Eggshell Calcium Carbonate Leavening Part 1

3:13 AM in 1, Aqua, calcium, carbonate, eggshell, leavening, part

A few weeks ago, we were reading a 5 Acres and a Dream blog post about making homemade leavening from wood ashes (i.e., from potassium carbonate, K₂CO₃), and a reader in the comments section asked if calcium carbonate (CaCO₃) from eggshells, which also reacts with acid to release CO₂ gas (reaction below), could be used as a leavening agent.  We had been wondering the same thing for quite a while, and the realization that other folks were wondering the same thing provided the motivation we needed to finally get up and do some experiments.

Calcium carbonate (CaCO₃) reacts with acetic acid in vinegar to make calcium acetate, carbon dioxide gas (CO₂), and water (H₂O).

First, some eggshell chemistry.  Eggshells are about 95% CaCO₃, but the CaCO₃ is bound in a matrix of protein, with a proteinaceous membrane also attached. Thus, one might expect that eggshells would make a better leavening agent if the CaCO₃ could be isolated from the protein (and/or ground very finely) so that it would be more accessible to the acid during baking.  The question is, how to get rid of the protein?  Well have to either dissolve the protein away from the CaCO₃ or dissolve the CaCO₃ away from the protein and then regenerate it somehow.  Today well try the former.

Theres quite a bit of precedent for dissolving away the eggshell protein (or at least, most of it) with a strong base, such as sodium hydroxide (NaOH) or potassium hydroxide (KOH), but specific recipes are hard to come by.  Several articles refer to this original gem, the most useful being this one, which allows us to deduce that those guys boiled their eggshells in a 2.5 wt% NaOH solution for 5 minutes, which easily removed the membrane and part of the protein matrix.  They then increased the lye concentration to 10 wt% and boiled for a long time, finding that all the protein that could be removed was gone by about 7 hours.  They didnt give a lye-to-eggshell ratio, though.  Additionally, this patent references another patent (we couldnt track down the original) claiming that boiling eggshells in 3 wt% NaOH would reduce the protein content of the shells to < 0.1%, although the boiling time and lye-to-eggshell ratio wasnt specified.

A protein content of < 0.1 wt% sounds good enough to us, so we decided to follow that route most closely.  Having to guess on the time and lye-to-eggshell ratio, we decided that if we had to boil for more than half an hour and use more than a 1:1 ratio, that it wouldnt be worth our trouble. (In that case, wed just use Leighs ash-based leavening instead!)  Alright, experiment planned; lets do this!

Heres our recipe: 15 g NaOH, dissolved in 500 g tap water, with 15 g coarse-ground eggshells (1-2 mm particles) added.   Boiled for 30 min.  Wear safety glasses and gloves until everything is neutralized later on (see below).

As the mixture simmered, the lye water turned a cloudy yellow.  A good sign that were dissolving protein.

After boiling, we poured the liquid through a coffee filter (supported by a polypropylene funnel) into a quart jar.  The eggshells dont look that much different than before, except maybe slightly darker.  The pigment (they were brown shells) is still there.  The coffee filter is really slow, so something like an old t-shirt or terrycloth towel might be better.

The filtrate is still highly caustic, so be careful with it!  We wanted to neutralize it before doing anything else, so we added a couple tablespoons of our good ol red cabbage pH indicator, causing the filtrate to go from yellow to slightly-darker-yellow.  Note if youre following along at home--dumping the filtrate down the drain without neutralizing might kill some of your friendly septic system bugs, so please neutralize!

Then we added vinegar until it turned green, then blue, then finally purple, indicating a neutral pH.  (We had to add a few more tablespoons of pH indicator as it got more and more dilute, because the color changes started to get hard to see.) Now it can go down the drain or into the compost.

The next step is to repeatedly rinse the boiled eggshells to wash all the lye off.  These are the rinses (plus pH indicator), showing steadily decreasing alkalinity.  After the fourth rinse (which was with vinegar), the filtrate is neutral, the eggshells should be substantially free of lye (and hopefully protein!), and were good to move on (and take off our safety glasses and gloves).  We also neutralized the second and third filtrates with vinegar, too.  Safety note: working with lye on something youre planning to eat has the potential to cause some serious damage if you dont neutralize properly.  Be careful and only do this if youre comfortable with the chemistry! Also, make sure youre using pure lye, and not some cleaner that has lye combined with other chemicals.

Drying the lye-boiled eggshells makes them easier to work with. In the oven at 300 °F for 15-20 min ought to do the trick!

Time to make some experimental biscuits!  Five sets of three biscuits each.  Recipe per set: 0.5 cups all purpose flour, 0.25 teaspoon leavening, 0.125 (1/8) teaspoon salt, 1 tablespoon butter (in the bowls), 1 teaspoon apple cider vinegar plus milk (2%) to bring the volume up to 0.25 cups to make a faux buttermilk (in the glasses).  We processed the bowl contents in a food processor for about 5 seconds to cut in the butter, then added the "buttermilk" and processed for another 5 seconds to mix everything up, scooped the dough/batter into drop biscuits and baked at 400 °F for about 20 min.  The five sets differ only in their leavening: no leavening, lye-boiled coarse-ground eggshells, coarse-ground eggshells, fine-ground eggshells, and baking soda.

After baking, there a clear difference between the No Leavening control and the rest, but also between the baking soda and the rest.  Between the eggshell sets, the lye-boiled and the finely-ground are about equal, and slightly more risen than the coarse-ground.  However, all the eggshell sets are very close to each other, and closer to the control than to the baking soda.  Also, we didnt have enough room for all fifteen biscuits on this sheet, so we baked the third biscuit of the last three sets separately.  Their appearance was consistent with the biscuits here.  Hooray for reproducibility!

The textures are consistent with the appearance, but its hard to tell from the photos.  Also, the biscuits other than the baking soda set werent cooked all the way through after 20 min.  We put them back in the oven; after another 15 minutes they were no longer doughy, but they didnt rise any more.  The flavor of all the sets is decent, so the control set and the eggshell sets would make decent dumplings if youre into that sort of thing.  Overall, the conclusion from these experiments is that the eggshells provide some leavening effect, but not much.  For us, the ground eggshells dont really get the job done, and its definitely not worth the effort of boiling them in lye water to dissolve off the protein.

But were not done with these experiments yet!  Stay tuned for Part 2, where we dissolve and regenerate the calcium carbonate part, and see how that works as leavening!

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Aquaponics and iron magnesium calcium

2:40 PM in and, Aqua, aquaponics, calcium, iron, magnesium

One of the shortcomings for all aquaponics systems has been the ability to provide the systems with the right combination of trace elements to grow blooming plants. This is not to say that the nutrients in fish waste aren’t ample to grow tomatoes, cucumbers, peppers, squash, beans, zucchini, etc. because we have been able to grow them. However . . . fish waste alone doesn’t produce ENOUGH iron, magnesium, calcium and potassium to continually grow large amounts of these blooming plants. This is one of the key reasons that aquaponics has been slow to commercialize. It’s a fact that greens (lettuce, basil, kale, etc.) can be grown in almost any aquaponics system very successfully in almost any climate. But the trick is to consistently grow blooming plants that produce multiple crops of (example) tomatoes, peppers, cucumbers, squash, zucchini, and beans on fish waste alone because the required blossoming-supportive nutrients are quickly stripped out of the water and blooming plants cannot continually blossom and grow plants that produce fruit/vegetables without adding chemicals because of nutrient deficiencies; fish waste alone does NOT produce ENOUGH iron, magnesium, calcium and potassium to continually grow blooming plants that produce food in aquaponics. 

Aquaponics iron,  aquaponics magnesium, aquaponics calcium

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Aquaponics, ækw??p?n?ks, pisciponics http://aquaponics-commercial-backyard.blogspot.com.es/

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Eggshell Calcium Carbonate Leavening Part 2

8:23 AM in 2, Aqua, calcium, carbonate, eggshell, leavening, part

If youve been following this blog lately, you know that were engaged in a multi-week battle of wits with a pile of eggshells.  Specifically, were trying to figure out a way to isolate calcium carbonate from eggshells to use as a leavening agent.  The calcium carbonate is bound up in a matrix of protein that makes it less accessible for leavening action, so for maximum leavening effect, we have to either dissolve away the protein or dissolve away the calcium carbonate and then regenerate it.  Last week, we tried boiling ground-up eggshells in lye to dissolve away the protein.  (It didnt work very well, but at least the biscuits were tasty.) Today, we take a look at the other option--dissolving the calcium carbonate and regenerating it.

The first thought we had was that the CaCO₃ in the eggshells can be dissolved by the acetic acid in vinegar to make calcium acetate (Ca(Ac)₂), which can be decomposed to CaCO₃ around 400 °C.

Unfortunately, some of the eggshell proteins are also apparently soluble in vinegar, and when we made calcium acetate by dissolving eggshells in vinegar and evaporating all the liquid, we ended up with a light-brown colored solid, which yielded a gray powder after a clean cycle in the oven (which gets close to 500 °C).  We got a similar looking powder when we put ground whole eggshells through the oven clean cycle.

The product from calcining eggshells in the rocket silo was actually a little darker colored.  As a point of reference, were looking for CaCO₃ as a fine, white powder.

This is actually a problem thats bothered us since we wrote about grinding up eggshells way back when this blog was just an infant.  While its usually possible to burn organic matter (e.g., proteins) off of inorganic residue (e.g., wood ash, glass, stainless steel) at 400-500 °C (750-930 °F), eggshells hold on to the organic matter from their protein until 900 °C (1650 °F).  Unfortunately, at that temperature, our desired CaCO₃ has transformed into lime (calcium oxide, CaO).  Thus, its no surprise that when we put a pile of eggshells in our oven and set it to the clean cycle, our pile came back grayish-colored instead of the white color of pure CaCO₃. (Although, we were surprised at the time since we hadnt done much reading on the topic!)

So, were 0-for-2 on getting our pure CaCO₃ out of the eggshells at this point, but its worth noting two things.  First, while we havent been able to get pure CaCO₃ from eggshells, the gray powders from either the decomposed eggshells or the decomposed calcium acetate react much more vigorously with vinegar than the raw eggshells.  Still not as vigorously as baking soda as the video below shows, but bubbles abound nonetheless.  So, maybe the gray powders are worth trying as leavening. 

Second, can we approximate a best-case scenario for obtaining pure CaCO₃ from eggshells?  Yes! We can get a bag of pure CaCO₃ for a couple bucks at the local homebrew store.  So while our blog post declaring victory on purifying CaCO₃ from eggshells will have to wait until another day, we can still see what a best-case scenario for eggshell-based leavening would look like. Biscuit baking time!

Same recipe as last time, but only four sets this time: no leavening, gray CaCO₃ from eggshells, white CaCO₃ from the homebrew store, and NaHCO₃ (baking soda).  Very similar results as last time, too.  The gray CaCO₃ biscuits are definitely more risen than the no leavening control, and similar to the biscuits we baked last week from raw and lye-boiled eggshells.  The white CaCO₃ biscuits were noticeably more risen than the gray CaCO₃ biscuits, but still couldnt hold a candle to the baking soda biscuits.

The textures of both sets of CaCO₃ biscuits were similar to last weeks results, too. Not completely cooked through at the 20 min mark, while the baking soda biscuits were definitely done. 

The effect is more pronounced for banana bread.  Can you guess which loaf used gray CaCO₃ from eggshells as leavening? (Hint: its not the one on the right--that one had baking soda.) The grand conclusion from all these experiments?  Even though the CaCO₃ releases carbon dioxide gas when mixed with an acid (same action as baking soda), the slower reaction kinetics mean that eggshell-based leavening cant get the job done.

Have you ever baked with eggshells or tried to isolate CaCO₃ from them?  How did it turn out?

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