Copper chemical reactions?

Prairiepiss

The Scrubbers are and were on the down hill side of the take off correct?

So there really isn't any way for them to release zink and it get back into the column. But they could be tainted with zink that comes from the column.

And with the collection at the bottom plate. I know I said it would be more likely that its coming from the boiler. I still beleave that. But what if the plates above holding a higher ABV liquid keeps the zink dissolved. Where the lower ABV on the bottom plate can't? This could mean it coming from the column? But I still beleave its the boiler. I know the test shows little in the backset. Call it a gut feeling. Or crazy. Was just throwing that thought into the pot.

CothermanDistilling

I am guessing the body of the heating element now...

Philter

Was just reading John Palmer's information on metallurgy for homebrewers. It's interesting that galvanic corrosion can occur even on the same piece of metal (see highlight below). I'm thinking that if the offending metal becomes pitted and/or corroded, this would snowball

Corrosion All corrosion is basically galvanic (that is, related to electrical currents that are induced when two metals are in contact with an electrolyte). While this statement may be an overgeneralization, it helps explain how and why corrosion occurs. The electrochemical difference between two adjacent metals creates a battery. If there is an electrolyte present, such as water or beer, then an electric current will flow and the more active of the two metals will ionize. These metal ions will readily combine with oxygen to form oxides or other corrosion products. Corrosion can also occur between two adjacent areas on the same piece of metal, if the presence of dirt, a chemical or a scratch can make the two areas seem electrically different from each other.

Kudos on the time & effort you have put into tracking down your problem and sharing it with us. I've never seen those test packs before.

jbierling

@RedDoorDistillery said: And the backset is getting contaminated with Zinc after the run.

I shouldn't have mentioned the backset, because its from a different copper still with the same wash. I mentioned this, but it just confused matters.

Were the tests on the scrubbers done on New Scrubber or Used ones? If Used ones I would suggest you run the Zinc test on a New Scrubber and see if you get a positive Zinc Test. Zinc Test on New Scrubber... Bingo..

I rinsed part of one of the copper scrubbers that had been contaminated with the "metal" and tested the fluid that dripped off. I haven't tried the same thing with a brand new copper scrubber. But, the copper scrubbers were located after the dephlegmator on the downhill so they're completely separated from the plates.

You don't want to let the Column drip anything back into the still water.

Why not? What would happen if a citric wash was boiled in the still?

Test water for Zinc. If no Zinc in heated water. It must be coming from the column somewhere. But I am going to bet it is the Boiler or Elements. If it is not the Scrubbers.

Can't be the scrubbers.

@Smaug said: That's why they call it distillation.

Of course, but testing the distillate (assuming the test is even valid for alcohol) effectively rules out the stainless scrubbers (since they're in the condenser). Maybe I should have pointed that out.

@CothermanDistilling said: Like RedDoorDistillery said, then a similar test on an externally heated (gas fired) boiler would be the next logical test..

I don't have a gas boiler and not any more wash (yet).

@Prairiepiss said: The Scrubbers are and were on the down hill side of the take off correct?

So there really isn't any way for them to release zink and it get back into the column. But they could be tainted with zink that comes from the column.

All correct.

@CothermanDistilling said: I am guessing the body of the heating element now...

Body - meaning the base or the "tubes"?

As far as I can tell, the elements I'm using are stainless -- perhaps nickel and stainless. I don't think the bases are though but I can't find any documentation for any heating elements that specifies what the bases are made out of. There are plenty of elements that are listed as zinc plated copper but I'm not using any of those (easily identified as they are shiny).

Does anyone use all copper elements like this?

Given its length I would have guessed it was LWD -- not MWD. Any idea on what its watt density really is?

@Philter said: All corrosion is basically galvanic (that is, related to electrical currents that are induced when two metals are in contact with an electrolyte).

Could vapor ever be an electrolyte? The one problem with blaming the elements is that the copper scrubbers were never in liquid contact with the wash.

Kudos on the time & effort you have put into tracking down your problem and sharing it with us. I've never seen those test packs before.

I have some iron and chromate tests too, but those required more liquid than I had (only drips off the copper scrubber). I would have preferred sending this to a proper test lab, but most of them never responded to my inquiry. The one that did, gave me a quote of $500 and when I specified exactly what I had and wanted tested, never responded. So these test strips were the next best thing.

Manofconstantsorrow

Vapor can conduct current, Have you had the opportunity the check the Ohm ressistence from your ground connection at your panel ground buss bar to any part of your boiler peferible not where the element connects to your keg? If you see 1-4 you should be ok any thing higher and I would look at a better grounding solution. I would also check the ressistence of the elements themselves just as a sanity check so to be sure you haven't designed some new electro plating process.

Next check your water supply for iron sulfate ("Woodworkers use ferrous sulfate solutions to color maple wood a silvery hue") and manganese. Either one or both of these can cause the silver deposits you are seeing in steam boiler systems.

Good luck, not sure if this points you in the right direction but my guess is it's something in your water supply, check your water softener or filter system if you have one.

MOCS

Manofconstantsorrow

When I mean your water supply, it may be just the water itself, (but you mentioned it doesn't happen with other mashes) or a chemical reaction with your water and your mash ingredients. You probably mentioned but what is the PH of the water you are using?

RedDoorDistillery

@jbierling Ahh if the Copper Scrubbers are downhill no worries about them being the issue.

As far as my comment on not letting the column drip back in the boiler. This is to isolate the variable of boiler from the column to narrow down where the issue may be coming from. If you took the column off the boiler, boiled acidic wash in the boiler and tested for Zinc and was positive. You know it is happening in the boiler.

If the results of the boiler test were negative put the column back on and test again. Run the acidic steam up the column and reflux it back into the boiler. Test the backset. If the test is now positive it must be something in the steam path in the column.

Simple process of elimination is all I was suggesting. Remove as many variables as you can. Test for Negative and add back in a variable. Test again and so on till you get a positive test.

jbierling

@Manofconstantsorrow said: check the Ohm ressistence from your ground connection at your panel ground buss bar to any part of your boiler

There isn't really any feasible way to test such a connection. The panel is at least 50ft away. I do want to take more steps to triple check everything is properly grounded though.

Next check your water supply for iron sulfate ("Woodworkers use ferrous sulfate solutions to color maple wood a silvery hue") and manganese. Either one or both of these can cause the silver deposits you are seeing in steam boiler systems.

Do you have any pictures of what this looks like. The best I can do is this.

what is the PH of the water you are using

Right around 7ish.

@RedDoorDistillery said: Simple process of elimination is all I was suggesting. Remove as many variables as you can. Test for Negative and add back in a variable. Test again and so on till you get a positive test.

Understood. I'm doing my best. I want to get to the bottom of this.

I've done a couple more low wine runs over the past two days. No silver and no detectable zinc in anything I've tested.

Prairiepiss

You can check the ground wire back to the panel connection. Using a VOM set to VAC. Check voltage from the neutral to one of the hot wires. Then check the same hot wire to the ground. They should both be the same volts. Just realized you may not be here in the states. Duh. I would still test voltage from ground to the hot wires. To tell you the truth. I would be checking every thing that could be checked with a VOM.

Mountaineer

Take a pic of your heating elements and post them. I have heating elements that said that they were stainless steel. well the stainless steel coating flakes off and you are lefty with the metals from the elements. It happened to me. I couldn't figure it out. It was the heating elements.

punkin

I can't see how that could possibly go anywhere except the bottom of the boiler. I mean flakes is flakes, not liquid metal... we are talking about temperatures under 100 C here.

jbierling

@Prairiepiss said: To tell you the truth. I would be checking every thing that could be checked with a VOM.

I'm moving the system soon and will be having everything rewired. I'll ask the electrician to double check everything.

@Mountaineer said: Take a pic of your heating elements and post them.

This is what a new one looks like. I could take a picture of the used ones later today/tomorrow, but the new ones look exactly like this:

@punkin said: I can't see how that could possibly go anywhere except the bottom of the boiler. I mean flakes is flakes, not liquid metal... we are talking about temperatures under 100 C here.

These are not bits of metal. They're light enough where they get enough buoyancy (bonding with something else?) to float and stay suspended somewhat in the water. Some do sink to the bottom though.

Prairiepiss

Unless you tell that electrician what to check. I wouldn't go by what he says. No offence to any electricians here. But every one of them I know. Doesn't event carry a VOM. I had to show two of them how to use one. We are talking licensed electricians. One has been doing it for 40 years. I was dumb founded when he didn't know how to use a VOM proper. He said all they use is a thumper. To check that they have voltage. They don't even care what the voltage is. Just that it has volts. But they generally don't troubleshoot things like this. They just run wires and hook them up. If they don't get voltage. It's a circuit breaker, switch, wire, or plug.

And the base of those elements aren't stainless steel. The outside of the element itself may be SS. But the base isn't.

Manofconstantsorrow

@jbierling said: I've done a couple more low wine runs over the past two days. No silver and no detectable zinc in anything I've tested.

This would lead one to believe that it is not caused by your elements unless your wash is having some kind of reaction the the coating of your heating elements and you can also rule out the composition of the materials in your still you are not producing enough energy when stilling to melt copper, tin or lead let alone stainless steel, Punkin also alluded to this earlier.

The only way for this to be happening is through some form of electro plating which would imply you have some form of stray voltage in your still and since its happened with different elements the odds of both having the same failure to cause this are too great for my pea size brain to calculate, also you've never mentioned seeing any material degradation, which by as much as you state it has happened you would have surely seen by now.

Since you've never mentioned being shocked by your rig it is reasonable to assume you have a proper ground, but if you do not have a panel setup/controller though which you are running your elements how are you regulating power to them? It is this connection which must have some type of ground is where you need to verify the ground to the still not you main 100 or 200 amp main panel which services your house, you could but it shouldn't be necessary if you think that is in question any 3 prong outlet can provide you ground back to the main panel. "Also I hope that you would have some type of GFCI employed to prevent yourself from being electrocuted."

I believe you will find it has more to do the something in your water and mash ingredients as the catalyst of your issue and the heat is just help this reaction along. I would list your ingredients and have my water tested for trace elements some of which may be on the neutral scale as your PH reading you provided suggests. Also remember you stated it now happened in a rye wash which it had not before, so you need to see what was common, i.e. your water. Most counties and or universities offer some sort of extension programs which will test drinking water supplies for a nominal fee.

Sorry I am unable to provide you with a picture of the reaction of ferrous sulfate and manganese but I can tell you I work in commercial steam power generation plants and see the effects of this type of thing on a regular basis.

MOCS

grim

SOLUBLE COMPLEXES OF COPPER AND ZINC IN WHISKEY DISTILLERY SPENT WASH (PDF)
J. P. Quinn, T. W. Barker, R. Marchant
Journal of the Institute of Brewing
Volume 88, Issue 2, pages 95–97, March-April 1982

Just jump right down to the conclusion, some interesting comments on zinc and copper complexes. Thoughts it might be related to maillard reaction outputs. Either way, it's higher in spent mash than the source water, so it is still a possibility.

Based on the chemistry involved, it doesn't look like a simple metals test is going to work.

Manofconstantsorrow

zinc carbonate and zinc gluconate (as dietary supplements), any chance you are using some type of supplement as yeast nutrient? Ok maybe I'm reaching now?

jbierling

Well, another rye mash, another coating of silver. The funny thing is that the mash and the backset don't really show any great amount of zinc on the test strips.

@Prairiepiss said: And the base of those elements aren't stainless steel. The outside of the element itself may be SS. But the base isn't.

For sure. I wish I knew of an element that was completely stainless or copper. To my knowledge, none exists.

@Manofconstantsorrow said: reaction the the coating of your heating elements

As far as I can tell, there is no coating.

some form of electro plating

From what I understand of electro plating, the metals actually bind -- even tenuously. But the silver isn't really being attached to the copper, its more just collecting on the copper I'd say. Its easily rinsed off. Is there any electro plating that behaves like that?

also you've never mentioned seeing any material degradation

Correct, although its hard to tell with the bases. I can be somewhat confident in saying though that if the "metal" was coming from the elements (not bases) or the scrubbers, I think the missing material would be fairly obvious by now.

Its really hard to say that the silver is coming from the boiler. I can say that the silver is more prominent lower in the column, but I now wonder if there is some sort of reaction between the bubble tees and the copper. I wonder if its possible to electrically separate them somehow.

Since you've never mentioned being shocked by your rig

Never ever. It would scare me half to death of it ever had.

how are you regulating power to them

I'm not other than turning them on/off. I have barely enough power (that should be changing today) to run the still at all.

list your ingredients

I think I have before but they are: 1. Rye. 2. Enzymes (SanExtraL, Saczyme...) 3. US-05 yeast.

That's it.

water tested for trace elements

We've had the basic water test. Nothing of interest was noted.

@grim said: Just jump right down to the conclusion

I'll give it a read.

@Manofconstantsorrow said: zinc carbonate and zinc gluconate (as dietary supplements), any chance you are using some type of supplement as yeast nutrient? Ok maybe I'm reaching now?

No nutrient and there is no way at this point I'd put anything with zinc in the name anywhere near the still.

grim

Question - you mentioned a puke event one time earlier, do you use any kind of anti-foam? If not, I'm almost wondering if it's worth a shot to see if it's getting carried up on the surface of bubbles (maybe not a full-blown puke, but enough for it to settle on the plates), or if it's being carried up by straight vapor and reacting with the copper to form that kind of weird colloidal paste.

Yeast and Malt both contain zinc compounds, it doesn't necessarily need to come from anywhere else.

jbierling

@grim said: Question - you mentioned a puke event one time earlier, do you use any kind of anti-foam?

I have gotten the silver with and without anti-foam. I had the same thought that might be the cause, but I can confidently say that it is not.

The puking happened without anti-foam. This run I did use it. Both ended up with silver.

grim

I'd love to try to replicate, malted or unmalted rye? I don't have any of the Novozyme laying around right now, but it sounds like it's just a straight alpha/gamma - are you using any others? If you don't want to post your protocol, PM me and I'll try to replicate as best I can with the enzymes I've got. I don't have any US-04 laying around either, but I've got some other Fermentis dry ale yeasts I can try. I use Ale yeasts almost exclusively anyway, and never saw this.

I've run 100% malted rye mashes with enzymes before, ale yeasts, only difference is I use White Labs nutrients at standard label dosages.

jbierling

Here's the protocol:

Add 70 gallons of water at 158F. Add 6.0lb rice hulls then 150lb of malted rye. Temp drops to 146F. Add 60g enzyme. Rest 90 min. Temp drops to 130F. Sparge. Add 15 gallons of sparging water. Add enzyme at 122F->116F. Pitch US-05.

Nothing else. No other enzymes.

punkin

@jbierling said: but I now wonder if there is some sort of reaction between the bubble tees and the copper. I wonder if its possible to electrically separate them somehow.

Really? On your tees and plates only of the thousands that are in operation round the world?

And the reaction is making molten metal that does not solidify?

I don't have the answer except to say that it has to be something in your wash, not part of your still. Wish i could be more help. Were you not going to send the goop off to be analysed?

grim

Nah, nothing is melting, but there doesn't need to be melting for something like this to occur. Other than the heating element (because it is an unknown), this has nothing to do with the equipment. Stainless is generally stainless, and copper is generally copper, neither of which would be so far off as to physically corrode/react in such a manner.

I am no chemist and it's been 3 evenings since I stayed in a Holiday Inn Express, but I believe there are enough metals in yeast and malt to cause this (in various forms). Realize that there only needs to be very trace amounts of complexed metals in that paste to give it the metallic sheen. The fact that it doesn't happen with other washes proves this out, it's unique to this recipe/process.

It's reacting with the plates because copper is reactive (whether it be temporarily exposed copper, or copper oxides). It's been too long since college chemistry to speculate on what the reaction is. I will say the fact that this might be galvanic in nature is plausible, but would need to be tested.

If you want to play, clean up a copper fitting and hang it from one of the plates using a piece of fishing line, this will isolate it electrically. I suspect that it'd receive the same coating.

jbierling

@punkin said: And the reaction is making molten metal that does not solidify?

I don't think anyone said metal was melting.

Were you not going to send the goop off to be analysed?

If I could find a reasonable/workable lab, yes. I wasn't able to find one and resorted to test strips for the time being.

I think its prudent to suspect everything until it can be ruled out by the process of elimination and/or testing. The thing is, if I analyze the wash, who is going to analyze the 304 if the wash comes back clean? Chemical analysis on the scrubbers? The bases of the elements? Where does it end? When we're all broke? The same elements have been used by thousands with success. The same stainless scrubbers have been used by thousands with success. And as you've pointed out the same with the bubble caps/plates.

I think its safe to say that what I'm doing is unique in its combination of parts and materials. But what thing or combination of things is causing this? I think I'm doing everything I can to try to run down the cause. But there are limits to what I can do.

@grim said: If you want to play, clean up a copper fitting and hang it from one of the plates using a piece of fishing line, this will isolate it electrically. I suspect that it'd receive the same coating.

Thanks for the thoughtful response. I think that's an excellent idea for something concrete to try. I have extra caps I'll hang from a fishing line. It will isolate it from the stainless. But if it did get a coating I think it would just prove that direct contact between the stainless and copper is not the cause. Wouldn't the stainless and copper still be electrically connected by a potentially mildly conductive wash vapor?

So today in this life of this distiller, I moved the still to its new home at my location and the still has a brand new diet of fresh electricity so that as I liked repeating today one can "now witness the full power of the fully armed and operational Death" Distiller. Doesn't quite have the same ring.

I had a lengthy conversation with the electrician about things to test and ways to test them so hopefully I can soon rule out any chance of a stay volt or two going places they should not go. He seemed to think though that if there was some sort of electrical problem with stray voltage it would likely been immediately apparent.

punkin

I can't see electricity being conducted by vapour. Things are getting weirder.

jbierling

@punkin said: I can't see electricity being conducted by vapour. Things are getting weirder.

@Manofconstantsorrow said: Vapor can conduct current,

Don't know myself which is why I'm here.

Manofconstantsorrow

Pure Ethanol is a polar solvent that can conduct electricity, weird I know but true. However distilled water vapor and gasoline are considered an electrical insulator.

Manofconstantsorrow

@jbierling said: Wouldn't the stainless and copper still be electrically connected by a potentially mildly conductive wash vapor?

If you not tingling when you touching the still, I think it is safe to rule this out.

@jbierling said: I had a lengthy conversation with the electrician about things to test and ways to test them so hopefully I can soon rule out any chance of a stay volt or two going places they should not go. He seemed to think though that if there was some sort of electrical problem with stray voltage it would likely been immediately apparent.

If you running a GFCI this is a true statement.

BenStiller

@Manofconstantsorrow said: Pure Ethanol is a polar solvent that can conduct electricity, weird I know but true. However distilled water vapor and gasoline are considered an electrical insulator.

If I am not mistaken, pure water, just like pure ethanol or mixutres of pure ethanol and water, conduct verly little electricity. Distillation is a method to produce pure water or ethanol and the conductivity of the resulting liquid will depend on how much electrolytes are reintroduced by the distilllation process. Ethanol can conduct eletricity like water does, but electrolytes are needed.

One on my intuitions on why you observed the problem with wash and not with low-wines was that the low-wines are less conductive and prevent conduction between things that were otherwise isolated in the boiler. (not sure what that could be so I did not speculate).

As far as I know, vapors at atmospheric pressure are non-conductive.

Manofconstantsorrow

NIOSH Pocket Guide to Hazardous Chemicals

Ethanol

Flash Point:          -5°F
Ignition Temperature: 793°F
Specific Gravity:     0.79
Vapor Density:        1.49
Vapor Pressure:       44 mmHg
Boiling Point:        173°F
Flammable Range:      3.3%–19% (LEL–UEL)
Conductivity:         Yes
Smoke Character:      Slight to none
Toxicity:             Lower than gasoline
Water Solubility:     Completely
Reference:            The National Institute for Occupational Safety and Health (NIOSH)

I work in power generation so believe me when I say it can conduct electricity, even a mist which has less density then the vapor confined in a still can allow electrical current to jump.

And water needs ION's to conduct current. IMHO