Wednesday, May 13, 2009

What's Chile And Rust Got To Do With Miracle Grow?





YOU KNOW----- JUST KEEP READING (and thanks... I guess.)

OH yeah, one more thing... please comment at the bottom of the page, anonymously is fine.  Just say, I came here to look for Chili, or Miracle Grow, or whatever... it fascinates me... regardless of whether you read this silly essay, or post, or what have you.  Thanks.

In late World War II, the British who had huge industrial concerns in Chile, mining Nitrate, saw the writing on the wall, as it were, and abandoned their mines, "closing them", they said, leaving a huge unemployed Chilean population.  The reason the British were forced to do this, is the same reason that rain is so much more nourishing to plants, by volume, than tap water.  The Haber-Bosch Process.

It might not surprise you to discover that subsequent to the discovery of the contents of the atmosphere we breathe, it occurred to chemists that it would be mighty nice to mine the air instead of salt pits in Chile for the chemicals necessary for fertilizer and the nascent arms industry.  Why was it not until 1909 that not even a tinkling stream of nitrogen could not be extracted from the atmosphere we breathe?  The problem was the triple bonds that atmospheric nitrogen enjoys, that makes it inert.  Triple bonds are, as you might imagine, extraordinarily strong, and so require fairly clever chemistry, somewhat high energy, and as would turn out to be the case, the help of a catalyst to break them and free the nitrogen and turn it eventually with hydrogen to ammonia.  

The first chemist to accomplish this feat with any success, though at extremely low volumes of ammonia, was Fritz Haber, a German (and later Nazi sympathizer, among other things.) in 1909.  His process, as cited in Wikipedia was taken up by the company BASF which is today a huge multinational... huge.  BASF apparently had a Carl Bosch working for them who seemed right for the monumental task of perfecting a process that could only produce a few cups of ammonia an hour, which wasn't even enough to clean the washrooms of Berlin.  Not by a long shot.

BASF's Bosch succeeded in his task in relatively short order, production scale ammonia being manufactured for the first time in 1913, at a factory in Oppau, Germany.  Just a few years later the ammonia produced (pretty much exclusively in Germany on the industrial scale) went completely into the German munitions (in the making of saltpeter for blackpowder production) for World War One.  Some have said without the Haber-Bosch process the Germans would have had no access to the Chilean Saltpeter, crucial at that time to the entire globe for making munitions.  It is surmised this would have meant they  could not have fought without their new factories and the Haber-Bosch process.  Wow, score one for science.  Making war... in as direct a way possible.

Ah, but the delights of the Haber-Bosch process don't end there.  First, a quick overview of what the mysterious process is, without too much technical detail (though you should look it up, for I'm no genius and let me tell you the chemical equations are as transparent as can be from one to the next.  It's as easy to read the equations as what I am about to tell you.)

There are two significant problems in the production of what farmers in Indiana (and illegal methamphetamine laboratories) and everywhere in the modern world call "anhydrous."  That's ammonia, like the stuff beneath your sink, but without any water. This makes it more efficient to deploy by the ton on agricultural fields.  No water also makes anhydrous more efficiently react with the water in the soils of a field, rather then applying a solution which is subject to all the vicissitudes of runoff and other forces taking the cherished nitrogen away from a relatively thin zone where modern crops require it.   

Ammonia production, again requires two things:


and  Nitrogen

Everybody knows that when you stick an electrical current through water, bubbles attach themselves to the positive and negative portions of the circuit, and those bubbles are in fact hydrogen for one and oxygen for the other.  This is electrolysis, and it was the way they made hydrogen when the Haber-Bosch was invented.  Today, due to the vastly less expensive expenditure in energy (chiefly, what do you know, electricity!) required, methane (CH4) is used instead.  

You'll remember that when I wrote my entry below about Sythesis gas a few weeks ago I admitted being blown away by my sudden realization as to how it was (I had always wondered) that all those people in the past managed to kill themselves by, "sticking their heads in the oven."  Turned out that back in our grandparents day, and for a goodly period of the industrial revolution, Synthesis Gas, or gas made from wood or coal was the norm in the home and factories.  Synthesis gas varies based on the stuff it's made out of.  Technically it can be made out of just about anything that's biomass, and my mentioning Lignin a few entries below, is appropo here, for Lignin gives Syngas a little extra boost in methane, for reasons I promised you (sort of, just above) not to go into for our purposes here.  But to put it simply, Synthesis gas is mostly carbon monoxide, which you may not know, is most of the stuff you see sputtering out of a log, burning, when you first light a fire, before the log begins (late in the fire) to burn it's actual cellulose and remaining lignin alone.  Usually Synthesis Gas will contain about a third carbon dioxide, a third carbon monoxide and a third methane, if you are producing it with the crude methodology of the late nineteenth century.  I could achieve that with a Weber grill in my backyard and some clever tinfoil craftsmanship.  

Why all this chitchat about Sythesis gas?   Because a modern method getting hydrogen out of methane uses steam, over a catalyst and is called steam reforming:  it does exactly that.  First it takes methane and steam and turns them into carbon monoxide and hydrogen (a little like burning wood.)

Then it runs those gases through other processes to end up with carbon dioxide and hydrogen.  The hydrogen is separated and one part of the two is available for the ammonia.   Haber-Bosch process will provide the second part.  

The thing to remember about the Haber-Bosch process is that while it changed the earth forever, in a sense making the human race "more fertile" in real terms, more able to support higher populations.  And more able to slaughter them in war.  The process is none the less very simple.  It's complexity is not in the chemistry (though it was the chemists who got the Nobel prize, Haber and Bosch in 1918 and 1931. Thanks Wikipedia)  really, but the engineering, which allows the chemistry to happen at a rate and scale that is relevant to municipal, national, and today international markets and needs.  

It's a little like fusion.  The concept of fusion certainly doesn't need proving in a lab, we have a full time proof off concept in the Sun, long ago described by spectrum analysis, showing the proper isotopes delivered in the fusing of hydrogen and helium.  Proof.  It's the engineering of fusion, on Earth, that is not possible.  Seem obvious to you, right?

Same with Haber-Bosch.  It wasn't that chemists didn't know how the chemistry should work, it was that they literally didn't have the engineering chops to bring the reactions to the proper temperature and pressure to create industrially relevant quantities of ammonia to scale.  They had a lot of help from engineers, and in a few years solved the problem with BIG pipes and valves, ect.

Good lesson to remember in many walks of life.  Not always the know how.

The basic chemistry was, you won't believe this, taking magnetite, a type of rust as the catalyst (talk about a cheap catalyst) and basically placing it in a sealed, heated and high pressure circuit of pipe full of air (with continuously new air being added at pressure) and hydrogen.    The air, at pressure, obviously is mostly nitrogen and the catalyst, with the heat and pressure causes a conversion of the nitrogen and hydrogen to ammonia, in discreet stages, about fifteen percent per cycle of the process.  Eventually after enough stages, five or six, an almost hundred percent conversion occurs.  A somewhat faster rate than two cups an hour.

It's a bit more complicated, but not much, and it worked like a charm in 1913, just in time for the First World War as I mentioned before.  If you would like one of these machine's of your own, Wikipedia mentions that Kellog, Brown and Root (who commonly advertise and underwrite rich people media of choice like public television and radio, and the Arts) will happily provide the engineering for you.

So why am I telling you this.  Well... I read a book about this process, as I mentioned, last year or the year before.   I was completely amazed by the importance of this process to war and modern agriculture (two things that are fetish interests of mine.)  I don't remember the process being even mentioned to me in any science class or history class of my youth.  Do I need to repeat that Germany utilized this industrial process to produce weapons, and maintain it's power during World War One?  Remember what happened to Germany after the War?  And all the problems that defeat compounded until a certain mad man took that country by a storm?  Now I am not saying that Haber-Bosch caused the rise of Hitler, but I am most definitely interested in how it played a role in Germany's "independence" and capacity to view itself as a viable, even unbeatable power.  How could someone not be curious? 

But that's not really the reason I keep mentioning the process.  Though I need not tell you again how much it interests me.  The main reason I find the process a potent and interesting subject is the downstream effects that are the result of the not entirely obvious life cycle of anhydrous ammonia, and to some extent nitrates and nitrites.  

I won't go into numbers, but I will say, once, that 100 million tons of nitrogen fertilizer is produced by this process per year.   One billion tons in one decade.  A fairly round number, should you interest yourself in more research.  Even I can add, multiply, divide, and subtract the number one.  Add your zeros later.

So, a lot of nitrogen is used as fertilizer, so what.  Well... all that nitrogen came from the atmosphere, in a form that was what started this whole conversation in the first place:  a stable, inert form.  It isn't like water, where it might be ice, or it might be rain, or it might be the steam off your morning tisane (that's tis sahn, nice try.)  This is atmospheric nitrogen, playing a role in virtually no ecosystem save the tiny one it plays in the roots of legumes (big human numbers, tiny earth numbers.)  And suddenly mankind, in 1913, despite his previous use of mines of nitrate, which granted were being exported from Chile at the rate of (about) 2.5 million metric tons, (2.275 million US tons) through 1931 (when the Haber Bosch Process began to catch up with it, and after the First World War.) that was 2 percent of our present annual production.  
This issue is that we suddenly increased our usage in 1913, of chemically active nitrogen: nitrates (they develop due to oxygenation of nitrogen in the environment).  This chemically active nitrogen is a happy part of the fertility of only agriculture.  And many folks, today (proponents of sustainable and organic agriculture)  regard them as not a happy part of fertility at all.  Nitrates get out of the fields and enter the water supply, poisoning streams, fish, wildlife, and people (for example: blue baby syndrome.  Nitrates in agriculture are applied like most applications of products in agriculture in a manner for a guaranteed yield in crops.  This leads in many, not all, cases to an over application of nitrate to the environment, due to an under utilization, or poor application of fertilizer.  Eventually the nitrate ends up in runoff, a stupid euphemism for the water table and greater watershed of the system that every farm is part of.  People don't like to consider themselves and their property as part of a larger system that they then feel they are some how a mere part of.  This is to be fair, more an issue of education, and mere ignorance, than maliciousness on the part of farmers.  In the final analysis the watershed absorbs enormous quantities of runoff of nitrate.  This from the moment fertilizer (anhydrous, or liquid/dry nitrate, miracle gro, what have you) is applied begins to poison or cause problems to the environs outside the small circle of intentionality that the farmer or person applying the nitrogen intended.  The nitrate, or nitrite ends up in the environment, and once the natural world has passed down the watershed and absorbed it's effects, there is usually so much that human drinking water has absorbed it as well.  This effectively renders all fresh water in agricultural areas polluted, and dangerous (depending on time off year, ect.) to human consumption, which in the modern world is in fact common sense.  A fairly depressing result for what is supposed to be a blessing to mankind.  Don't you think?
Lastly, what began this entire inquiry... why is rain more fertile than tap water?  Because, for all the nitrate that pollutes fresh water systems, rain picks up volatilized ammonia in the atmosphere.  Over half of all anhydrous simply evaporates into the atmosphere, to react with, and be taken up by the water vapor and rain.  Then the rain falls, with this load of nitrogen, significantly increasing the growth of plants when compared to tap water.  Scary.


No comments: