Reactive Distilling Techniques

Distillation methods and improvements.

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Reactive Distilling Techniques

Post by Single Malt Yinzer » Tue Jan 15, 2019 6:12 am

DISTILLED ALCOHOLIC BEVERAGE PRODUCTION USING REACTIVE DISTILLATION TECHNIQUES By Jacob David Rochte

https://d.lib.msu.edu/etd/16407/datastream/OBJ/view" onclick="window.open(this.href);return false;" rel="nofollow
The goal of this research was to couple industrial beverage distillation with a chemical reaction to create a flavored spirit without adding anything after the final distillation. Ethanol reacted with butyric acid in the final distillation over Amberlyst® 15 to create ethyl butyrate, which gave the spirit a fruity smell comparable to Juicy Fruit® gum.
Reactive distillation combines the two unit operations of a chemical reaction and a distillation into one. This technique is useful for reactions that need a special condition that can be achieved through distillation. For example, it could be that the equilibrium of the reaction over a catalyst strongly favors the reactants, and the product is more volatile than either reactant. A column could be packed with the catalyst and ran such that the reactants vaporize up to the catalytic section, react, and the product boils off as the distillate, thus removing the product and driving the reaction in the favorable direction.
After the low wines are distilled, the ethyl butyrate needs to be created over a catalyst. Amberlyst®
15 has been chosen for this system as it is an industry standard for esterification.
Amberlyst 15: Polymer Supported sulphonic acid - https://www.hindawi.com/journals/isrn/2012/480989/fig4/" onclick="window.open(this.href);return false;" rel="nofollow
Amberlyst® 15 wet was obtained from MilliporeSigma®. This catalyst has a styrene-divinylbenzene matix with strong acidic sulfonic groups. It is a suitable replacement for the standard liquid sulfuric acid used in esterification. It can be used multiple times and cannot contaminate the distilled spirit with a strong acid.
The catalyst was supported in the pot and column in a mesh pouch. If the catalyst is used in the pot without containment, the system "pops" because there are many smooth beads on the bottom of the pot next to the heating element.
A provisional patent application has been filed for this process.

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Re: Reactive Distilling Techniques

Post by Single Malt Yinzer » Tue Jan 15, 2019 6:19 am

In short what he is doing is using Amberlyst 15 as a catalyst instead of using Sulfuric acid to encourage esterification. It's still a strong acid that is encourages esterification but it is bound to the polymer resin so it cannot come over into the distillate like sulfuric can. As such you can use as much as you want to get close to 100% esterification of available organic acids and there will be none of the acid in the finished product.

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Re: Reactive Distilling Techniques

Post by just sayin » Wed Jan 16, 2019 7:14 pm

Thanks Yinzer! You post fascinating stuff! Don't stop.

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Re: Reactive Distilling Techniques

Post by manu de hanoi » Mon Jan 28, 2019 1:38 pm

esters (heads) often having a lower boiling point than ethanol (heart), I would expect a slow refluxing on a long column to promote esterification because the esters move up the column as soon as they are formed (and so the equilibrium is moved in favor of esters )

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Re: Reactive Distilling Techniques

Post by LWTCS » Mon Jan 28, 2019 1:57 pm

manu de hanoi wrote:esters (heads) often having a lower boiling point than ethanol (heart), I would expect a slow refluxing on a long column to promote esterification because the esters move up the column as soon as they are formed (and so the equilibrium is moved in favor of esters )
100%

This is why 100% reflux for prolonged periods does not always make the cleanest " neutral". High ABV is not necessarily the same thing as "neutral".
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Re: Reactive Distilling Techniques

Post by Evil Wizard » Mon Jul 06, 2020 1:14 pm

I've been following this guys research since i first saw it in early 2019.i think its simply the most profound breakthrough in distilling in a decade or so. I can't wait to integrate it into my continuous distiller for amping up the flavour profiles of whiskies and rums. I need a shop desperately.
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Re: Reactive Distilling Techniques

Post by LWTCS » Mon Jul 06, 2020 2:46 pm

Evil Wizard wrote:
Mon Jul 06, 2020 1:14 pm
I've been following this guys research since i first saw it in early 2019.i think its simply the most profound breakthrough in distilling in a decade or so. I can't wait to integrate it into my continuous distiller for amping up the flavour profiles of whiskies and rums. I need a shop desperately.
Do you have a continuous rig already?
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Re: Reactive Distilling Techniques

Post by Yummyrum » Mon Jul 06, 2020 3:37 pm

LWTCS wrote:
Mon Jul 06, 2020 2:46 pm
Evil Wizard wrote:
Mon Jul 06, 2020 1:14 pm
I've been following this guys research since i first saw it in early 2019.i think its simply the most profound breakthrough in distilling in a decade or so. I can't wait to integrate it into my continuous distiller for amping up the flavour profiles of whiskies and rums. I need a shop desperately.
Do you have a continuous rig already?
Evil Wizards still is in this topic
viewtopic.php?f=1&t=5432&p=7568240#p7568240

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Re: Reactive Distilling Techniques

Post by Evil Wizard » Wed Sep 23, 2020 3:45 pm

Yes that's the one, I haven;t given it its own thread yet, though I have rebuilt the bottoms heats exchanger and added some thermometers. It runs great. I'm starting work on the rectifying section for continuous heads removal.
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Re: Reactive Distilling Techniques

Post by Corsaire » Tue Oct 13, 2020 1:23 am

Based on my limited research (I'm not a smart man) I get that the resin it's bound to is polystyrene? That's not something I'd readily put in my still. The stuff sounds awesome, but I'd want to know if it's safe.

Also, this spec sheet from a Polish manufacturer specifically says: This product is not food, feed or pharmaceutical grade. Therefore, this product can neither be used asingredient/additive in the manufacturing of food, feed or pharmaceutical products. The use of the product is in theresponsibility of the purchaser.
http://files.brenntag.pl/00155D4267041E ... BB132E00C4

Are there different sources? My 2 minute search led me to a Belgian site that didn't list prices, a Finnish one that seems promising but expensive, and well, Alibaba, which I wouldn't trust.

Does anyone have more info on the safety of this? I get that as a catalyst, nothing should be leached out. I'll reread the paper tonight, but did they do tests on the final product for anything other than the esters and alcohols in chapter 6.4.4?

Edit:
Link to the Safety Data Sheet found on the Finnish site. Seems good to me, but I'd appreciate if people who know this kind of stuff could check it out:
https://www.fishersci.fi/store/msds?par ... anguage=en

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Re: Reactive Distilling Techniques

Post by Evil Wizard » Thu Jan 21, 2021 7:18 pm

I have integrated into my continuous still a port for putting mesh cartridges of Amberlyst in the vapor path.

I've also obtained lab samples of the ten major carboxylic acids and the ten higher alcohols. This will let me dope the vapour path on the fly for custom esterification.

I haven't bought the (Canadian version of) Amberlyst but have a reputable source. Turns out the manufacturer recommended me the first guy I had already asked; he looks after our water softening and RO systems.
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Re: Reactive Distilling Techniques

Post by manu de hanoi » Thu Jan 21, 2021 11:42 pm

Evil Wizard wrote:
Thu Jan 21, 2021 7:18 pm
I have integrated into my continuous still a port for putting mesh cartridges of Amberlyst in the vapor path.

I've also obtained lab samples of the ten major carboxylic acids and the ten higher alcohols. This will let me dope the vapour path on the fly for custom esterification.

I haven't bought the (Canadian version of) Amberlyst but have a reputable source. Turns out the manufacturer recommended me the first guy I had already asked; he looks after our water softening and RO systems.
This is a bad idea, these things arent designed or rated for food production. You'll get a great continuous estherification by simply adding a generous height of column above the heart's takeoff. Just bleed the heads slowly, they will bake in the heads column section for the entire run.
At least that's my experience, for rhum I was looking for that "juicy fruit" chewing gum taste, and got it this way.

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Re: Reactive Distilling Techniques

Post by LWTCS » Fri Jan 22, 2021 7:13 am

manu de hanoi wrote:
Thu Jan 21, 2021 11:42 pm
Evil Wizard wrote:
Thu Jan 21, 2021 7:18 pm
I have integrated into my continuous still a port for putting mesh cartridges of Amberlyst in the vapor path.

I've also obtained lab samples of the ten major carboxylic acids and the ten higher alcohols. This will let me dope the vapour path on the fly for custom esterification.

I haven't bought the (Canadian version of) Amberlyst but have a reputable source. Turns out the manufacturer recommended me the first guy I had already asked; he looks after our water softening and RO systems.
This is a bad idea, these things arent designed or rated for food production. You'll get a great continuous estherification by simply adding a generous height of column above the heart's takeoff. Just bleed the heads slowly, they will bake in the heads column section for the entire run.
At least that's my experience, for rhum I was looking for that "juicy fruit" chewing gum taste, and got it this way.
That's very interesting. Any feedback on that with the whiskey production?
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Re: Reactive Distilling Techniques

Post by Evil Wizard » Fri Jan 22, 2021 10:19 am

I've been looking around to see how flavour companies generate these esters for food use if not through resin. Nothing yet.

I wonder about instead adding a pool of H2SO4 in the reflux area instead of resin. The boiling temp is above 300c.

I'm coming at the continuous operation in a non traditional way and avoiding super tall columns. I'm after a full flavour strip, followed by a traditional finish run though I will play around with a second column. My concern about adding height relates to creating back pressure in the beer column and driving more alcohol out of the tails. (With my PID controlling flow input from bottoms temp, this would slow down my input rate)

Currently getting 40% abv distillate and 0.5%abv bottoms, 96LpH wash input of 10%abv. I'm building a purifier (can also thump) to try and trap fusels, it might bump the abv a bit.
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Re: Reactive Distilling Techniques

Post by Single Malt Yinzer » Wed Jan 27, 2021 4:37 pm

Evil Wizard wrote:
Fri Jan 22, 2021 10:19 am
I wonder about instead adding a pool of H2SO4 in the reflux area instead of resin. The boiling temp is above 300c.
Would it not get flooded out by the spirit? It's SG is 1.84 so it might stick around a bit but eventually get push down to the boiler? If it's highly miscible then it will definitely get pushed down.

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Re: Reactive Distilling Techniques

Post by manu de hanoi » Thu Jan 28, 2021 12:25 am

Evil Wizard wrote:
Fri Jan 22, 2021 10:19 am
I've been looking around to see how flavour companies generate these esters for food use if not through resin. Nothing yet.

I wonder about instead adding a pool of H2SO4 in the reflux area instead of resin. The boiling temp is above 300c.

I'm coming at the continuous operation in a non traditional way and avoiding super tall columns. I'm after a full flavour strip, followed by a traditional finish run though I will play around with a second column. My concern about adding height relates to creating back pressure in the beer column and driving more alcohol out of the tails. (With my PID controlling flow input from bottoms temp, this would slow down my input rate)

Currently getting 40% abv distillate and 0.5%abv bottoms, 96LpH wash input of 10%abv. I'm building a purifier (can also thump) to try and trap fusels, it might bump the abv a bit.
nothing wrong with playing around (with acid catalysis of esterification), but if you want to avoid too high a column you can simply bleed heads as you would normally do, then after the run, re run them in a small batch column still under full reflux for a few hours to promote esterification. Beware of chemicals, if it's not food grade, the producer wont mind using poisonnous things. I tell you that, because more a decade ago, I fancied adding sodium hydroxyde (lab grade) to pinaple juice, and ended up with a diarhea I remember to this day.

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Re: Reactive Distilling Techniques

Post by Evil Wizard » Thu Jan 28, 2021 5:20 am

Hi guys, thanks for the replies. Yinzer I was thinking of putting a dish in the top of the column and dripping H2SO4 into it on a timer maybe. The still's design has the incoming wash injected as vapour in an upwards direction 6 inches below the lyne arm, and there is a plate about 8 inches below the injection point. There is no boiler but a steam injection point beneath which there is a U shaped water trap.

Manu there is no dephlagmator and the upwards pressure is limited to the pressure created by the height of the water in the water trap so I don't have a "normal" bleeding of heads. This is the beer column you understand, not sure if I'll build a second (rectifyer?) column yet.

I'm really trying to trap all possible congeners in the strip distillate so I'm hoping to grab any higher alcohols that would normally drop out of with the bottoms water. I had thought to try and esterify them up top with whatever carboxylic acids are around. Do you have any notes on trapping them in alternate ways? Perhaps some internal cup with a side draw above the steam injection point? My column is packed in that region.
The huge continuous Armagnac still at work has a fusels draw at the bottom 3 plates of the first (offset) column.

Manu, just wanted to say hey, seen you around forever. I think I read about you consulting on a distillery in Northern Europe years back, or was it Japan? Oh and got any spp for sale still?

I'm guessing that all the Sodium Citrate produced from Lye and Pineapple gave you a severe diuretic effect causing the diarrhea, yes? Gross. Did you decant it off the precipitate before drinking?
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Re: Reactive Distilling Techniques

Post by manu de hanoi » Thu Jan 28, 2021 7:51 am

Evil Wizard wrote:
Thu Jan 28, 2021 5:20 am


Manu there is no dephlagmator and the upwards pressure is limited to the pressure created by the height of the water in the water trap so I don't have a "normal" bleeding of heads. This is the beer column you understand, not sure if I'll build a second (rectifyer?) column yet.

I'm really trying to trap all possible congeners in the strip distillate so I'm hoping to grab any higher alcohols that would normally drop out of with the bottoms water. I had thought to try and esterify them up top with whatever carboxylic acids are around. Do you have any notes on trapping them in alternate ways? Perhaps some internal cup with a side draw above the steam injection point? My column is packed in that region.
The huge continuous Armagnac still at work has a fusels draw at the bottom 3 plates of the first (offset) column.
I suggest you post a drawing of your still, I dont get it
Manu, just wanted to say hey, seen you around forever. I think I read about you consulting on a distillery in Northern Europe years back, or was it Japan? Oh and got any spp for sale still?
I dont remember the consulting, and still sell spp
I'm guessing that all the Sodium Citrate produced from Lye and Pineapple gave you a severe diuretic effect causing the diarrhea, yes? Gross. Did you decant it off the precipitate before drinking?
I didnt decant

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Re: Reactive Distilling Techniques

Post by Evil Wizard » Thu Jan 28, 2021 8:18 am

My drawing skills are limited but I'll give it a go.

Can I ask how much for 8L of packing? All I've seen for sale are the spiral spring packing, which are not prismatic though they use the term.
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Re: Reactive Distilling Techniques

Post by Stibnut » Tue Feb 23, 2021 12:34 am

I've got a contribution the opposite direction: removing unwanted compounds in a neutral.

One thing I've been doing lately is adding sodium borohydride (NaBH4) along with sodium/potassium carbonate to the low wines for my neutrals to eliminate aldehydes and ketones. Acetaldehyde, acetone, isobutyraldehyde, isovaleraldehyde, and furfural are all rapidly reduced to alcohols by borohydride. Meanwhile the carbonate takes care of the esters and fatty acids; you can use NaOH or KOH more efficiently, but I like the improved safety in using a chemically weak but still moderately strong base. The base helps to stabilize the borohydride, which reacts rapidly with water and more slowly with alcohols if it's in a neutral or (especially) acidic environment. It still reacts in alkaline solution but more slowly, fizzing gently with hydrogen and lasting long enough to fully reduce aldehydes and ketones. The amount I use is no more than 0.25 g/L of low wines, which should be easily enough to reduce everything it can easily deal with.

The source I've used is an Estonian supplier who sells in small quantities mostly to chemistry hobbyists. I first ran across him on eBay when I was teaching myself chemistry in a kind of hardcore way, doing Grignard reactions and the like in my apartment. The prices are pretty good for hard-to-find reagents but he can take a while to ship. Link here.

I've had pretty good results so far. There's still one major headsy compound I can't get rid of this way - acetal aka 1,1-diethoxyethane - and the foreshots/early heads still have a sort of stinging odor associated with it. Fusel alcohols are also unaffected, so proper tails cuts depend on your ability to sense fusels as opposed to the "wet dog" odors which come mostly from short/medium-chain fatty acids.

If anyone tries this, please know that it gives off hydrogen as it reacts with water and alcohols, so don't close your low wines container airtight and take extra care not to have any open flames or sparks near it. Add it only to low wines; a wash is far too acidic and it will decompose rapidly, releasing a whole bunch of foam filled with hydrogen and destroying the borohydride before it can react with all the aldehydes. It is also moderately alkaline and could cause eye damage; for similar reasons it would not be a good idea to add to a final spirit. Otherwise, it is pretty safe; the products of its reactions are harmless borates including borax.

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Re: Reactive Distilling Techniques

Post by Evil Wizard » Tue Feb 23, 2021 2:31 pm

Thanks Stibnut, that's really neat. Anything to avoid larger columns at this point, my basement is already full.

How long do you wait after adding the sodium carbonate? What ph do you try and take it to?
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Re: Reactive Distilling Techniques

Post by Stibnut » Tue Feb 23, 2021 10:42 pm

A pH of at least 11 is sufficient to stabilize it so that it would be active for several hours, easily long enough to reduce any aldehydes or ketones. It'll fizz with hydrogen during that time as it slowly decomposes.

What I did last time is that I made a solution of about 80 mL of 40% potassium carbonate, added about 2 g of borohydride to that solution, dissolved it, and then used this solution to treat 10 L of low wines. It seemed to work fine to add both the carbonate and the borohydride at the same time that way. I let it all react overnight and did the spirit run the next day. I used potassium carbonate because it's more soluble, but realistically I don't think I'd have had a problem using 20% sodium carbonate. As long as the pH is high enough that esters get saponified, the borohydride will last long enough to do its job.

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Re: Reactive Distilling Techniques

Post by Evil Wizard » Wed Feb 24, 2021 2:14 am

Sweet. You mean 0.2g not 2g right?
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Re: Reactive Distilling Techniques

Post by Stibnut » Wed Feb 24, 2021 9:47 am

0.2 g/L or 2 g for the whole 10 L of low wines.

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