How Are The Raw Salts Made Anyway?

MGRox · Dec 21, 2015

Did a little looking to see how all these salts for nutes are acquired / manufactured. A few of them were not quite what I expected.

-Ammonia (Anhydrous)
It all starts with Ammonia created by the Haber Process
"The process converts atmospheric nitrogen (N2) to ammonia (NH3) by a reaction with hydrogen (H2) using a metal catalyst under high temperatures and pressures:" "hydrogen gas obtained is from natural gas."....."Over 80% of the total cost of manufacturing NH3 is natural gas."
N2 + 3 H2 → 2 NH3 (ΔH = −92.4 kJ·mol−1)

-Urea
First Anhydrous ammonia is reacted with CO2 to produce Ammonium Carbamate.
"It is prepared by the direct reaction between liquid ammonia and dry ice.
Ammonia and carbon dioxide is excessively fed to a synthesis reactor in this process. Ammonium carbamate is produced as an intermediate in this reactor and can then be dehydrated to urea."
2 NH3(l) + CO2(s) → H2NCOONH4
NH2CO2NH4 → NH2CONH2 + H2O
***NOTE: There is NO Urine in Urea.....but there is Urea in Urine.

-Nitric Acid
"Nitric acid is made by reaction of nitrogen dioxide (NO2) with water."
3 NO2 + H2O → 2 HNO3 + NO
"Nitrogen dioxide typically arises via the oxidation of nitric oxide by oxygen in air"
2 NO + O2 → 2 NO2
"In commercial settings, Nitric Oxide is produced by the oxidation of ammonia (normally at 850 °C) with platinum as catalyst:"
4 NH3 + 5 O2 → 4 NO + 6 H2O

-Ammonium Nitrate"Nitric acid and ammonia are used to make ammonium nitrate. ....The two materials are mixed together in a tank and a neutralization reaction occurs, producing ammonium nitrate."
HNO3 + NH3 → NH4NO3

-Phosphoric Acid
"Phosphoric acid is the starting material for most of the phosphates that are produced industrially. It is obtained from the reaction of the apatite mineral with sulfuric acid."
"Wet process phosphoric acid is prepared by adding sulfuric acid to tricalcium phosphate rock, typically found in nature as apatite."
Ca5(PO4)3X + 5 H2SO4 + 10 H2O → 3 H3PO4 + 5 CaSO4·2 H2O + HX
(where X may include OH, F, Cl, and Br)

-Mono Ammonium Phosphate
"NH4H2PO4, is formed when a solution of phosphoric acid is added to ammonia until the solution is distinctly acidic. It crystallizes in tetragonal prisms."
2NH3 + H3PO4 → (NH4)2HPO4

-Diammonium Phosphate
Similar to mono Diammonium Phosphate is made by a reaction of phosphoric acid and ammonia. Mono Ammonium Phosphate is first made, then it is further reacted to ammonia to produce diammonium.
2NH3 + H3PO4 → (NH4)2HPO4
NH4H2PO4 + NH3 → (NH4)2HPO4

-Calcium Nitrate
"also called Norgessalpeter (Norwegian saltpeter). Nitrocalcite is the name for a mineral which is a hydrated calcium nitrate that forms as an efflorescence where manure contacts concrete or limestone in a dry environment as in stables or caverns."
"It is produced by treating limestone with nitric acid, followed by neutralization with ammonia:"
CaCO3 + 2 HNO3 → Ca(NO3)2 + CO2 + H2O
Ca(NO3)2 + H2O + NH3 → 5Ca(NO3)2.NH4NO3·10H2O
"The fertilizer grade (15.5-0-0 + 19% Ca).....contains ammonium nitrate and water, as the "double salt" This is called calcium ammonium nitrate." "Formulations lacking ammonia are also known: Ca(NO3)2·4H2O (11.9-0-0 + 16.9%Ca)"

-Potassium Nitrate
"On industrial scale it is prepared by the double displacement reaction between sodium nitrate and potassium chloride."
NaNO3 (aq) + KCl (aq) → NaCl (aq) + KNO3 (aq)

-Monopotassium Phosphate
Monopotassium phosphate is produced by the action of phosphoric acid on potassium carbonate.
3K2CO3 +2 H3PO4 ------> 3CO2 + 2K3PO4 + 3H2O

-Potassium Carbonate
"Potassium carbonate is prepared by the electrolysis of potassium chloride. The resulting potassium hydroxide is then carbonated using carbon dioxide to form potassium carbonate...."
2KOH + CO2 → K2CO3 + H2O

-Potassium Chloride
"Potash ores are typically rich in potassium chloride (KCl) and sodium chloride (NaCl)...."
"In the evaporation method hot water is injected into the potash which is dissolved and then pumped to the surface where it is concentrated by solar induced evaporation. Amine reagents are then added to either the mined or evaporated solutions. The amine coats the KCl but not NaCl. Air bubbles cling to the amine + KCl and float it to the surface while the NaCl and clay sink to the bottom. The surface is skimmed for the amine + KCl which is then dried and packaged for use as a K rich fertilizer"

-Potash
"Potash refers to potassium compounds and potassium-bearing materials, the most common being potassium chloride (KCl). The term "potash" comes from the Middle Dutch word potaschen ("pot ashes", 16th century). The old method of making potassium carbonate (K2CO3) was by collecting or producing wood ash (an occupation carried out by ash burners), leaching the ashes and then evaporating the resulting solution in large iron pots, leaving a white residue called "pot ash". Approximately 10% by weight of common wood ash can be recovered as pot ash. Later, "potash" became the term widely applied to naturally occurring potassium salts and the commercial product derived from them."

-Potassium Sulfate
"Potassium sulfate is produced according to the following reaction, which is conducted in so-called Mannheim furnaces"
2 KCl + H2SO4 → 2 HCl + K2SO4

-Magnesium Sulfate
"It is often encountered as the heptahydrate sulfate mineral epsomite (MgSO4·7H2O), commonly called Epsom salt..."
"The heptahydrate can be prepared by neutralizing sulfuric acid with magnesium carbonate or oxide, but it is usually obtained directly from natural sources."

-Calcium Sulfate (Gypsum)
"The main sources of calcium sulfate are naturally occurring gypsum and anhydrite which occur at many locations worldwide as evaporites. These may be extracted by open-cast quarrying or by deep mining"
As well from other sources commonly (see phosphoric acid reaction above);
"In the production of phosphoric acid from phosphate rock, calcium phosphate is treated with sulfuric acid and calcium sulfate precipitates"

-Calcium Carbonate
"The vast majority of calcium carbonate used in industry is extracted by mining or quarrying. Pure calcium carbonate (e.g. for food or pharmaceutical use), can be produced from a pure quarried source (usually marble)."
"Alternatively, calcium carbonate is prepared from calcium oxide. Water is added to give calcium hydroxide then carbon dioxide is passed through this solution to precipitate....precipitated calcium carbonate (PCC)"
CaO + H2O → Ca(OH)2
Ca(OH)2 + CO2 → CaCO3 + H2O

-Calcium Chloride
"Calcium chloride can be produced directly from limestone, but large amounts are also produced as a by-product of the Solvay process."
"The Solvay process or ammonia-soda process is the major industrial process for the production of sodium carbonate (soda ash)."....."The Solvay process results in soda ash (predominantly sodium carbonate (Na2CO3)) from brine (as a source of sodium chloride (NaCl)) and from limestone"
2 NaCl + CaCO3 → Na2CO3 + CaCl2

-Sulfur
"Elemental sulfur occurs naturally as the element (native sulfur)..... Being abundant in native form, sulfur was known in ancient times, being mentioned for its uses in ancient India, ancient Greece, China, and Egypt. Sulfur is referred to in the Bible as brimstone."
"Today, almost all elemental sulfur is produced as a byproduct of removing sulfur-containing contaminants from natural gas and petroleum. The element's largest commercial use (after mostly being converted to sulfuric acid) is to produce sulfate and phosphate fertilizers"

-Sulfuric Acid
"Sulfuric acid is produced from sulfur, oxygen and water via the conventional contact process (DCDA) or the wet sulfuric acid process (WSA)"
"sulfur is burned to produce sulfur dioxide...then oxidized to sulfur trioxide using oxygen in the presence of a vanadium(V) oxide catalyst...The sulfur trioxide is absorbed into 97–98% H2SO4 to form [URL='https://en.wikipedia.org/wiki/Oleum']oleum (H2S2O7), also known as fuming sulfuric acid."[/URL]
S (s) + O2 (g) → SO2 (g)
2 SO2 (g) + O2 (g)

2 SO3 (g) (in presence of V2O5)
H2SO4 (l) + SO3 (g)→ H2S2O7 (l)

MGRox · Dec 21, 2015

So...with a bit of natural air and some hydrogen (most abundant element in the universe); we can make a beginning nutrient, .....ammonia. Simply adding CO2 (in a reactor) or catalyzing at high temps with an electrode (along with water and air); we are now capable of producing- ammonia, nitric acid, ammonium nitrate and urea. We can react the nitric acid with a bit of limestone and also add Calcium nitrate to the list. Now, if we take some sulfur (or pyrite) and a bit of lead along with water and nitric oxide; we can also produce sulfuric acid. Taking the sulfuric acid to some appetite and we now also have phosphoric acid; which can be further reacted with ammonia to add MAP and DAP. If we further take some potash ore / mineral and add hot water / evaporate, then react with sulfuric; we also have Potassium Sulfate. Last if we get a little epsomite (or even react sulfuric with an oxide) we can also have magnesium sulfate.

Obviously the above is a very simple and general way of acquiring all of this. However, aside from reactors and 2 specific electrodes; we basically only need air, water and a couple minerals to make a fairly complete nute from scratch. Pretty darn cool if you ask me.

sixstring · Dec 21, 2015

It all sounds fairly simple and organic.

MGRox · Dec 21, 2015

yea lol. I've been running with the whole Mr. Mackey "Salts are bad, M'kay". Just hadn't taken the time to look it all up. I was delightfully surprised.

I know one big negative against salts is its "connection to oil"....evidently that is only related if looking at Sulfur....

Tnelz · Dec 21, 2015

Really awesome post bro. Love for you to set up a link on my thread. Not to steal anything but this is awesome information.

sixstring · Dec 21, 2015

yeah theres alot of stuff that just comes from the earth and sthen some that has to be processed and then a bunch of dif ways to process.wish i knew how jr peters makes all there salts cause i really like the stuff.but then again maybe i dont wanna know how its made lol.

MGRox · Dec 21, 2015

@Tnelz no worries and Done!

@sixstring yea I really wanted to find who was making all the salts, but that is easier said than done. I read most of the calcium nitrate is made in Norway. Also, one of the last 6-7 items shown (didn't note which); Dow produced 35% of the need for the US. Outside of that, I could not find any specific companies.

Though there is some pretty large legal loopholes to jump through to produce many of those salts; I imagine that 3 companies (or so) produce the entirety of raw salts......that are chemically derived that is.

sixstring · Dec 21, 2015

Thought i read somehwere that the world's supply of either potassium or phosphorus was going to run out in my lifetime but i cant remember where or what i read that in.fyi im 46 and figure i will be lucky to hit 70 lol.

sixstring · Dec 21, 2015

The more i think about it i think it was phosphorus

Sativied · Dec 21, 2015

Good thread, reminds me of looking into "petroleum-based" fertilizer.

http://environment.nationalgeograph...uying-guides/fertilizer/environmental-impact/

That nonsense from national geographic is debunked in (amongst other articles), by an organic grower:

Dabominable · Dec 21, 2015

Very informative! I know the whole having salts in the name with the sulfate/carbonates used to scare me off. Then i started using stuff like k-mag, and potassium sulfates. Good, good stuff. Amazing break down, even the laman like me can understand it!

Quantrill · Dec 21, 2015

Nice work, MGRox. A couple notes.

http://www.ipni.net/specifics-en

Historically, K2SO4 was made by reacting KCl with sulfuric acid. However, it was later discovered that a number of earth minerals could be manipulated to produce K2SO4 and this is now the most common method of production. For example, natural K-containing minerals (such as kainite and schoenite) are mined and carefully rinsed with water and salt solutions to remove byproducts and produce K2SO4. A similar process is used to harvest K2SO4 from the Great Salt Lake in Utah, and from underground mineral deposits.

In New Mexico (USA), K2SO4 is separated from langbeinite minerals by reacting it with a solution of KCl, which removes the byproducts (such as Mg) and leaves K2SO4. Similar processing techniques are used in many parts of the world, depending on the raw materials accessible.

The process used to manufacture MKP fertilizer on a large scale is not the neutralization of phosphoric acid with potassium carbonate as you detailed. Rather it is described here:http://www.google.com/patents/US4678649

Before the global market opened up to China, almost all the MKP fertilizer was produced by Rotem Amfert Negev, but now even they subcontract some production in China.

none of this is to say your post was wrong, as the methods you describe, as far as I know are real, just not the way these two fertilizers are produced on a large scale.

MGRox · Dec 21, 2015

Thanks to all for the kind comments.
@Sativied xD very nice video; it's done well! As you mentioned too, nice from an organic buff.

@sixstring tyvm for bringing that up with P reserves. I was not aware of it...so I had to snoop lol.
That is definitely a concern. Evidently there is some research / testing going on to at least help some (i.e. reduce leeching / runo-off). The last link is probably the best. They found that using "drinking water treatment residues" (not wastewater) can increase the P-sorption ability of soils. Not Ironically they are using Ca, Fe or Al compounds to lower the run-off by as much as 80%. >>>so anyone that wants to start a business *coughs* start making p-sorbing reactors of Ca-WTR and selling it at a premium. Heck even sell the WTR directly for soil application. haha.
http://csis.org/files/attachments/100922_Kauwenbergh_Presentation_0.pdf
http://gsrpdf.lib.msu.edu/ticpdf.py?file=/article/penn-phosphorus-5-11-12.pdf
https://edis.ifas.ufl.edu/ss513

@Quantrill tyvm for those additions! Yea the minerals are listed on the wiki page with K2SO4; but they noted "typically" being done chemically, so I didn't mention the minerals. I definitely want the most common methods to be presented for sure and it's good that you have them brought up.
With the MKP, I was not aware of that process; another great addition! One of the resource links above had mentioned yet another process for high purity (using high temps, silica and coke), but noted it was less common. With the note in your patent link about no chlorine; I'm assuming that's the process(es) for 0-0-52, whereas the original must be for 0-0-50. Yes, no?

Quantrill · Dec 21, 2015

yes, the rotem amfert Negev folks are the ones that make the 0-52-34 MKP, and I am pretty sure they make it for Haifa and Yara as well. As seen in their msds, the brand names , Multi-MKP(Haifa brand) and Krista MKP(Yara) are listed right next to PeaK(ICL/rotem anfert negav brand).

If you are talking about the 0-0-50 and 0-0-52 potassium sulfate, I believe both GSL and SQM use the salt brine solar evaporation method. Rather I know GSL uses the solar evaporation of salt brine for their OMRI registered 0-0-50, which actually has a typical analysis of 0-0-52.3 but they only guarantee a minimum of 0-0-50.

How Are The Raw Salts Made Anyway?

MGRox

MGRox

sixstring

MGRox

Tnelz

sixstring

MGRox

sixstring

sixstring

Sativied

Ruler of the Whorled

Dabominable

Quantrill

MGRox

Quantrill

Latest posts