Sediment in finished bottles

[bluestar]

On 11/7/2018 at 5:46 AM, PeteB said:

It is not necessarily from barrel only, I get the flocc in 2 of my unaged spirits, in one it forms at 50%abv.

I would like to know more about what you are describing, because you should not get flocculation from unaged spirit. You can get louching if you have a source of fusel oils in the distillate, when you drop the proof. Flocc can occur even at higher proofs, louching will not. If you are making whiskey, you should not get louching either, unless you are going deep into the tails.

[PeteB]

7 hours ago, bluestar said:

I would like to know more about what you are describing, because you should not get flocculation from unaged spirit. You can get louching if you have a source of fusel oils in the distillate, when you drop the proof. Flocc can occur even at higher proofs, louching will not. If you are making whiskey, you should not get louching either, unless you are going deep into the tails.

I describe Flocc as clumps of cloudiness that very gradually settle to the bottom of the container. I describe Louching as looking like a small amount of milk tipped into water. It does not clump or settle out but will vanish when adding high strength alcohol.

Are we talking about the same thing?

I make an unaged rye spirit. I dilute with rain water to 40%abv then leave in a settling tank for about 6 weeks. A white substance precipitates to the bottom of the container then I filter the clear top into bottles.  For aged whiskies I do the same procedure and a very similar substance settles on the bottom of the tank, usually, but not always, when below 45%abv. I also distil a product made with ginger root. I dilute that to 50%abv and it also forms what I call Flocc. By shining a torch into the settling vat I see little "clouds " forming that very gradually sink to the bottom.

[bluestar]

14 hours ago, PeteB said:

I describe Flocc as clumps of cloudiness that very gradually settle to the bottom of the container. I describe Louching as looking like a small amount of milk tipped into water. It does not clump or settle out but will vanish when adding high strength alcohol.

Are we talking about the same thing?

I make an unaged rye spirit. I dilute with rain water to 40%abv then leave in a settling tank for about 6 weeks. A white substance precipitates to the bottom of the container then I filter the clear top into bottles.  For aged whiskies I do the same procedure and a very similar substance settles on the bottom of the tank, usually, but not always, when below 45%abv. I also distil a product made with ginger root. I dilute that to 50%abv and it also forms what I call Flocc. By shining a torch into the settling vat I see little "clouds " forming that very gradually sink to the bottom.

Thanks, I appreciate the additional information. I am very into the science of this, since I am a Ph.D. physicist that in my science career actually studied the flocculation both theoretically and experimentally (although that was for simpler polymeric materials, not whiskey per se).

Yes, phenomenologically, it is as you described, although fundamentally the mechanism matters to meet the definition of either, not just the appearance. Flocculation (also agglomeration, depending on appearance) is the coming together in solution of (usually) oligomers or polymers so that they form concentrated masses that effectively drop out of solution. In fact, they may still be solvated, but the agglomerations (flocculate) become visible: the clouds or flakes we observe. Since generally the flocc is formed from oligomers or larger molecules, a clean fresh distillate will not produce these since larger molecules don't come across in the distillate, except maybe deep into the tails. I don't see it in my white spirits, and why I expressed my surprise at your seeing it.

Can I ask another question: when you proof down, are you using distilled or RO water? White precipitate is also formed in spirits if mineral salts are in the water added for proofing, and these will precipitate organic-salt complexes in fresh distillate after some time. This is not the same as flocc, since it is creation of an insoluble organic salt by the addition of the minerals to the solution containing the trace organics. This is what @Jedd Haas was alluding to earlier in the thread.

[PeteB]

Thanks Bluestar. Sorry about slow reply I have been travelling. (visiting distilleries and marketing in Japan)

I dilute with carbon filtered rain water that has been stored in an old large concrete tank.

I have a simple pot still and do run feints quite late when compared with some. Especially for rye, peated and the ginger. 

[Foreshot]

On 11/9/2018 at 11:07 AM, bluestar said:

I am a Ph.D. physicist

yeah, that's probably why I had to google every third word in your reply. Keep that coming! We need more science to help us make better products.

 

4 hours ago, PeteB said:

I dilute with carbon filtered rain water that has been stored in an old large concrete tank.

You're probably picking up contaminants from both the water and the concrete (including salts). Carbon won't fix all of it.  

[bluestar]

7 hours ago, Foreshot said:

yeah, that's probably why I had to google every third word in your reply. Keep that coming! We need more science to help us make better products.

 

You're probably picking up contaminants from both the water and the concrete (including salts). Carbon won't fix all of it.  

Yup, that could be it, the concrete will provide calcium and some magnesium salts, and may be alkaline (check the pH). Generally, those salts will cause precipitation of organic salts or general cloudiness. If you are going to use that water, you need to do reverse osmosis.

[PeteB]

Firstly I am not concerned about the Flocc or whatever it is. Jim Murray's Whisky Bible has scored 7 of my whiskies Liquid Gold in the last 4 years including best whisky in Southern Hemisphere this year. I don't plan to change my production methods. That is not quite right because I am continually developing new products.

I was intrigued when Bluestar said the flocc was caused by barrels only, but from what he said since, I think the reason I get Flocc in white spirits is because I cut further into tails than most people.

I have not tested the pH of my rainwater, but whatever it is I doubt that I will attempt to correct it because if it "aint broke dont fix it"

Thanks for the discussion, we should never stop learning.

Pete

[et1883]

On 7/30/2018 at 3:56 PM, bluestar said:

Yes, this is flocc of oligosaccharides from barrel aging. Generally, it depends on the type of barrel and size. Large medium to heavy chars don't show much of this behavior. Small light chars, or any direct exposure to toasted oak will have a greater likelihood to form the flocc. You can remove by chill filtering, but it will change the flavor profile and mouth feel of the whiskey. We get this in a couple of our whiskies, but we consider it a feature, not a bug, since we are NCF for a reason.

How do you present that feature to the less-informed-consumers who may not know that the haze/flocc is harmless and/or composed of flavor elements?    The mainstream products are, well, what they are, but also clear (or transparent) to a fault.   part of distilling is education, do you add that to labels or advert to pre-advise consumers?  

[PeteB]

Sullivans Cove whisky from Tasmania  has won world's best single malt several times.

Look at this video to see how they are now dealing with it. 

https://sullivanscove.com/journal/flocking-and-filtration/ 

[PeteB]

If you are exporting whisky to China make sure there is no flock. A friend has a shipment held up at the moment because their rules say the product must have no solids.

( On 7/31/2018 at 8:56 AM, bluestar said:

Yes, this is flocc of oligosaccharides from barrel aging. Generally, it depends on the type of barrel and size.................)  

I occasionally get flock in some products that are not barrel aged even at 50%abv

[Glenlyon]

We do have some sediment in some of our products. We tried all kinds of ways to clear it up, but we're so small some of the tried and true filtration systems are a bit beyond our current financial capacity. We've found gravity and racking gets rid of most debris and then we tell our clients that we produced a natural product with limited filtration and they have no problem with that. In fact, sometimes, they prefer that idea.

[et1883]

1 hour ago, Glenlyon said:

We do have some sediment in some of our products. We tried all kinds of ways to clear it up, but we're so small some of the tried and true filtration systems are a bit beyond our current financial capacity. We've found gravity and racking gets rid of most debris and then we tell our clients that we produced a natural product with limited filtration and they have no problem with that. In fact, sometimes, they prefer that idea.

Glenlyon, agree that natural product focus is  on the market, and we can not forget that this is an agricultural product after all!   our slight clouds disappear with a single- or double bottle shake, and are otherwise clear, but let it sit (and who lets whisky just sit???!) and the minor cloud wisps can show up again. 

[et1883]

9 hours ago, PeteB said:

Sullivans Cove whisky from Tasmania  has won world's best single malt several times.

Look at this video to see how they are now dealing with it. 

https://sullivanscove.com/journal/flocking-and-filtration/ 

that's a great video, btw, and nice articulation of what's happening. 

[Dehner Distillery]

On 3/14/2018 at 2:11 PM, whiskeytango said:

I am getting sediment in our finished bottles.  We do a 5 micron out of the barrel and into the proofing tank then .45 into the bottles I have even tried .2 micron but they seem to clog really fast and the finished product turns out the same.  It goes in crystal clear but after a couple months on the shelf we are seeing a almost milky substance that settles in the bottom of the bottles.    

Any suggestions?  

We use ro water and 2 x 1micron filters. You might want to check the TDS of your RO water and make sure you use really good filters.

[et1883]

compare the TDS of your current water, and set aside a bottle of just the water.  if "it's the water" as Olympia beer commercial used to say about water from Tumwater, WA, you would see the same substance.  if not, then it's possibly what sullivan's cove says, above.   good luck!

 

[bluestar]

On 11/3/2019 at 2:13 PM, PeteB said:

Sullivans Cove whisky from Tasmania  has won world's best single malt several times.

Look at this video to see how they are now dealing with it. 

https://sullivanscove.com/journal/flocking-and-filtration/ 

It is a very good video, the only error is they describe the flocculant as being from fats and oils. That is not quite correct, it is longer hydrocarbons (like fats and oils), but generally it is oligosaccharides (long sugars) that may also be partially binding with some protein fragments and many a small quantity of fats or oils.

[bluestar]

On 11/3/2019 at 1:00 PM, et1883 said:

How do you present that feature to the less-informed-consumers who may not know that the haze/flocc is harmless and/or composed of flavor elements?    The mainstream products are, well, what they are, but also clear (or transparent) to a fault.   part of distilling is education, do you add that to labels or advert to pre-advise consumers?  

Education is a challenge. We have not done this yet, but others have put information on the bottle providing information, which is probably a good idea.

[PeteB]

I did hear ( not sure how reliable) that some of the bigger guys use ultrasonic to break up the flock and apparently I'd does not re-form. I have noticed that vigorous shaking makes it disappear but it eventually re-appears but not as obvious.

[Silk City Distillers]

Might be some truth to that.  I've had some bottles on display here at home that have had floc, that I'd shook to remove.  Just going through the cabinet this morning after reading that comment, I'm not seeing a ton of floc.  One of the bottles I know I shook (one of my batch 1 bottle 1) - appears a little "dusty" at the bottom, but no floc.  Makes me wonder if the structure is somewhat crystalline - and for some reason, won't re-form in the same way once disturbed.

But playing devil's advocate - being transported is going to shake bottles up pretty well - from bottling, to packaging, to palletizing, delivery, forklifts, etc.

[PeteB]

11 hours ago, Silk City Distillers said:

 Makes me wonder if the structure is somewhat crystalline -...

But playing devil's advocate - being transported is going to shake bottles up pretty well - from bottling, to packaging, to palletizing, delivery, forklifts, etc.

I have always thought flock was a crystalline structure. Can't remember if I heard it as fact. If it is crystalline then it would naturally take time to form at ambient temperature. At lower temperatures a solution holds less dissolved solids which would speed up crystal formation, hence chill filtration works.  Freshly diluted whisky has not had time to grow large crystals and much of the compounds are still in solution  while " bottling, to packaging, to palletizing, delivery, forklifts, etc" . Flock would form in the following weeks as it sits on a shelf.

[bluestar]

4 hours ago, PeteB said:

I have always thought flock was a crystalline structure. Can't remember if I heard it as fact. If it is crystalline then it would naturally take time to form at ambient temperature. At lower temperatures a solution holds less dissolved solids which would speed up crystal formation, hence chill filtration works.  Freshly diluted whisky has not had time to grow large crystals and much of the compounds are still in solution  while " bottling, to packaging, to palletizing, delivery, forklifts, etc" . Flock would form in the following weeks as it sits on a shelf.

It is NOT crystalline in any conventional sense. The oligosaccharides are long chain polymers, some branched. Flocculation is a process of condensation, like crystallization. But crystallization usually either means the molecules are coming out of solution as ordered crystallites, or possibly hydrated but still ordered crystallites, the flocculation is a formation of only partially ordered or even disordered mats, flakes, and/or globules of the polymers, often still partially hydrated. The oligosaccharides are generally fairly soluble, but if there are hydrophilic parts, those parts will bond to similar parts of other oligosaccharides by hydrogen bonding, possibly with bridging water; and for hydrophobic parts, those may cluster together expelling any hydrating water. Generally, the oligosaccharides have both hydrophilic and hydrophobic parts, and when flocculating, try to align to minimize energy with each kind of part finding its own. In addition, any residual protein fragments, fats, or oils may also find their way to bind to the appropriate parts. But since the oligosaccharides are often atactic polymers, they can not form crystals, nor condense enough to form a true solid. Hence, their cloud-like, wispy structures. Generally, the flocculants take long times to form, although more quickly at lower temperature. Heating or even aggressively shaking can often resolublize them, although the longer they are out of solution, the more difficult this appears to be.

[PeteB]

OK, lets call the flock "clusters" not "crystals".

My observation is that after a period of time these clusters can be broken up by vigorous shaking and they disappear for some time. Eventually a small amount of fine sediment settles on the bottom of the bottle.

If shaking pushed some of these compounds back into solution I would have thought the "clusters" could re-form.

I would be very interested if someone has access to an ultra sonic device to test if this type of vibration could break the clusters down so fine that they would not be visible.

[bluestar]

3 hours ago, PeteB said:

OK, lets call the flock "clusters" not "crystals".

My observation is that after a period of time these clusters can be broken up by vigorous shaking and they disappear for some time. Eventually a small amount of fine sediment settles on the bottom of the bottle.

If shaking pushed some of these compounds back into solution I would have thought the "clusters" could re-form.

I would be very interested if someone has access to an ultra sonic device to test if this type of vibration could break the clusters down so fine that they would not be visible.

The fact that this process seems to change over time is part of what I researched. It is because of various possible reasons. For example, the initial flocculant may actually not be the lowest energy state, just how the product initially came out of solution, which is a kinetic process, not necessarily equilibrium. Since shaking can put it back into solution, it may not go back in the same way as was prior to flocculation, which means if it precipitates again, it may not have the same kinetic pathway, and may form a different type of cluster. Moreover, because oligosaccharides are made up of chains of sugars, they have the similar instability in solution that sugars do, in that they can undergo isomerization reactions and hydrogen-bonding rearrangements that change their isomeric and configurational structure, and then they will flocculate back out of solution in a different form. For those that are not aware, as an example, there are multiple structures of as simple a sugar as D-glucose, and in solution, the two most stable cyclic forms will interconvert continuously, through a linear open form. At equilibrium, there will be about a 1:2 ratio of the two cyclic isomers, with only a percent of the linear intermediary at any moment. Now, imagine that kind of reactivity can also exist in polymers of saccharides, and then if they are in close proximity to each other, reactions might occur that change their structure before they are redissolved by agitation. Subsequently, since they are now different molecules, the may form a different, and likely more stable, precipitate. Finally, the polymer chain itself may break and reform. The reactions can even be enhanced by the bonding energies between the flocculated polymers, and other reactions inhibited by the steric hinderance due to the clustering. All this to say, it is not surprising that the process of redissolving and precipitating again is not fully reversible for this class of compounds.

[SlickFloss]

On 11/23/2019 at 7:07 PM, bluestar said:

It is NOT crystalline in any conventional sense. The oligosaccharides are long chain polymers, some branched. Flocculation is a process of condensation, like crystallization. But crystallization usually either means the molecules are coming out of solution as ordered crystallites, or possibly hydrated but still ordered crystallites, the flocculation is a formation of only partially ordered or even disordered mats, flakes, and/or globules of the polymers, often still partially hydrated. The oligosaccharides are generally fairly soluble, but if there are hydrophilic parts, those parts will bond to similar parts of other oligosaccharides by hydrogen bonding, possibly with bridging water; and for hydrophobic parts, those may cluster together expelling any hydrating water. Generally, the oligosaccharides have both hydrophilic and hydrophobic parts, and when flocculating, try to align to minimize energy with each kind of part finding its own. In addition, any residual protein fragments, fats, or oils may also find their way to bind to the appropriate parts. But since the oligosaccharides are often atactic polymers, they can not form crystals, nor condense enough to form a true solid. Hence, their cloud-like, wispy structures. Generally, the flocculants take long times to form, although more quickly at lower temperature. Heating or even aggressively shaking can often resolublize them, although the longer they are out of solution, the more difficult this appears to be.

Hey bluestar are the oligosaccharides from hemicellulases in the barrel? My thoughts being lower char levels don't burn these up as much 

 

thanks for sharing your knowledge

[bluestar]

On 12/13/2019 at 8:13 AM, SlickFloss said:

Hey bluestar are the oligosaccharides from hemicellulases in the barrel? My thoughts being lower char levels don't burn these up as much

thanks for sharing your knowledge

hemicellulose (hemicellulase is an enzyme). They can be. I think you are probably right about low char levels, we see it the most on exposure to char 1 or toast without char.