Using marble as a buffer

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Re: Using marble as a buffer

Postby GrassHopper » Wed Dec 28, 2016 1:10 pm

Gleaned this from an article on the net and found it interesting.

Chemical composition of marble

Marble is composed primarily of calcite, dolotimite, or perhaps serpentine and other similar minerals. The exact chemical composition of marble will greatly vary dependong on the location and the minerals or impurities present in the limestone during recrystallization. Typically, marble is composed of the following major constituents: 38-42% Lime (CaO), 20-25% Silica (SiO2), 2-4% Alumina (Al2O3), 1.5-2.5% various oxides (NaO and MgO), and 30-32% various carbonates (MgCO3 and others).

Also read that white marble has the least amount of other minerals, which seems reasonable.

So, if marble typically contains between 38-42% lime (CaO), and 30-32% various carbonates, of which some are not calcium, it would seem that the percentage of calcium carbonate available to buffer
the Ph would be less per volume vs using near pure calcium carbonate in the form of shells, crushed shells or other purer forms. Not that this is bad, just that it will take more surface area to accomplish the goal. I think it's well worth this thread by Badmotivator to find out if this is another viable source though.
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Re: Using marble as a buffer

Postby Badmotivator » Wed Dec 28, 2016 11:26 pm

GrassHopper wrote:Gleaned this from an article on the net and found it interesting.
...


Totally interesting. Thanks for bringing that.

I'm not a chemist. Do any of those possible components raise any kind of alarms for anyone?
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Re: Using marble as a buffer

Postby NZChris » Wed Dec 28, 2016 11:40 pm

Badmotivator wrote:I'm not a chemist. Do any of those possible components raise any kind of alarms for anyone?

Not for me. They are all components of marl which has been used for rum for decades.
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Re: Using marble as a buffer

Postby Badmotivator » Fri Dec 30, 2016 11:05 pm

NZChris wrote:Keep a close eye on the pH. If it goes over 7, you will probably throw it out. My understanding of muck holes is that they are dosed with marl, which would indicate that the commercial operators are testing and controlling pH. I'd love to know what they aim for, but nobody's telling.


In my dunder I am cultivating lactobacillus (optimal pH 6), proprionibacterium (optimal pH 6.5), clostridium butyricum (optimal pH 6.5) and acetobacter (optimal pH 5.4-6.3). My hope is that these critters will produce loads of carboxylic acids which will be esterified in the still. I am going to aim for pH 6-6.5. I hope the marble can make that easier. :)
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Re: Using marble as a buffer

Postby NZChris » Sat Dec 31, 2016 12:24 am

To complicate things, some of the commercials have a trash cistern, which is where they produce the acetic acid to be blended with the muck hole (which we might be calling a dunder pit) to create an essence. My trash cistern always smells beautiful and we use it in the kitchen, but my muck hole always smells so bad I have never been brave enough to use it, even blended with the trash cistern :(
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Re: Using marble as a buffer

Postby der wo » Sat Dec 31, 2016 2:59 am

Badmotivator wrote:In my dunder I am cultivating lactobacillus (optimal pH 6), proprionibacterium (optimal pH 6.5), clostridium butyricum (optimal pH 6.5) and acetobacter (optimal pH 5.4-6.3). My hope is that these critters will produce loads of carboxylic acids which will be esterified in the still. I am going to aim for pH 6-6.5. I hope the marble can make that easier. :)

I don't think marble will rise it to pH 6. You need for example calcium hydroxide for it. On the other hand I don't know, if you really need pH 6. The original dunder pits have a much lower pH I think. Ad they use only marl and lime (weak pH risers).
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Re: Using marble as a buffer

Postby workpress » Thu Feb 16, 2017 5:47 pm

Wow a topic that I know about.....

Marble and limestone are essentially the same "rock". As a printmaker we used to let new students print on marble as it is up to 5 times more resistant to nitric acid and a lot harder and 1/8 the cost as compared to Bavarrian limestone (the best stone to print on in the world)

If you want to use marble I would suggest Corinthian marble the whiter the better as any grey streaks or other colours represent impurities. A good tile store can supply this or a place that makes tomb stones and memorial markers.

In the ohio valley for instance of the United States any rock quarry will have good limestone chunks look for those without crystals in them as the crystals are an impurity.

There is also a type of limestone called Indiana limestone that is relatively hard yet almost completely composed of tiny shells it is crap to print on but may be an option for added calcium.

Hope this helps

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I hope this helps
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Re: Using marble as a buffer

Postby der wo » Fri Feb 17, 2017 1:01 am

Marl is lime and clay, says at least google translator. :D
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Re: Using marble as a buffer

Postby pounsfos » Tue May 23, 2017 10:57 pm

how did we get along with this test?

I would love to be able to just buy a big thing of marble or some type of it, dunk it in the fermenter and leave it.

Might go exploring and try this in my next ferment as mine always go down to about 3.5ph, I always have to adjust
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Re: Using marble as a buffer

Postby ShineonCrazyDiamond » Sun Jul 02, 2017 7:49 am

Hey Badmo... just wanted to stop in and thank you for the idea. I was struggling with oyster shells in a large batch, 50 gallon, ferment. Seemed like they got stuck on the bottom under the trub, and I was still having ph issues. Got me a slab of high carbonate marble, and boy did it work. I'm going to post it in my large batch thread, but wanted to share here as well because I was inspired here :thumbup: Thanks to you, another giant :clap:

So, I used this once in a 40 gallon rum ferment. As you can see, I used 25.4% the first time! I thought this stick was going to be an indefinite tool, but I may have to bring a bottle to the marble guy :shock:

The physical change is amazing, too.

1497913636462451253483.jpg


img20170702_111754.jpg


I did not take ph readings. But my rum went from 1.091 to 1.018 with no issues. And you could just see the fizzing around the slab keeping it balanced. But the best is that it went the whole length of the ferment.

Thanks Badmo. :wave:
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Re: Using marble as a buffer

Postby der wo » Sun Jul 02, 2017 8:18 am

Are you sure the 25.4% marble is solved? Perhaps most of it lays at the bottom of the fermenter?
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Re: Using marble as a buffer

Postby ShineonCrazyDiamond » Sun Jul 02, 2017 8:33 am

Well, that is a good point, der.

So fortunately I just stripped yesterday, and left everything in the bottom, with a gallon of liquid. So, on your thought I just went out there and drain the rest of the liquid off. Here is a pic of the solids.

img20170702_122417.jpg


Most of that is my yeast cake, but it is a little grittier than usual. But a very fine grit mixed with the yeast. If I we're to scrape everything out, it might be 1/2 cup with everything including the yeast? It definitly did not make up the majority of the marble.

Perhaps the more relevant number is the 2 lbs 11 ounces. The percent is just a factor of my random beginning marble size.

Even if I subtract, say, 11 ounces, there is still 2 more lbs to account for. The realistic use is somewhere between 20% and 25% for this example, for 40 gallons of rum.
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Re: Using marble as a buffer

Postby der wo » Sun Jul 02, 2017 8:58 am

Much less sediment than I thought.
Please SCD, I don't get the numbers. Could you please fill the form:

I made ___gal/l rum wash and dropped in ___lbs/kg marble. After the fermentation the marble weight ___lbs/kg. I think in the sediment is ___lbs/kg marble.
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Re: Using marble as a buffer

Postby ShineonCrazyDiamond » Sun Jul 02, 2017 9:25 am

Sure thing. For prespective, I just now scrapped what I could from the fermenter. It weighed 5.3 oz (.33 lb). This included yeast and liquid from suspension, so not complete. But there was still some smeared around the bottom after scraping, but it was negligible. I'm going with 5.3 oz, and the gage of measurements should come close to balancing themselves out.

I made 40 gallons of rum, and dropped in 10 lbs 9.3oz ( 10.58 lbs). After fermentation the marble weighs 7 lbs 14.3oz ( 7.89 lbs). I think the sediment is 5.3 oz (.33 lbs) marble.

:thumbup:
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Re: Using marble as a buffer

Postby der wo » Sun Jul 02, 2017 9:54 am

I calculated it for my small mashes (and metric measurement). Your wash consumed roughly twice the amount marble than my washes garden chalk.
Yes, that's much more. But not totally unrealistic. Perhaps it's because the garden chalk lays at the bottom all the time and forms there a layer with high pH. If this is true, an upright marble sheet would solve better than even fine powdered calcium carbonate.
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Re: Using marble as a buffer

Postby ShineonCrazyDiamond » Sun Jul 02, 2017 12:27 pm

That is exactly why I wanted to try it. When bumping up to large batches, shells would stay on the bottom. Then I would use pickling lime, and either use the clear milk of lime in ineffective doses, or dump in the lime, and let it sit on the bottom in my yeast bed. I did this once, and my mash turned green, because all the lime was eating the blue coloring of the hdpe barrel I mash in.

Only ferment I ever dumped.

This seems to work really well. I talked about it here, also

viewtopic.php?f=3&t=65703&p=7478337#p7478320
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Re: Using marble as a buffer

Postby DBCFlash » Tue Jul 04, 2017 3:48 am

I just remodeled the bathroom and I have quite a few decent sized pieces of marble tile left over. I live near the ocean so oyster shells are easy to get, free if you take a walk on the beach. I like the idea that the bar of marble doesn't just lay on the bottom like the oyster shells do. Might be time to try the tiles.
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Re: Using marble as a buffer

Postby Badmotivator » Tue Jul 04, 2017 11:37 am

SCD, I am really pleased to hear that your use of marble was helpful. Thanks very much for the report.
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Re: Using marble as a buffer

Postby NZChris » Tue Jul 04, 2017 12:49 pm

ShineonCrazyDiamond wrote:That is exactly why I wanted to try it. When bumping up to large batches, shells would stay on the bottom. Then I would use pickling lime, and either use the clear milk of lime in ineffective doses, or dump in the lime, and let it sit on the bottom in my yeast bed. I did this once, and my mash turned green, because all the lime was eating the blue coloring of the hdpe barrel I mash in.

Only ferment I ever dumped.

I've seen product (not likker) go green and stinky when the pH went over 7, so the color might not have been from the barrel.
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Re: Using marble as a buffer

Postby NZChris » Tue Jul 04, 2017 12:57 pm

When using anything that adjusts or buffers pH, I keep records of the weights and the pH. Without both numbers, I wouldn't have a clue how well it was working, or if I need to adjust how much to use next time.
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Re: Using marble as a buffer

Postby Old Town » Sun Dec 03, 2017 4:08 pm

Reading this thread and all the talk on my first rum thread has inspired an experiment. One plain,one with shells,and one with a slab of marble. Track the weight of the shells and marble and the ph of all three plus the amount of time it takes to ferment.
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Re: Using marble as a buffer

Postby Badmotivator » Sun Dec 03, 2017 5:37 pm

Old Town wrote:Reading this thread and all the talk on my first rum thread has inspired an experiment. One plain,one with shells,and one with a slab of marble. Track the weight of the shells and marble and the ph of all three plus the amount of time it takes to ferment.


I'm all ears!
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Re: Using marble as a buffer

Postby Pikey » Sun Dec 03, 2017 5:42 pm

Old Town wrote:Reading this thread and all the talk on my first rum thread has inspired an experiment. One plain,one with shells,and one with a slab of marble. Track the weight of the shells and marble and the ph of all three plus the amount of time it takes to ferment.


I'm in the "Saltbush" camp - so I'll be very interested in hearing the result too from a relative newbie without an axe to grind ! 8)
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Re: Using marble as a buffer

Postby Badmotivator » Wed Feb 07, 2018 10:22 pm

I had an un-buffered rice ferment that appeared to be stuck due to an extremely low pH of 3.66. The SG hadn't moved for days, seemed high, and a sample bucket I ran through the still showed that it only had a couple of percent ABV.

I threw in one of my marble bars (oh! the degassing/reaction was exciting!) and took measurements.
data.jpg

pH.jpg

SG.jpg


It looks like pH rose steadily and veered toward an asymptote of, what, like 4.7?

I expected to see more of a curve to the SG line, but I suppose there are a lot of moving parts in that function.

I guess I should just stick some marble in every grain ferment from now on for some insurance against a repeat of this problem. :)
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Re: Using marble as a buffer

Postby jonnys_spirit » Thu Feb 08, 2018 4:22 am

What kind of yeast did you have in there?

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Re: Using marble as a buffer

Postby LBHD » Thu Feb 08, 2018 5:45 am

Badmotivator wrote:I had an un-buffered rice ferment that appeared to be stuck due to an extremely low pH of 3.66. The SG hadn't moved for days, seemed high, and a sample bucket I ran through the still showed that it only had a couple of percent ABV.

I threw in one of my marble bars (oh! the degassing/reaction was exciting!) and took measurements.
data.jpg

pH.jpg

SG.jpg


It looks like pH rose steadily and veered toward an asymptote of, what, like 4.7?

I expected to see more of a curve to the SG line, but I suppose there are a lot of moving parts in that function.

I guess I should just stick some marble in every grain ferment from now on for some insurance against a repeat of this problem. :)



If the SG was stuck for several days, the yeast were probably out of the budding/reproducing cycle and a relatively linear consumption line makes sense to me -

cool data, thanks!
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Re: Using marble as a buffer

Postby Badmotivator » Thu Feb 08, 2018 8:08 pm

jonnys_spirit wrote:What kind of yeast did you have in there?

Cheers!
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Just your basic bread yeast.
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Re: Using marble as a buffer

Postby Badmotivator » Tue Feb 20, 2018 11:23 pm

I had an interesting result on my most recent experiment with marble: Nuthin' much, but with charts!

I was fermenting about 35 lbs of dry COB on the grain. After cooking, converting, and cooling I split the batch into four buckets. Volume was about the same in each, graininess was about the same, yeast pitch rate was about the same. I put marble chunks on the bottom of bucket 1. I put marble sticks, standing up, in bucket 2. I kept buckets 3 and 4 as controls. As the ferment went on I checked the pH and the SG (by refractometer) of each bucket every once and a while.

I expected:
1. The treated buckets would show less acidity than the control buckets, with the difference increasing over time.
2. The SG of the treated buckets would fall faster than the control buckets, especially as the control buckets grew very acidic.

I don't think the data show this, really. Here are the tables of data and the charts.

1T and 2T have marble, 3C and 4C do not.

COB ferment pH table.png

COB ferment pH chart.jpg


COB ferment SG table.png

COB ferment SG chart.png


There are only small differences in pH at any point, and those differences don't tell a very coherent story. One of the treated buckets ended up at the same pH as one of the control buckets. Hmmmm. The bucket with the vertical rods of marble diverged from the one with marble on the bottom, and its pH stayed slightly higher. That was a pretty minor effect though. The SG chart tells the story pretty clearly: for this fermentation, the marble didn't help at all.

Now probably this ferment wasn't even tempted to get dangerously acidic, so the buffering didn't really matter. I'm considering saving some of the backset from this batch and doing a sour mash experiment to complement this one. My guess is that the effect of having marble in a sour mash ferment will be more significant.
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Re: Using marble as a buffer

Postby shadylane » Wed Feb 21, 2018 12:25 am

Thanks for the experiment :thumbup:
I wonder if :lol:
A sugar wash had been used for the test instead of a mash.
Would the marble act as more of a buffer?
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Re: Using marble as a buffer

Postby Badmotivator » Wed Feb 21, 2018 12:33 am

shadylane wrote:Thanks for the experiment :thumbup:
I wonder if :lol:
A sugar wash had been used for the test instead of a mash.
Would the marble act as more of a buffer?


I’d be happy to run that experiment some time. Does a high-gravity TPW usually “boink” if it’s not buffered?
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