Sciencemadness Discussion Board

Iron catalyzed sulphuric acid production

MeshPL - 18-7-2015 at 06:10

Hello everybody!
Reading wikipedia i got an idea: how to produce sulphuric acid at home cheaply and easily. Not sure, if it will work though.
According to: https://en.wikipedia.org/wiki/Sulfuric_acid, the following reactions can occur (and do in rocks):

2FeS2 + 7O2 + 2H2O --> 2FeSO4 + 2H2SO4

2FeSO4 + H2SO4 + 1/2O2 --> H2O + Fe2(SO4)3

FeS2 + 7Fe2(SO4)3 + 8H2O --> 15FeSO4 + 8H2SO4

Presence of iron sulphates as a catalyst increases the rate of reaction, allowing the second and third reaction to work. Pre-adding some kind of ferric salt as a catalyst would be a good idea.

If I would bubble enough air through FeS2 slurry, and stop before all FeS2 dissolves (I don't want the second reaction to waste my H2SO4), I should be able to disstil H2SO4 out of the solution.

I also got an idea to replace FeS2 with elemental sulphur. According to wikipedia "List of standard Electrode Potentials", the following reactions would potentialy occur. Note the need of iron catalyst this time:

S + 2H2O + 2Fe2(SO4)3--> SO2 + 4FeSO4 + 2H2SO4

SO2 + 2H2O + Fe2(SO4)3 -->2FeSO4 + 2H2SO4

2FeSO4 + H2SO4 + 1/2O2 --> H2O + Fe2(SO4)3

Would that be at least possible?

byko3y - 19-7-2015 at 06:29

It's nice to see someone trying to invent the same shit people have been doing for 400 years.
https://books.google.com/books?id=O4rzzkUQyzIC&pg=PA8&am...
Fe2S + O2 + H2O -> FeSO4 -> Fe2(SO4)3
Fe2(SO4)3 -> Fe2O3 + SO3
Maybe some day the idea of oxidizing the SO2 with nitrate salt will draw your attention.

[Edited on 19-7-2015 by byko3y]

MeshPL - 19-7-2015 at 07:15

For some reason I cannot view, that book...

Quote:

Fe2S + O2 + H2O -> FeSO4 -> Fe2(SO4)3
Fe2(SO4)3 -> Fe2O3 + SO3


The second reaction seems to require high temperature. I'm well aware of the process for SO3 production requiring roasting of iron sulphates, but I was curious, if you could do that without roasting, just distilling H2SO4 at thge right time out of pyrite slurry, to maximise the yield.

Also, is oxidation of elemental sulphur by iron (III) possible?

[Edited on 19-7-2015 by MeshPL]

byko3y - 19-7-2015 at 10:01

I'm pretty sure that many of you reactions require high temperatures. However I might be wrong and you will invent a new way of producing sulfuric acid.
Some time ago I posted an idea about doing almost the same using copper as a renewable source of sulfate. http://www.sciencemadness.org/talk/viewthread.php?tid=62575&... It has one beautiful property - CuS is completely insoluble in sulfuric acid, thus making it possible to collect precipitate and obtain a pure H2SO4. Drawbacks: toxicity and odor of H2S; some oxidation reactions might be tricky.
Also, you might already know that copper is used by enzymes for aerobic oxidation.
UPD: I forgot to mention that the iron catalyst is actually one of the options as a contact catalyst. AFAIK, it requires high temperatures, which leads to decomposition of formed SO3 into SO2, thus leading to lower yields. Palladium has highest reactivity, but unfortunutely it also reacts with impurities, that's why SO2 coming into catalyst bed should be exceptionally pure. Palladium-based contact process was used in the industry (somewhere at 1900-1920) until vanadium catalyst was discovered, which is less vulnerable for poisoning.

[Edited on 19-7-2015 by byko3y]

unionised - 19-7-2015 at 10:07

Quote: Originally posted by byko3y  
It's nice to see someone trying to invent the same shit people have been doing for 400 years.
https://books.google.com.ua/books?id=O4rzzkUQyzIC&pg=PA8...
Fe2S + O2 + H2O -> FeSO4 -> Fe2(SO4)3
Fe2(SO4)3 -> Fe2O3 + SO3
Maybe some day the idea of oxidizing the SO2 with nitrate salt will draw your attention.

Congratulations on posting a link to a Ukrainian web site.

This thread needs to remember that geology has plenty of time on its hands.

aga - 19-7-2015 at 12:05

Interesting point.

Perhaps reaction formulae should come with a clue as to the time taken in various conditions, a bit like catalysts are noted.

    star
H ==> Pb (2.3 billion years +/-486.25 million)
    hot


[Edited on 19-7-2015 by aga]

MeshPL - 19-7-2015 at 22:21

Quote:

star
H ==> Pb (2.3 billion years +/-486.25 million)
hot


No, lead requires supernovae to form. As far as I remember nothing stable heavier than iron can be formed in regular stars in reasonable quantities. So:

Supernovae
Anything ==> Pb (~few seconds)
F****** hot, high pressure

Note: the reaction is dangerous and may result in splashing of reaction mixture everywhere. The yields are low, and there are many by-products including gold, platinum, iridium etc. which will need to be removed.


Quote:

I'm pretty sure that many of you reactions require high temperatures.


Maybe... electrode potentials, measured for 20C, indicate, they MAY occur.


Quote:

This thread needs to remember that geology has plenty of time on its hands.


In case of mines, acid mine drainage can occur within a few years... also geology cannot bubble fresh air through slurry of pulverized matterial.

Boffis - 20-7-2015 at 06:48

No, nature works the other way round and pours the water through a porous aerated honeycomb full of sulphides! Very effective!

The process of pyrite oxidation is complex and often bacterially assisted but the key process in the formation of free sulphuric acid is the precipitation of the basic potassium ferric hydroxide sulphate minerals such as jarosite KFe3(SO4)2(OH)6 at about pH 2-3 from solutions containing normal ferric sulphate rough according to:

K<sub>2</sub>SO<sub>4</sub> + 3Fe<sub>2</sub>(SO<sub>4</sub>;)<sub>3</sub> + 12H<sub>2</sub>O &rarr; 2KFe<sub>3</sub>(SO<sub>4</sub>;)<sub>2</sub>(OH)<sub>6</sub> + 6H<sub>2</sub>SO<sub>4</sub>

This equation is only illustrative of the formation of one mineral and there are a vast number of natural iron sulphates.

DSCN2744.JPG - 1.5MB Curpocopiapite forming on openpit walls in Kazakhstan


DSCN2748.JPG - 1.2MB The iron precipitates but the copper stays in solution!!

DSCN2735.JPG - 1.4MB Copper sulphate encrusted blocks eastern Kazakhstan

AJKOER - 20-7-2015 at 11:11

Per Boffis comment "bacterially assisted", Wikipedia's ( link: https://en.m.wikipedia.org/wiki/Acidithiobacillus_ferrooxida...) says, to quote:

" Acidithiobacillus ferrooxidans (syn. Thiobacillus ferrooxidans) lives in pyrite deposits, metabolizing iron and sulfur and producing sulfuric acid."

[Edited on 20-7-2015 by AJKOER]