/fruity esters with a change to a high ester forming yeast. I'm about to try safbrew WB06 in a single malt wash. It's a Bavarian brewers yeast specifically made to produce high esters and phenols in wheat beer. It's not cheep at $9.00 a pack, but if it will produce the end result I'm looking for it will be worth every penny. The other thing I've been reading about, but have not tried yet, is to ferment at a temperature that's way higher than normal. This stresses the yeast and can make it produce esters. I haven't tried this yet because I don't know if the results would be constantly reproducible. I will post my results with the WB06...it's just a thought, it may help you too.

I'd be interested with your results with WB06. I do ferment at a high temp to try to get more esters from the yeast (I pitch at 100°F using Lallemand Instaferm bread yeast, 3gm/gal). The ferment will rise to ~105°F when in the active phase. I'm sure that this is not optimum, but damn it is a very vigorous ferment with about a 2hr lag. I currently ferment under airlock but I think that I'll try an open ferment to encourage an infection. BTW, my mash/ferment size is generally 55 gal total.

I'll probably go back to airlock ferment to control infections so I can play with acids. But, if I can find a sweet spot without having to resort to acids, I'd be happy. On the other hand, I'd like it to be repeatable. As with all engineering, it is a tradeoff.

[MDH]

Low aeration, low pitch rates, high temperature, select strain = more fruitiness.

Try WYEAST 1968, 1187, WLP023, Lallemand British Ale. Believe Derek Bell at some point used White Labs' strain Saccharomyces Trois.

[der wo]

Der Wo, I don't know if you can get it there, but have you tried the "Wild Turkey 101". It has a pretty standard rye bourbon grain bill i.e. 75% corn, 13% rye, 12% barley. This about the same grain bill that I use. It has floral/fruity notes that I can't replicate. I wonder if this is due to a lactic infection and a sulfuric acid ph control that allows for higher esterification. The floral/fruity notes are something that I would love to get in my bourbon. As a matter of fact, this is in part why I started this thread.

I drank Wild Turkey only once, in a bar. But in a bar I often like something and at home I don't. Or otherwise. This is really strange. For example I tried two times Highland Park 12 in a bar and I didn't like it. But now I have a bottle at home and it tastes good!
Back to the Wild Turkey: I think it was the cheaper 81 proof one. I liked it, because of the deepness, I thought perhaps deep toasted wood gave it cinnamon. And dried fruits, not floral things. And for that low price it's a good quality. Before I buy a Maker's Mark I would buy the Wild Turkey 81 next time. You see, I tasted different things than you. But I don't trust my taste in a bar...

You should make experiment No.1 with lactic acid soon. Then your view on commercial spirits will change probably. You will get a solid opinion, which spirit has lactic esters and which one not.