I've been rereading Pournelle's _Falkenberg_ series, and I've just
        had my grey-matter stirred (again).

        A simple sentence implied that frontier worlds were using Veggie-
        Oil as diesel fuel.

        If Veggie-Oil *can* be used in that capacity, and we already know
        that IC engines can use methane and alchohol, then this raises the
        question:

        "Why are we Dependent Upon Foreign Petroleum and not only starving
         our own farmers, but allowing Farmland to remain useless?"

        Why the heck are we paying for imported material we can substitute
        for so easily? Is this "literature-license" that assumes some sort
        of "breakthrough" in engineering? From what I recall from my
        grandfathers (endless) lectures on Diesel/IC and machining
        stories, (he was a master master machinist and other), there is no
        reason for *not* using veggie-oil for diesels, which are more
        useful (efficient?) than IC engines.

        Seems to me that we could, in a single generation: dump the
        Mideast, revive the dying Farming-Capability of this nation and 
        clean up our environment as an incidental.

63 responses total.

  I disagree with your premise that our country has lost its agricultural
capability.  Farmers are in decreased demand largely due to technological
advances.  Their transfer to other fields is a natural result of this.
Farm acreage has remained relatively steady since 1920 (between 0.9 and
1.2 billion acres), while productivity has skyrocketed, and the farm
population has diminished from 30% of our workforce to under 2%.  We also
find it more economical to import many crops from other countries than to
grow them domestically.
 
  Also, farmland is not a renewable resource itself - nutrient depletion
can be combatted, but you can only sustain so much soil erosion before a
region is infertile.  Many farms in the Midwestern flood a couple of years
ago were stripped down to clay, because the farms were left bare between
crops to save money.
 
  But on the question of vegetable oil as a fuel, I would guess that the
answer to the question of "why don't we do this" is strictly economic - it
would be more expensive or inconvenient to run automobiles on vegetable
oil than on diesel fuel.

   not really. to run a car on corn liquor, all you need to do is dry out the
fuel tank and adjust the carburetor a bit (and probably your brakes, too).

"Honey, we're out of salad oil.  Could you run down to the gas station?"

Veggie oil powered diesels have been around for a long time.  I remember
reading about a guy who drove his VW Rabbit diesel coast to coast, fueled
by used veggie oil from McDonalds fries fryers.

        So, what I am hearing is that it can/could be done, yet it is more
        "economical" to import a 'strategic' resource than to change a few
        federal/state mandates and use our farms more productively?

        Farmers tend to plant 'garbage' crops periodically to maintain the 
        soil - those crops get mulched right back into the soil before the
        next viable planting. "Flash Floods" are rather difficult to
        predict, but not impossible. Sounds like lousy planning. I presume
        those farms were huge, eh? Federal Disaster Relief? I also suppose
        that no one thought about using a couple hundred tons of river
        silt to provide a soil basis?

I recall reading one assesment of corn alchocol for fuel:  To replace gasoline
use, we'd need more more farmland than we currently have.

When the Diesel was invented they were used in stationary power
applications and run on anything that burned - including powdered coal!
The reasons that petroleum became the primary fuel was both economic and
because of byproducts of combustion.  Vegetable oils pyrolize to some very
tough, refractory gums, which interfer with operation, in addition to
their much greater cost. Powdered coal never came into favor for mobile
operations for self-evident reasons (cough, cough...). 

>  So, what I am hearing is that it can/could be done, yet it is more
>  "economical" to import a 'strategic' resource than to change a few
>  federal/state mandates and use our farms more productively?
 
  My contention is that there are factors (price is a biggy) that
currently make using diesel fuel more desirable than using vegetable
oil in diesel engines, in most cases.  I'm confident in this position
even without knowing many technological details, just because of the
economic principles involved.
 
  I don't equate using vegetable oil as "changing a few federal state
mandates and using our farms more productively," or using diesel fuel
as "importing a 'strategic' resource."  Diesel fuel and vegetable oil
can both be produced domestically or imported.  The ratio of domestic
production to importation of either is guided largely by economic
factors.

        OK, thanks.. The gumming problem I can vaguely recall from Gramp's 
        lectures.. (I wonder what additive would resolve this?).

        So.. What I guess the consensus is, is that it's more economical
        to merely depend on imported petroleum?

        I'm not exactly sure why this would be true, let alone desirable,
        but it sure sounds ludicrous.

        As far as the ethanol issue: you are suggesting that we have 
        insufficient productivity to support a heavy level of alchohol
        in the IC engines? Hmm... If corn is but one starch which we
        could convert, I rather wonder about this..

        Anyone have any figures, or know a site which has them, pertaining
        to the yield of alchohol per bushel of anything?

>        So.. What I guess the consensus is, is that it's more economical
>        to merely depend on imported petroleum?
 
Whether the petroleum is imported or produced domestically, there does
seem to be a broad international consensus that it is the preferred fuel.
 
>        I'm not exactly sure why this would be true, let alone desirable,
>        but it sure sounds ludicrous.
 
I'm quite certain that the average cost per mile traveled (factoring in
maintenance, manufacturing differences, and whatever) is the biggest factor.
I don't see what's ludicrous about that.

It is not ludicrous economically. It is somewhat ludicrous if the social
situation is such that supplies might be interrupted. There has been talk
about "energy self sufficiency", but that is much more expensive, or at
last more politically difficult, than maintaining a big military to ensure
that imported fuel keeps flowing, or at least our governments have wanted
to approach it that way. 

I have been a sometime-follower of sci.energy on Usenet News, and
the topic comes up periodically.  Every so often a story comes around
of a school system which takes the fryer oil from the cafeterias,
filters out the bits of fish breading and french fries, and dumps
the oil into the buses.  It works.  If the oil is free, there's no
reason not to burn it in the engines.

There are a couple of problems with doing this on a large scale, if
I understand it correctly.  The first is that oil as it's made now is
a high-grade, high-cost product, intended as food.  The second is that
the oil is quite viscous and doesn't spray well out the fuel injectors,
leading to incomplete combustion and smoke.

There's no reason not to burn used vegetable oil, after filtering it.
If you can get $1/gallon out of it instead of having to pay to have it
pumped, that's just terrific.  The other problem can be dealt with by
means of a bit of chemistry.  Mix vegetable oil, a bit of methanol and
lye, and the oil gets converted to glycerine, methyl esters of the
fatty acids, and a bit of soap-like stuff.  The glycerine pays for the
process.  You have to be careful or the unwanted byproducts may gum
up your expensive fuel-injection pump, though.

If I have enough time maybe I can dig up the Usenet article which
E. Michael Smith wrote about trying this at home.  Don't hold your
breath, my time is extremely limited.  :(

You don't get any methyl esters with that mix, for what its worth. Glycerine
is a terrible fuel, as its incomplete combustion product is acrolein, which
is *extremely* irritating. That's probably an argument against vegetable oils
themselves. I'd also venture to say that the resulting soap will gum up the
works - putting soap into a gas tank is a form of sabotage.

If you combine methanol and a fatty acid, you get a methyl ester and
water.  The glyerine is not part of the fuel fraction, it is a seperate
product (which pays for the operation).

Vegetable oils are esters of fatty acids and glycerol. With methanol
instead of glycerol, one can make methyl esters of fatty acids. However
both are easily broken down by alkalis. The reaction is called
saponification. You will not get a methyl ester of methanol and fatty acid
in an alkaline solution. To make the methyl ester of the fatty acid
requires doing it in a non-aqueous solvent (for simple esters, pure
sulfuric acid is used). This would be extremely expensive. You would be
better off burning the methanol and vegetable oil mix directly. 

In addition, recovering the glycerol from the products of saponification
is quite difficult. Normally the soaps are *precipitated* with salt, and
the solution concentrated by evaporation, when the glycerol will separate
from the concentrated salt solution. The glycerol must still be
concentrated further by evaporation. The process is conducted commercially
in the soap industry, but the product glycerol certainly doesn't pay for
the expense of doing it. Selling the soap does. So much byproduct glycerol
is produced that its market price is low.  (Incidentally, one of the
projects in my senior chemical engineering laboratory course is
concentrating glycerol in a two-effect evaporator. My students will concur
that it is difficult and inefficient.) 

The proposal seems to be to take a vegetable oil, which is difficult and
expensive to recover from the source plant, and then decompose it by
saponification to make a fatty acid, which can be converted only with
difficulty (and great expense) to the methyl ester, and expect to pay the
high cost of doing this with the relatively inexpensive byproduct
glycerol. 

Well, here are an international expert on fuels and one of Usenet's
premier experimenters, expounding on the subject.  They say you're wrong.

Here's what I saved from some postings of 2 years ago.  As you can
see, mixing methanol, vegetable oil and lye (NaOH) does indeed form
two layers, methyl esters of fatty acids and glycerol.  You *can* try
this at home.  Warning:  LONG!  267 lines follow.

From: B.Hamilton@irl.cri.nz (Bruce Hamilton)
Newsgroups: sci.energy,sci.chem
Subject: Re: Fats and Oils and Esters (oh my!) Was (Re: alternate fuel
vehicles) Date: Sun, 11 Sep 1994 08:31:15 GMT Organization: Industrial Research
Limited Lines: 146 Message-ID: <B.Hamilton.2.2E72C052@irl.cri.nz> References:
<34170i$8av@eve.adam.com.au> <CvFt7t.BDo@cygnus.com> <CvGvI1.Gx6@cygnus.com>
<34adp2$e2@golem.wcc.govt.nz> <Cvq2Iv.2L0@cygnus.com> NNTP-Posting-Host:
131.203.199.233

In article <Cvq2Iv.2L0@cygnus.com> ems@cygnus.com (E. Michael Smith) writes:
>In article <34adp2$e2@golem.wcc.govt.nz> hamilton_b@ix.wcc.govt.nz writes:
>>This has been around for ages. 
>Yes, it has.  I just didn't realize how easy it is!

Yup, the  Austrians have had several plants running for ages. There are several
plants that produce 500t/pa of rapeseed oil methyl esters and one that produces
10,000 t/pa and 1992 they were building a 15,000t/pa plant.

>>Anyone really interested in this
>>should contant the NZ Liquid Fuels Management Group ( PO Box 17 
>>Wellington N.Z.) as they financed several large scale technical 
>>evaluations and fleet trials of various esters in the 1970s. 
>I'll do that.  Can I order a generic list of reports, or is
>it necessary to order each one by report number?

You will have to specify the report number. I suspect the reports will also
be available in the US, and the copy of the final Liquid Fuels Trust Board
report LF 6020 has an ISBN of  0-478-00407-9. If you have too many problems,
email me, our library will have some of the them. They may be filed under the
Liquid Fuels Trust Board rather than LFMG.
 
>>For the
>>shorter chain ones ( butter starting at C4, coconut about
>>C6 ) then either the ethyl or butyl esters were prepared.
>How?  I could not get ethyl or iso-propyl esters to form
>at room temp with NaOH.  Did I not wait long enough or blend
>well enough?  

There are two competing reactions, the methanolysis and the
hydrolysis. If water is present ( used cooking oils are partially oxidised, and
do tend to dissolve more water. If the sample is dry, the methanolysis
is significantly faster, but if the reaction is continued for too long the
hydrolysis can dominate.

>>Their advantage over the pure oil is in the life of a
>>modern diesel engines - experience has shown that using
>>triglycerides can result in abnormal fuel/lubricant 
>>interactions that lead to early engine failure. 

>Hmmm...  What kind of 'interactions'?  If there is a report
>on this as well, I'll just order it...

The quick and diry answer is in the Journal of High Resolution Chromatography
v15 p609-612. Sept 1992  "Quality Control of Vegetable Oil Methyl Esters used
as Diesel Fuel Substitutes : Quantitative Determination of Mono-,Di-, and
Triglycerides by capillary GC " Christina Plank & Eberhard Lorbeer.
"Since incomplete tranesterification of vegetable oils can lead to significant
contamination of the vegetable oil methyl esters with MAGs,DAGs and TAGs,
continuous quality control of the product is essential. Long term engine tests
have shown that the presence of TAGs and partial glycerides and partial 
glycerides in the fuel causes serious problems through formation of engine
deposits: carbonization of the injection nozzle,piston, and valves, and 
formation of sludge in the lubrication system have been reported [ Energy
in Agriculture v2 ( 1983 ) p369 ]. The incomplete combustion of glycerides
also leads to the formation and emission of hazardous acrolein, derived from
glycerol. In Austria, a limit to the permissible levels of MAGs,DAGs, and TAGS
in rapeseed methyl esters has been introduced in std ONORM C 1190...."

This is slightly different to NZ where we specified 0.05%max. MAG.  
...
>>The problem ( its mentioned above ) is the removal of 
>>monoacylglyccerides, and much of the process optimisation

>Why do you need to remove them?  (And what conditions favor
>their formation?)  If it is just phase separation, then I'd
>think finding an additive to keep the phases mixed would be
>as easy or easier a solution?

No, it's far more complex than that - you have to balance the reaction
such that esters are favoured. Remember that you _want_ phase
separation to remove the glycerol phase. There are three possible
economic catalysts for the tranesterification. 
-Potassium carbonate, good phase separation, slower and the reaction
 doesn't seem to go as far.
-Sodium Methoxide, the method favoured by industry, and the mechanism
  is identican to NaOH. Current safety rules may adversely affect this choice.
- Sodium Hydroxide, can provide pure produvct in one batch step ( compared
   to two for the above ). Timing is critical and it has the worst phase 
   separation characteristics. It is the cheapest, so as long as the reaction 
   is controlled it works OK, but it will produce the most soar ( highly 
   undesirable as it can contaminate the product with unwanted products.).

Both sodium hydroxide, and sodium methoxide dissolve in MeOH.
None of the catalysts  would give >99% conversions without the glycerol
phase being separated. If you wish to extend diesel, then the product has
to be about 99.9+% pure.

>>work in the above reports is focussed on that. The 
>>presence of MAGs can result in temperature-related separation
>>that blocks fuel systems. 
>Hmmm... why does it 'block' the fuel system?  Is it not a 
>flamable liquid? ...

MAGs have 2 OH groups, they aren't greatly soluble in Esters.
They are high melting point  solids...

>I'm somewhat interested in knowing what reaction conditions are
>needed to make ethyl and iso-propyl esters.  Any info?

In general the increase C1,C2,C3, requires more aggressive conditions,
they are feasible, but as C1 works for common oils, they weren't 
extensively investigated.
 
>It takes about 20 minutes with sporadic simple stirring.  Maybe
>I'll try heating and blending with ethanol ...

The important point is to ensure the glycerol easily separates,
and that the reaction doesn't go too far, you can add hot water
to stop the reaction.. It's usually monitored using American Oil
Chemist's Society methods for free and combined glycerol,
acid value, and hydrolysis valves.


>>>>Maybe it is because methanol is more reactive?
>>No, it's mainly to do with viscosity, mixing, water content, and 
>>ratio of components, obviously the "reaction rate doubles for 
>>every 10C increase" rule also has a significant effect. 
>The iso-propanol was completely disolved in the cooking oil, so
>I think there was something other than mixing involved in getting 
>it to react...

Sure, but the rate of the reaction is dependent on temperature
( 50-60C about right, ratio of catalyst (  usually given as a mass% of the 
triglyceride), regardless of the solvent, and 3 moles of methanol,are required
for one mole of combined glycerol , thus 4.5 moles= 50% excess
If soap isn't considered a problem then a good procedure is refluxing
0.6% NaOH with 100% excess methanol for 30minutes, and if MAGs are
a problem then an additional treatment og ).2% NaoH will take the MAGs to
<0.2%.  

>>The important point is to avoid the production of soaps, as
>>they will give separation problems between the lower glycerol
>>layer and the upper ester layer, and they represent lost
>>product.
...
>>there should  be no fatty acids to make soap.

>Ah, but given the choice of 'disposing of a lye waste stream'
>and reacting it with a bit more oil to make some soap product ...
>I think I'll take the soap as a safer more valuable alternative.

That's not the choise, the problem is the soaps will increase the
dissolution of undesirable impurities in the esters.

                       Bruce Hamilton



Newsgroups: sci.energy,sci.chem
From: ems@cygnus.com (E. Michael Smith)
Subject: Re: Fats and Oils and Esters (oh my!) Was (Re: alternate fuel
vehicles) Message-ID: <CvpxGn.Msn@cygnus.com> Sender: news@cygnus.com
Nntp-Posting-Host: cygnus.com Organization: Cygnus Support, Mountain View, CA
References: <34170i$8av@eve.adam.com.au> <CvFt7t.BDo@cygnus.com>
<CvGvI1.Gx6@cygnus.com> <dbrewsteCvJ2yL.EH1@netcom.com> Date: Tue, 6 Sep 1994
17:19:34 GMT Lines: 97

In article <dbrewsteCvJ2yL.EH1@netcom.com> dbrewste@netcom.com (Dick Brewster)
writes: >E. Michael Smith (ems@cygnus.com) wrote: >: In article
<CvFt7t.BDo@cygnus.com> ems@cygnus.com (E. Michael Smith) writes:

>Much good stuf deleted...

Thanks!

>: The suspected excess cooking oil was subjected to additional methanol
>: and it seemed to react away to make more 'product'.  This was done
>: with excess methanol.  In this case a methanol layer remained on the
>: top (confirmed by smell and flamability), along with a lye crystal
>: layer on the bottom, with 'product' in the middle.

An addendum:  When left to sit overnight, the lye crystal layer seems to
swell and become more waxy looking.  When subjected to tactile examination
(i.e. when you stuff you hand in it while preparing to wash the sucker...)
it IS waxy.  It is also soluable in water making a slighly milky solution
and suds.  i.e. It's soap ;-)  

First Conclusion:  Don't leave the lye in overnight or you just waste lye.

Second Conclusion:  Any excess lye in the product (dust specks...) will
react to make soap that is an OK lubricant and relatively neutral chemically.

Another addendum:  When reacted with excess methanol, and left to stand for
a long time (day or two) you get a light layer of 'product' on top that
seems to be relatively good Diesel fuel analog and a heavy layer of 'stuff'
on the bottom that looks thicker and almost like yellow cooking oil.  But
it was thicker than the original oil.  Flame tests showed an alcohol flame
(after some heating).  Driving off the alcohol (i.e. watching the pretty
colors until the flame goes out ;-) left behind a sticky residue that was
water soluable with milky solution and suds.  More soap ;-)

Third Conclusion:  Excess methanol, unlike excess lye, hangs around.  You
don't want excess methanol in your Diesel injectors, so don't use excess
methanol when making methyl-esters...  

Fourth Conclusion:  Heavy layers on the bottom can NOT be concluded to
be left over un-reacted cooking oil, since they may just be an alcohol
solution of soap.

>: It would seem that there is a bit more work needed to find the best
>: proportion of methanol to cooking oil for any given oil...

I vote for excess oil... since you do not want left over methanol in
the fuel and since any excess NaOH will become soap.  Oh, and in an
excess of oil, the left over oil can be easily reacted in the next batch.

>: When I've got the time, I'm going to try this with 5 gallons of 
>: cooking oil and some racing fuel methanol, then do a long run
>: in the ol' Benz ... 

I've bought the Soybean oil.  Now I'm looking for a few gallons of 
methanol...

>An outstanding report!
>Please keep the info coming

Why, thank you ( BLUSH !) 

More info:

I got some anhydrous iso-propanol from the pharmacy.  It is completely
soluble in the soybean oil.  It also does not react.  The lye crystals
are not prone to forming soap either.  It would seem that isopropanol
is not a candidate for room temperature reaction with NaOH catalyst.

I got some pure ethanol from the pharmacy as well (denatured, but 
anhydrous).  It, too, did not react.  It also did not disolve in the
cooking oil.  The lye crystals DID form soap overnight.

There was a slight indication of contamination of the alcohol and/or
cooking oil with some minor amount of 'reactant'.  I don't know if this
was from the denaturant, or if the ethanol does make ethyl-esters, but
just at so slow a rate that the NaOH ends up in soap before much can
be made... And I'm not willing to wait days and days and ... 

I think there is the potential to use ethanol, given some book time
looking for reaction rates and favorable conditions (heating?).

In Conclusion:  It looks like the 'best' process (so far!) is to use
an excess of cooking oil (I'd suggest about 15% by mass of methanol)
and crystalline lye; mixed and left to stand for about 1 hour; with
a stirring or shakeing every 10 minutes or so.  Then decant the 
product and any left over cooking oil, and start a new batch.
Discard the lye at the end of the day (or go ahead and let it sit
overnight to make soap.  It wasn't half bad soap ...  ;-)

Next:  Making a BIG batch and driving to work on it.  
Probably next weekend's project ...   'Kitchen Science' is Soooo much fun ;-)

-- 

E. Michael Smith
Manager of Stuff
Cygnus Support

Sigh...there you go again - wanting free consulting.

If that's your only response, I don't think you read #16 in the context
of your #15.

The problem really is that #16 is so long. It would require real time to
study, more than to just read and respond on line. I read incorrect
statements in it as it streamed by, but it would require an effort to
respond properly to each. One thing though - the original statement of the
proposal was misleading relative to what appears to be suggested in the
"long" version. 

The thumbnail sketch of #16 is that:
1.)  Esterification of liquid vegetable oils does occur with MeOH and NaOH,
     at room temperature.
2.)  Among other entities, the government of Austria does this at pilot scale.
3.)  People have done this at a kitchen scale as well.

And since the methyl esters make halfway decent diesel fuel, the
question in #0 is answered pretty well also.

I have now read through post #16. There is no evidence there that
transesterification occurs in the proposed mixtures. The descriptions of
what these kitchen khemists observe would agree with there being a
methanol layer on top, an unreacted vegetable oil layer in the middle, and
a lye/soap/micelle layer on the bottom.

I found web sites concerning the above claims, but their domain,
billboard.com, is inaccessible. 

I also found information on the web that European countries are making
methyl esters of rapeseed (canola) oil for diesel fuels. I did not find a
detailed process description. This would appear to be a subsidization of
agriculture (as fuel ethanol is in the US). 

The state of California seems to support some studies of this. I found at
http://www.energy.ca.gov/energy/abcafv/chap09/chapter09.html a general
description of the process, as follows: 

"The fuel is made by a catalytic chemical process called
trans-esterfication, using an alcohol (such as methanol) and a catalyst. 
Methanol is mixed with sodium hydroxide and then with soybean oil, letting
the glycerine that is formed to settle. This forms fatty esters which is
then separated into two phases, which allows easy removal of glycerol in
the first phase. The remaining alcohol/ester mixture called methyl soyate
is then separated and the excess alcohol is recycled. The ester are sent
to the clean-up or purification processes which consists of water washing,
vacuum drying and filtration." 

This is, to a chemist, "hand waving" and more promotional than
informative. 

So, cite specific chemical reactions used, and their reaction conditions,
from professional or refereed journals, and we'll have something to
discuss.

I found the Mother Church of the biodiesel lobby at
http://www.ag.uiuc.edu/~nbb/fuelfacts.html You have to read between the
lines to figure out what is going on, but what that appears to be is to
sell the government on the idea of using fatty acid methyl esters -
biodiesel - so they will buy it for government vehicles, thereby
indirectly subsidizing the soybean industry. They do report a cost
estimate: 

"Biodiesel costs rank well with other alternatives. The cost of biodiesel
depends on the market price for vegetable oil.  In general, biodiesel
blended at a 20 percent level with petroleum diesel costs 30 - 40 cents
per gallon more than just diesel. Given the other advantages of biodiesel,
though, an emission management system with biodiesel is a least-cost
alternative. A study by Booz-Allen & Hamilton, Inc., found fleets using a
20 percent biodiesel blend would experience lower total annual costs than
other alternative fuels."

If we take diesel oil to cost $1.00 per gallon, the oil price is $0.80 in
that gallon of 20% ester mix, which will cost ca. $1.35 per gallon. That
makes the ester price $2.75 per gallon. I would look into that claim of
"lower total annual costs" *very* carefully. 

There is another disturbing aspect of this hype, which is similar to the
one for fuel ethanol. Both proposals use *foodstuffs* to convert to motor
fuels, in a world with widespread famine and starvation. Yes, I know its
all economics....much to our discredit. 

Found some information on transesterification, in fact for vegetable oil
and methanol. It can be conducted in the absence of water using a strong
Lewis acid such as BF3 as the catalyst. Water - and certainly "lye" -
would stop the reaction and saponify the oil. Separating the reaction
products is a bit of a chore, though, as there will be an equilibrium
between methanol, the oil (triglyceride), the methyl ester, and glycerol.
I have not found precise conditions and reaction product compositions, or
the thermochemistry from which to calculate these. (And I'm not making a
project out of this - unless someone wants to front the venture capital). 

        So, the gist of it is that it:

        1) it is feasible;
        2) it can be developed further;
        3) it reduces the need for petroleum, but doesn't fully replace
           the need for oil?

        #3 may be my conclusion on the last few postings, so I might be
        off again.

        As far as feeding the world, forget it... Tanstaffl - they can buy
        the stocks or they can grow their own.. This is one of the reasons
        I was wondering in the first place: being dependent upon foreign
        reserves is damn near insane in this day and age..

        Interesting... All the references are basically University or
        State Studies.. Nothing from the feds (I think I saw none) and, of
        course, nothing from the Oil Companies.. Interesting.

How about eat the food and walk or bicycle instead of sitting in a motor
driven vehicle?  (I know.  Been there, done that.)

In the USA it appears biodiesel would come mostly from soy beans. The meal
that is left after the oil is expressed is a protein rich food, and used I
think mostly for cattle - or tofu. 

The oil companies are not likely to get into biodiesel - though they have
a large investment in the fuels needed for the cultivation machinery. (I was,
in fact, wondering whether the diesel oil required to cultivate the crop
might not exceed the biodiesel fuel obtained from the crop - just a thought.)

In regard to your "gist": 

1. Yes, it is feasible. That is, the chemical process can be carried out. The
reason for the chemical processing is essentially to remove the glycerol,
which forms gums and produces noxious combustion products. However, it is very
expensive. Coal liquifaction would be cheaper.

2. It will be devloped further if the biodiesel obby has any say in the
matter.  8^}

3. I suspect that converting all the vegetable oil that *could* be produced
nationally, would replace only a small fraction of the current fuel
consumption. That's a guess: I'd be interested in the numbers. I think
this is why the biodiesel lobby is fishing for only 20% of the diesel fuel
alternative market. 

One condition of economy for biodiesel is that there is a market for the
rest of the soy bean. It is a fine protein source, but if we produce all the
biodiesel fuel we can, we will not have a domestic market for that much
soy meal, so would have to find overseas markets. So, to balance that trade,
it is logical to buy cheaper petroleum fuels from overseas. The fact is, the
whole world is inescapably connected, and there is no hope of being fuel
independent anymore.

  As long as we'd be curbing free market forces, and subsidizing certain
industries, we could ban beef consumption, which would drive up domestic
soy demand.  A lot of US beef is imported from South America, so this
would further efforts at a closed market economy.  Cattle also use a lot
of farmland which could otherwise be used to produce crops for human
consumption or biodiesel fuel.

Sort of a choice between steaks or cars - only in America.

        Yeah, I can see banning cattle... After all, they only use about
        0.1% of the materials that mariculture like Tuna require ;-)

        I dunno, guys.. I think the numbers are waay skewed, and I've
        never suggested using soybeans, myself. However, even if reduces
        the imports by that 20%, it sounds worthy of investigation.

        Same with methanol-based fuels.. Besides, if ya break down in the
        boonies, you can always throw a party - the potables are in the
        tank ;-)

        Say, <efg> we could swap soya-meal for Indian cattle! <chuckle>


        Still and all, what other alternatives have we got to BURNING the
        very petroleum we depend upon for lubricants, synthetics, etc?

        What else is proposed "out-there"? Are we supposed to wait a
        couple milennia for new petroleum deposits? Granted, we might
        someday manage Fusion, and we can bootstrap Rickenbacher Reactors
        immediately, but what are we gonna' be driving..? A bank of
        12-volt batteries..? (Then, you also have to set up the
        'hitching-posts' to charge them as well.) Are we going to strap
        wheels on sail-boards?

Conservation would serve for quite a while to slowly reduce our energy
consumption. The whole shebang - smaller cars, lower speeds, cooler homes
in winter and warmer homes in summer, and many other similar things. But
America doesn't *want* to. The temporary solutoin is staring us in the
face, but it would be "inconvenient". If American's are so greedy, they
rather deserve having a future energy disaster. 

        "America" is also hamstrung..

        Known for years that underground homes would save up to 70% of
        energy for heat/cool, but building codes refuse to allow such
        construction <shrug>.

        Preformed & insulated wall-panels are available, without any wood
        used throughout.. Modular as well.. Costs are too high and, while
        perfect for underground interior walls at the least, they are not
        acceptable to many building code regs.

        Blaming "America" is real handy, when there are Politico's and
        Lobbies and even "nature-lovers" and "industrial-abuse" folks
        that contribute..


        Always wanted to build underground; always liked the efficiencies.
        Always stymied by the codes..

There's an earth (half-buried) house right down the street from me, is that
what you are talking about?

BTW, a local building inspector was featured in the Observer recently.  He
mentioned that A2 has the most clay of some type in the world, and whenever
you build a house you have to do really good waterproofing to compensate for
the lack of natural drainage thru the soil.

        Essentially: the "half-buried" is what the codes will allow,
        though.

        Most of michigan is sand, rock/gravel or clay.. Love dem Glaciers!

The only preformed and insulated panels I've run across is the stuff where
styrofoam is sandwiched between two sheets of OSB.  Stress skin, R control,
insulated panels, or whatever.  I suspect one could do the same with other
materials beside OSB but you may then have to use some sort of posts & beam
construction to take the load.  An architect just down the street from
us put an addition on his house using R Control panels.  For some reason
the project has been in stagnation since the middle of summer.  Code or $
problems, I suspect.  His exposed OSB is starting to turn gray.  Not good.

Hi.  I'm sort of back.  No time to respond to the above for a little while.

Back to this, writing off-line....
 
Re #22:  Of course, the agricultural lobby is pitching the concept
based on use of virgin oils.  That's where the $2.75/gallon estimate
comes from, I'm certain.  However, there are other possibilities:
 
1.)  Turn waste oils into fuel.  If the input oil stream is close to
free and the processing is inexpensive, the bio-diesel could be quite
economical.  For instance, if waste fryer oil is $.10/gallon, methanol
is $2.00/gallon, processing is $.20/gallon of product and each gallon
of product requires 1 gallon of oil and 1/10 gallon of methanol, then
the resulting fuel costs $.50/gallon.  This is quite competitive.
 
This is inherently a small-scale technology.  Even potato-chip operations
probably cannot support a very large fleet of bio-diesel vehicles.
It also doesn't have a political constituency, since waste oil doesn't
increase farm sales.
 
2.)  Use oils from plants which are highly productive, but aren't
currently grown for food.  Since I'm not a botanist I don't know of
many candidates, but the existence of jojoba and hemp are suggestive.
 
Re #23:
>Water - and certainly "lye" -
>would stop the reaction and saponify the oil.
 
Okay, if that's your judgement, fine.  I believe the advocates on
this one and I'm sure I can scare up some scholarly evidence, given
a couple of weeks of M-Net being up.  Would you care to make a small
wager?  Suggest your prize.  If I win, I want your sneer for a month.
 
Re #29:  If you drink *methanol*, Pete, you're going to have a hell
of a hangover.  Go to bed blind drunk, wake up just plain blind....
if memory serves, the same liver enzyme which metabolizes ethanol to
acetyldehyde turns methanol into formaldehyde.  How well-preserved
do you want to be?  :/

Re #34:  On "This Old House" a season or two ago, one of the featured
projects was a barn.  It was nearly unsalvageable, so an essenanew building w
lsnarihlfootprint and shape.  Talwto s- panels, with skins of something like
plywood and foamed urethane in the middle.  The machine making the panels was
quite impressive; two continuous sheets of plywood slide in, a belt blocks the
sides, and a spray bar mixes the foam at the input end.  The foam expands and
hardens by the other end of the machine, where a saw clamps to the moving
panel-stuff and cuts it to length.  The pieces are stacked and move off on fork
trucks.  I'm not sure if the panels came to the site skinned with drywall or
not, but it would be a great time-saver.

The desired reaction is 

     GR3  +  3 MeOH  =  G(OH)3  +  3 MeR

where G is glyceryl, R is the fatty acid, and MeOH is methanol. The
molecular weight of GR3 is (depending on the oil) ca. 880, while that of
MeOH is 32, so the weight ratio of methanol to oil required is 96/880,
which is where Russ gets a volume ratio of about 1/10. However the
economic problems do not reside so much in the cost of methanol. 

The chemical problem is that that reaction is an equilibrium and does not
go to completion. Therefore an excess of methanol is used during reaction,
and the separation of purification of the MeR is complex and expensive.
This probably competes with the price of the oil itself in making the
product expensive. [I have not obtained the technical information on the
equilibrium, though I did find this reaction described as a laboratory
demonstation.]

A major cost in the "used cooking oil" scenario, is the collection system
required. Handling and transportation make up a large fraction of the cost
of everything, and the small lots of oil that would be collected would
drive up costs. Of course, only a complete economic analysis would put
numbers on this. 

In regard to the chemistry, I did find a mention that sodium methoxide is
a catalyst for the interesterification - though the book did say
"surprisingly".  Nevertheless, the reaction must be conducted in the
absence of water. Any water present will lead to saponification and loss
of the desired product.  I will accept your wager on this point. Our
"honors" are the stake. 

I am not saying it can't be done. It is done, in Europe, as a highly
subsidized process, much like the highly subsidized US fuel-ethanol
program (which has just run into some price fixing scandals by the primary
recipient of the government largess). What I am saying is that it is not a
viable alternative fuel for anything more than an expensive adjunct for a
small part of our fuel requirements. 

I found Bruce Hamilton and sent him a short question.  This is his reply:

From: B.Hamilton@irl.cri.nz
Date: Thursday, November 07, 1996 4:32AM

> Do you recall the methyl esterization thread of a year or
> two ago?  Would you have any scholarly-type references
> handy to describe the chemistry of the MeOH+NaOH version
> of the reaction?  I have a skeptic on my hands and no
> way to do database searches on chemical abstracts.

I recently inherited a number of US Dept of Agriculture
reports on the reactions, and I intend to add them to the
sci.chem FAQ when I get time. They are at home, so I'll try to
dig them out and send you the references, but one of the
best discussing the mechanisms of transesterification are the
papers by Bannon et. al. in Chromatography journals
eg "Literature Review of and Investigations into the development
of rapid procedures for the methoxide-catalysed Methanolysis
of Fats and Oils. J.Chromatography. v.247 p71-89 ( 1982 )
Also the book "Lipid Analysis" by W.W.Christie goes into
the mechanisms in detail. Peter Bain's paper referred to below
is also a good source, but it's probably not readily available.

[ From the sci.chem FAQ ]
27.8  How can I convert cooking oil into diesel fuel?

Diesel engines can run on plant and animal triglycerides such as
tallow and seed oils, however most trials have resulted in reduced
engine life, or increased service costs. The solution is to
transesterify the triglyeride into esters, taking care to avoid the
formation of monoacylglycerides that will precipitate out at low
temperatures or when diesel is encountered. There are several plants
in Austria that produce Rapeseed Oil Methyl Esters as fuels for diesel
engines. The economics of the process are very dependant on the price
of diesel and the market for the glycerol byproduct.

The common catalysts used to transesterify triglyerides are sodium
hydroxide, sodium methoxide and potassium carbonate. If the esters are
to be blended with diesel fuel, then a two stage reaction is usually
required to ensure monoacylglycerides are kept below 0.05%. Usually
this involves using 22g of methanol ( containing 0.6g of sodium
hydroxide ) and 100g of tallow refluxed for 30 minutes. The mixture is
cooled, the glycerol layer removed, and a further 0.2g of sodium
hydroxide is reacted for 5 minutes at 35C in a stirred reactor. The
glycerol phase is allowed to separate, and the ester phase is washed
with water to remove residual catalyst, glycerol and methanol. Note
that sodium hydroxide is the most cost-effective catalyst, but has the
worst tendency to form soaps. The catalyst and methanol can be
industrial grade without further processing, however care should be
taken to prevent additional water entering the reaction. [10].

The fuel can be converted into other esters, such as ethyl and butyl,
but it really depends on the availability of cheap alcohol along with
the desired properties of the fuels. The New Zealand government
investigated a wide range of techniques for turning various vegetable
and animal triglycerides into esters for diesel, and the reports cover
many aspects of the kinetics and efficiencies [11]. There is a general
overview of the current processes and technology available in Inform
[12]. A specific techniques for analysing the monoglycerides has been
published [13], however I have found that acetylation followed by
narrow bore ( 0.1mm ID ) capillary chromatography is faster and
cheaper.

[10] The Methanolysis of Tallow
     P.J.S.Bain
     Report of Investigation 2590 (1988)
     DSIR. PO Box 31-310, Lower Hutt, New Zealand.

[11] NZ Liquid Fuels Trust Board Reports LF1199 - LF1210
     Available ( for a fee ) from Liquid Fuels Management Group
     Limited P.O.Box 17, Wellington, New Zealand.

[12] Evaluating Vegetable Oils as a Diesel Fuel
     T.Murayama
     Inform v.5 p.1138-1145 (1994)

[13] Quality Control of Vegetable Oil Methyl Esters used as Diesel Fuel
     Substitutes: Quantititative determination of mono-, di-, and
     triglycerides by Capillary GC. C.Plank and E.Lorbeer J. High
     Resolut. Chromatog. v.15 p.609-612. (1992)

- Backtalk version 1.3.30 - Copyright 1996-2006, Jan Wolter and Steve Weiss