Sciencemadness Discussion Board - Nitrates from Swiss or French method - Planning for a year long experiment - need suggestions & help!

Nitrates from Swiss or French method - Planning for a year long experiment - need suggestions & help!

RogueRose - 28-9-2016 at 06:56

Ok, well I've seen a lot of posts on here about people stating a nitrate salt (KNO3, Ca(NO3) and maybe NaNO3) can be made from urine or urine and manure. It seems there is a wide range of how-to's and many seem to give contradictory steps.

Here is a quore on the Swiss and French method on the KNO3 page on Wiki:

Quote:

French method Niter-beds are prepared by mixing manure with either mortar or wood ashes, common earth and organic materials such as straw to give porosity to a compost pile typically 4 feet (1.2 m) high, 6 feet (1.8 m) wide, and 15 feet (4.6 m) long.[17] The heap was usually under a cover from the rain, kept moist with urine, turned often to accelerate the decomposition, then finally leached with water after approximately one year, to remove the soluble calcium nitrate which was then converted to potassium nitrate by filtering through the potash.

Swiss method LeConte describes a process using only urine and not dung, referring to it as the Swiss method. Urine is collected directly, in a sandpit under a stable. The sand itself is dug out and leached for nitrates which were then converted to potassium nitrate via potash, as above.

I have a 55 gallon steel drum as well as a 55gal polyetheleyne drum and I can use either for this. It's not 4ft tall, but it is 32" so it's not that bad. I would suspect some production is possible.

I have access to very lively garden soil (lots of bacteria) and a field that has soybeans at the moment, so maybe the nitrogen fixating bacteria could be harvested from the roots of these plants? Maybe mix the roots into the "slurry"?

I also have straw bales, bailed 2 months ago as well as some VERY dry (probably < 10% moisture) finely chopped grass clippings.

As far as manure, I live in a rural area and neighbors have cows, horses, chickens, ducks, turkey and others.

I will also have a good bit of access to oak ash (maybe some cherry & mulberry mixed in) this winter.

As far as urine, I think I will be stuck with using my own as I'm not harvesting from animals, lol

.

What I am not sure about is where it says that mortar or wood ashes are used in the french process. I guess this is for the Ca(OH)2 in the mortar and K2CO3 in the ashes?

I did recently try to leach about 1 cubic ft of oak ash using de-ionized water from a dehumidifier drain. I used about 3 gallons of water then filtered. I could not get the brown/red color out of the liquid but all particulate was removed down to a couple microns. This is what the result is after boiling the filtrate down:

The top right image is of the liquid in the pan. I had allowed a portion of the liquid to evaporate and it seemed to form yellowish/clearish crystals but they were very fragile and crumbled with slight pressure.

So I am wondering if the bottom of the drum should have some holes to allow for drainage. As the urine is poured in it will filter down through and various compounds will accumulate and maybe the water will percolate through.

Also, would it be good to add more manure weekly/monthly - and which is best?

I've heard fermented urine may be better as it has fermented into ammonia.

Are there any additives which would be beneficial like LOTS of coffee grounds? I know they have a high nitrogen content and I have access to about 10gal per day if I wanted that.

My goal is to be able to make some gun powder for musket hunting and doing it the truly authentic way. I'll do a complete documentation of the process if you guys are willing to give advice on what is the best way to do it.

The biggest concern is whether it needs to stay above freezing in the winter (will be tough). Maybe it will produce it's own heat and wrapping in fiberglass insulation will help keep heat in.

Maroboduus - 28-9-2016 at 07:39

The Brown liquid from oak ashes needs roasting to eliminate organic residues. Dry it in a hot stove then put it in a crucible in the hot coals of a fire. Not too much at once as it'll boil vigorously. Keep adding more as the boiling dies down until it's all in there and let it roast an hour or two. When it's cool dig the material out and dissolve in water and filter. It will be freed from most of those organic contaminants. That's crude Potash.

EDIT: firing crude potash is not a 'stinky' process. I have done it in my fireplace with no problem.

I don't know why you'd want that for making saltpeter, but it would be useful for making glass, or absolute ethanol, or potash biscuits(they used to use it to leaven biscuits before saleratus got popular).

EDIT: Nitrogen fixing bacteria is ubiquitous in the environment. I use a huge biological filter to fix the nitrogen in a 3000 gallon fish pond. I never seeded it with any bacteria, it just gets in there on its own. That thing must make a fair amount of nitrates, but boiling down all that water just wouldn't be worth it. The urine and manure methods should make more concentrated solutions worth boiling down.
As an initial experiment it might be worth using some fully composted manure and leaching that. Or some high nitrate soil. It'd be a pity to do all that futzing around with dung and urine for 6 months and not get a decent result, so why not see if the extraction works first?

[Edited on 28-9-2016 by Maroboduus]

[Edited on 28-9-2016 by Maroboduus]

aga - 29-9-2016 at 01:02

I have an experient like this out on the land somewhere with a 10 gallon bucket.

It stinks to high heaven, which is probably why i forgot about it until now.

The Swiss method with horses will get an input of several gallons of pee per day, which is pretty much imposible to match by a single human, no matter how much beer you drink.

Did i mention how much it stinks ?

Think i'll forget about it again.

ecos - 29-9-2016 at 01:50

how many gallons do this process need to get 100 gr of KNO3?

Marvin - 29-9-2016 at 06:26

Drums and buckets are a bad idea. Piles of earth/manure/urine/ash/limestone with straw and sticks and placed in layers are intended to let the air circulate. If things go anaerobic nitrates get destroyed. It needs protecting from rain, but other than that it is best kept as open as possible.

Digging dirt under stables works but it's a much less sophisticated method.

I don't know the ins and outs of the Swiss method, but the same principles will apply for good conversion.

The bacteria in legumes that fixes atmospheric nitrogen is not the right sort. The best bacteria comes from soil around established outdoor lavatories, from barns that are occupied by bats - that sort of thing.

Bert - 29-9-2016 at 07:11

Production of nitrate is a multi step process, carried out by several species of microorganisms. AND there are also microorganisms that will DEnitrify under some circumstances, destroying the product you are looking to optimize extraction of.

Here's a start.

https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3815407/

You may research this as a variety of historical/artisanal methods, or you may wish to look a bit deeper into the compost pile, perhaps you can do better than all those 18th-19th century production workers- Who were pre-Pasteur, but highly experienced "rule of thumb" saltpeter men...

Protium-1 - 29-9-2016 at 08:55

Its a cool project and there's no reason it shouldn't work. I remember my chem professor telling me that the detection of nitrate in well water is often a bad thing because it indicates that animal dung is nearby and possibly contaminating the well with bacteria also.

My question though is, what is the point of doing an extraction of the wood ash? It seems to me that by using the whole ash to percolate your dung compost extract through would act as a filter aid, similar to using Celite on top of a filter paper, and also an ion-echange medium which will release its K⁺ ions and trap any passing through Ca²⁺ ions within the ash matrix as insoluble CaCO₃.

I think that if you try to pass your dung compost extract through your obtained ash extract concentrate, you will end up with a layer of insoluble Ca compounds on top which will severely hinder any more dung extract from passing through, essentially a clogged filter.

[Edited on 9-29-2016 by Protium-1]

aga - 29-9-2016 at 09:09

Dung, Urine, Stench, Horses, Months of Effort .... or Ebay.

Sometimes the experience can be the same, but not often.

Maroboduus - 29-9-2016 at 16:33

Quote: Originally posted by aga

I have an experient like this out on the land somewhere with a 10 gallon bucket.

It stinks to high heaven, which is probably why i forgot about it until now.

.......

Did i mention how much it stinks ?

My Great Uncle had an experiment like that too. Unfortunately he lived in a studio apartment.

About a month ago I collected the leavings from the bottoms of a few dozen rabbit cages (dung, newspaper, left over rabbit food all soaked with urine) and put it in a 32 gallon trash can. I filled it 1/2 way with water and it's been fermenting and producing gas for the last month. This was just to use the nutrients for gardening, but I'm gonna tap out a few gallons of the horrible brown liquid and boil it down and see if I can get anything like nitrates out of it.

I also have a composter on site that gets all the kitchen refuse and some dried leaves as well as sludge from a 1200 gallon fish pond(A small one that isn't hooked up to the biological filter). It's the kind of composter where you dump stuff in at the top, and dig the results out at the botton from a trap door. I'm gonna try leaching some of the output from that as well. No crap or urine in the composter, unless that fish sludge counts, but rotten worm eaten veg must have some nitrogen in it. .
Will report results if good or bad.

Probably gonna leach some ashes too and make potash. I've never actually tried that late 18th century potash biscuit recipe. (Note to the British and other commonwealth types: these are American biscuits, fluffy hunks of cooked dough, not the twice cooked wafers you call biscuits)

Note to self: be careful not to confuse potash for biscuits with other 2 experiments.

RogueRose - 29-9-2016 at 19:52

I haven't read all the posts (wll later tonight or tomorrow) but it looks like a lot of good info. As for not sing a steel or plastic drum, that is fine. I can make a square (2ft x 2ft x 4ft maybe?? or 30" x 30" x 48-60" tall) out of 1/4" thick wood strips 1-3" wide and space them to give air flow. I can also line the inside or outside with something like chicken wire, wire mesh with 1/4 - 1/2" square's for the mesh, to hold smaller matter inside the container.

This process isn't soley to obtain a nitrate, although that is the compound I wish to produce. The goal of the process is to do it and find out how it works, how well, and how to make it better and what to avoid.

As for the ash water I boiled, that was simply to find out what soluble and possibly usable substances are available in wood ash. I had been making soap and was always told mixing ashes with the oils then cooking will give soap, but found that difficult to believe, and other stories of leaching lye from ash - so I decided to try myself and see what results I could obtain.

It is curious how in a chemistry forum that so many people "poo-poo" others experiments by saying "why not just buy it at (big box store) or online. This process and many others like it are EXACTLY what should be promoted on this forum, especially for beginners as this type of thing is pretty safe.

Anyway, thanks for the info guys I look forward to reviewing the posts in-depth.

I'm still wondering which type of manure is ideal for this - chicken, turkey, duck or possibly horse, cow, pig, goat (human even??).

Finally with the addition of urine, would there be benefit of allowing it to ferment first before adding to the pile?

If all else fails in this process I will take whatever is in this barrel/container and till it into the garden - unless others see a reason why this wouldn't be a good idea. The garden is 25x x 80ft (2,000 ft^2 or 222 yards ^2 0 so it is pretty big - IMHO)

Thanks again guys!

Marvin - 2-10-2016 at 04:04

Quote: Originally posted by Maroboduus

I filled it 1/2 way with water and it's been fermenting and producing gas for the last month. This was just to use the nutrients for gardening, but I'm gonna tap out a few gallons of the horrible brown liquid and boil it down and see if I can get anything like nitrates out of it.

You will probably get some, but fermenting is an anaerobic process. It destroys nitrates. So the more it ferments the less you would expect.

RogueRose,
A lot of people prefer tidy, pleasant smelling small scale chemistry. It's a personal choice, but as soon as they can find someone that will sell them nitrates they don't want to do experiments that will take them months and may attract the attention of the neighbours and the council air pollution department.

Maroboduus - 2-10-2016 at 06:34

The term 'ferment' was used loosely and inaccurately. it has been undergoing decomposition. The material is wet and porous after it expanded from the water added to it. It is in a loosely covered container (32 gallon bin) allowing air flow and does not have a strong ammonia odor. It DOES however have an odd smell less fecal than earthy which while different than ordinary shit-stink, may be indicative of only partially broken down nitrogenous organics. I only decided to tap some off at this time since the subject came up here. I actually have higher hopes for the fully cured compost I am leaching, but am not sanguine about the potential yield of either.

I used the term ferment because the only thing I've submitted to large scale microbial digestion in a trash can before was mash sweetened with sugar to make grappa.

I generally restrict myself to small scale organic chemistry, but wouldn't characterize it as pleasant smelling. Sure distilling essential oils and making esters can be nice, but bromoacetone hardly qualifies. Even the act of opening a fresh bottle of Hydrochloric acid is a far from pleasant-smelling experience. I don't mind diethyl ether, but tetrahydrofuran I find unpleasant.
Purines anybody?

As for the popular argument on this thread that 'someone will sell you nitrates';that applies equally well to just about every chemical made on this board. Obviously just getting a package of the stuff in the mail isn't always the point.
There's 2,5 methoxy 4 methyl nitropropenylbenzene available right now on Ebay, but if somebody posted here saying they had just made some you would not be likely to dismiss it by saying, "It's available on Ebay, go buy it" (although you might point out that it's a drug precursor that'll set off alarm bells at the DEA).

As for the air pollution problem. There is a vast difference between the odor of a reasonable sized manure pile properly located and the reek of the council flat next door where the neighbor went off the rails and started re-plastering the walls with his own fresh feces.