Re: [biofuels-biz] Re: hi ffa feed stocks

2002-09-08 Thread Appal Energy

Why not just drain off the small amount of glycerine (will also
contain some water) from the bottom of the esterification
reaction and decant the excess alcohol off the top (which will be
slightly glycerin stained and also contain some water)?

After doing so, you'll find that the transesterification can take
place with as little as 1-1.5 grams of sodium or potassium
catalyst if given enough alcohol and time.

No need to boil between acid and base stages.

Todd Swearingen

- Original Message -
From: David Teal <[EMAIL PROTECTED]>
To: 
Sent: Friday, September 06, 2002 4:44 PM
Subject: Re: [biofuels-biz] Re: hi ffa feed stocks


> One fact in common to all the recent contributors to this
thread has been
> the bad effects of water produced in the acid esterification of
FFAs;
> including saponification in the subsequent base
transestrification stage.
> Most of us like to keep things simple, so I contemplate a
boiling operation
> between acid and basic stages to evaporate the unwanted water.
This would
> apply to our Scottish lard chip fat supply.  The energy burden
need not be
> too onerous using heat exchangers to recover some of the
sensible heat
> (latent heat can't be easily recovered), and by using glycerol
as heating
> fuel.  I am a little worried about what boiling sulphuric acid
(albeit
> dilute at this stage) will do to ordinary piping and vessel
materials.
>
> David T.
>
>
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Re: [biofuels-biz] Re: hi ffa feed stocks

2002-09-07 Thread David Teal

One fact in common to all the recent contributors to this thread has been
the bad effects of water produced in the acid esterification of FFAs;
including saponification in the subsequent base transestrification stage.
Most of us like to keep things simple, so I contemplate a boiling operation
between acid and basic stages to evaporate the unwanted water.  This would
apply to our Scottish lard chip fat supply.  The energy burden need not be
too onerous using heat exchangers to recover some of the sensible heat
(latent heat can't be easily recovered), and by using glycerol as heating
fuel.  I am a little worried about what boiling sulphuric acid (albeit
dilute at this stage) will do to ordinary piping and vessel materials.

David T.


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Re: [biofuels-biz] Re: hi ffa feed stocks

2002-09-05 Thread Michael Allen

Dear Keith,

> Actually I did understand this, having checked it
> out a bit and 
> discussed it with a few people, but I understand it
> even better now - 
> thanks! What puzzled me and mainly why I asked was
> what you said 
> about methanol excesses. For the whole process,
> Aleks uses rather 
> less methanol than you'd probably have to use for
> high-ffa feedstock 
> by most other methods, especially single-stage base.
> Overall methanol 
> use, not just for the esterification first stage, is
> about 67% 
> excess, depending on the oil; your 9 to 12 times
> applies to the first 
> stage only. Well, that's all clear now.

Sorry if I mislead you in any way.
 
> By the way, there are tables showing the
> stoichiometric ratios for 
> different oils here:
> http://journeytoforever.org/biodiesel_meth.html
> How much methanol?
> 
> Re the condenser, that's one way, but it's hard to
> separate the 
> glycerine/FFAs/catalyst in the glycerine layer with
> the methanol 
> already removed. Maybe a better way is to drain off
> the glycerine 
> layer first, then evaporate off the excess methanol
> in the biodiesel 
> (it's about half-half in the biodiesel and the
> glycerine layer). 

We do indeed drain the glycerol from the biodiesel in
the reactor and we have even tried doing this while
the reaction is proceeeding as suggested by Aleks.
Theoretically, the removal of a product should push
the reaction to produce more product (Le Chatelier's
Principle) but we have not yet measured any benefits.

> After separating the glycerine layer 
>
(http://journeytoforever.org/biodiesel_glycsep.html),
> the rest of the 
> excess methanol can be recovered from the purified
> glycerine 
> (somewhat purified glycerine).

At present, we are setting the glycerol in trays and
using it as a soap and general grease remover around
the workshop. However . . . . one day . . .
 
> I'd appreciate a picture and diagrams, if that's not
> too much trouble, thanks.

Our Internet link is really running slowly at present
with many disconnections. I will try over the weekend
when traffic is less.

> So you are using the acid-base process as your main
> method, with both 
> the 100-l and the 1-tonne reactors? 

No. The 1 tonne reactor continues to use the
base-catalysed transesterification of molten
stearine/palmitin. The FFA of this feedstock is quite
low (less than 1%). 

We are exploring the acid-base process with HiFFA
feedstocks in the smaller reactor and in the
laboratory. We know that the process of refining the
crude palm oil reduces the FFA  to <0.5% by a process
of saponification using an almost stoichiometric
amount of sodium hydroxide dissolved in water. But the
resultant soap is largely a waste material.

Some of our crude palm oil comes in at 10%FFA and the
saponification process produces rather a lot of greasy
soap from such a feedstock. Even the palm-oil refiners
don't like this stuff (which is, of course, why it
easily procurable!) By adjusting the temperature, we
can remove this soap from the bottom of the
saponification reactor rather than skimming it off the
top but we still lose too much oil to make it an
attractive option.

Using Alek's acid-base process on such a feedstock has
the potential to replace this useless soap with methyl
ester. But it appears that any ester actually formed
with the acid catalyst is subsequently broken down and
saponified along with the palm oil in the
base-catalysed second reaction. The result is a spongy
mass of soap which is hard to separate from any methyl
ester which may have been formed. The main culprit is,
I believe, the water which was formed in the
saponification process. (But I could be wrong)

We haven't given up entirely on the 10% FFA feedstock 
but we are going to concentrate our immediate research
on the more usual and widely available 5% FFA crude
palm oil. 

>Some people have
> been having 
> trouble using it with crude palm oil
> (high FFA and high percentage of stearin), but not
> with olein palm oil.

We are "some people"!!
But we find that olein goes like a dream! We have even
put together a simple powered-roller reactor which
mixes the methoxide with the olein at ambient
temperature (30 degC) and takes less than 15 minutes
to form the ester. But we haven't tried olein with
HiFFA (yet). 

Any ideas would be welcome

Regards

Michael Allen

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Re: [biofuels-biz] Re: hi ffa feed stocks

2002-09-05 Thread Michael Allen

Dear Keith,

> Actually I did understand this, having checked it
> out a bit and 
> discussed it with a few people, but I understand it
> even better now - 
> thanks! What puzzled me and mainly why I asked was
> what you said 
> about methanol excesses. For the whole process,
> Aleks uses rather 
> less methanol than you'd probably have to use for
> high-ffa feedstock 
> by most other methods, especially single-stage base.
> Overall methanol 
> use, not just for the esterification first stage, is
> about 67% 
> excess, depending on the oil; your 9 to 12 times
> applies to the first 
> stage only. Well, that's all clear now.

Sorry if I mislead you in any way.
 
> By the way, there are tables showing the
> stoichiometric ratios for 
> different oils here:
> http://journeytoforever.org/biodiesel_meth.html
> How much methanol?
> 
> Re the condenser, that's one way, but it's hard to
> separate the 
> glycerine/FFAs/catalyst in the glycerine layer with
> the methanol 
> already removed. Maybe a better way is to drain off
> the glycerine 
> layer first, then evaporate off the excess methanol
> in the biodiesel 
> (it's about half-half in the biodiesel and the
> glycerine layer). 

We do indeed drain the glycerol from the biodiesel in
the reactor and we have even tried doing this while
the reaction is proceeeding as suggested by Aleks.
Theoretically, the removal of a product should push
the reaction to produce more product (Le Chatelier's
Principle) but we have not yet measured any benefits.

> After separating the glycerine layer 
>
(http://journeytoforever.org/biodiesel_glycsep.html),
> the rest of the 
> excess methanol can be recovered from the purified
> glycerine 
> (somewhat purified glycerine).

At present, we are setting the glycerol in trays and
using it as a soap and general grease remover around
the workshop. However . . . . one day . . .
 
> I'd appreciate a picture and diagrams, if that's not
> too much trouble, thanks.

Our Internet link is really running slowly at present
with many disconnections. I will try over the weekend
when traffic is less.

> So you are using the acid-base process as your main
> method, with both 
> the 100-l and the 1-tonne reactors? 

No. The 1 tonne reactor continues to use the
base-catalysed transesterification of molten
stearine/palmitin. The FFA of this feedstock is quite
low (less than 1%). 

We are exploring the acid-base process with HiFFA
feedstocks in the smaller reactor and in the
laboratory. We know that the process of refining the
crude palm oil reduces the FFA  to <0.5% by a process
of saponification using an almost stoichiometric
amount of sodium hydroxide dissolved in water. But the
resultant soap is largely a waste material.

Some of our crude palm oil comes in at 10%FFA and the
saponification process produces rather a lot of greasy
soap from such a feedstock. Even the palm-oil refiners
don't like this stuff (which is, of course, why it
easily procurable!) By adjusting the temperature, we
can remove this soap from the bottom of the
saponification reactor rather than skimming it off the
top but we still lose too much oil to make it an
attractive option.

Using Alek's acid-base process on such a feedstock has
the potential to replace this useless soap with methyl
ester. But it appears that any ester actually formed
with the acid catalyst is subsequently broken down and
saponified along with the palm oil in the
base-catalysed second reaction. The result is a spongy
mass of soap which is hard to separate from any methyl
ester which may have been formed. The main culprit is,
I believe, the water which was formed in the
saponification process. (But I could be wrong)

We haven't given up entirely on the 10% FFA feedstock 
but we are going to concentrate our immediate research
on the more usual and widely available 5% FFA crude
palm oil. 

>Some people have
> been having 
> trouble using it with crude palm oil
> (high FFA and high percentage of stearin), but not
> with olein palm oil.

We are "some people"!!
But we find that olein goes like a dream! We have even
put together a simple powered-roller reactor which
mixes the methoxide with the olein at ambient
temperature (30 degC) and takes less than 15 minutes
to form the ester. You can even shake them together
manually. But we haven't tried olein with HiFFA (yet).


Any ideas would be welcome

Regards

Michael Allen

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Re: [biofuels-biz] Re: hi ffa feed stocks

2002-09-02 Thread Keith Addison

Hi Michael

>(Sorry to be a tad pedantic and maybe a bit
>long-winded but it sort of goes with the patch as a
>Visiting Professor here in Thailand!)

Not at all, not long-winded, nice clear explanation, I'm sure a lot 
of people will appreciate that.

Actually I did understand this, having checked it out a bit and 
discussed it with a few people, but I understand it even better now - 
thanks! What puzzled me and mainly why I asked was what you said 
about methanol excesses. For the whole process, Aleks uses rather 
less methanol than you'd probably have to use for high-ffa feedstock 
by most other methods, especially single-stage base. Overall methanol 
use, not just for the esterification first stage, is about 67% 
excess, depending on the oil; your 9 to 12 times applies to the first 
stage only. Well, that's all clear now.

By the way, there are tables showing the stoichiometric ratios for 
different oils here:
http://journeytoforever.org/biodiesel_meth.html
How much methanol?

Re the condenser, that's one way, but it's hard to separate the 
glycerine/FFAs/catalyst in the glycerine layer with the methanol 
already removed. Maybe a better way is to drain off the glycerine 
layer first, then evaporate off the excess methanol in the biodiesel 
(it's about half-half in the biodiesel and the glycerine layer). 
After separating the glycerine layer 
(http://journeytoforever.org/biodiesel_glycsep.html), the rest of the 
excess methanol can be recovered from the purified glycerine 
(somewhat purified glycerine).

I'd appreciate a picture and diagrams, if that's not too much trouble, thanks.

So you are using the acid-base process as your main method, with both 
the 100-l and the 1-tonne reactors? Some people have been having 
trouble using it with crude palm oil
(high FFA and high percentage of stearin), but not with olein palm oil.

Thanks again, best wishes

Keith



>Hi Keith,
>
>In answer to your question:
>
>Lets start with a litre of oil.
>Ours has a density of 910.9 grams/litre so a Free
>Fatty Acid content of 5% on a weight basis means that
>5% of that 910.9 grams is FFA
>
>So one litre of oil with a FFA content of 5% (weight
>basis) contains 45.55 gms of FFA
>
>The chemical reaction of esterification is
>
>   H+
>R-COOH + CH3OH <=> CH3-OOC-R + H2O
>
>In other words, 1 molecule of acid reacts with one
>molecule of alcohol to give one molecule of ester plus
>one molecule of water .
>
>Using the molecular weights and choosing palmitic acid
>as the predominant fatty acid, we get that
>
>256.42 grams of palmitic acid needs 32.04 grams of
>methanol to produce 18 grams of water and 270.5 grams
>of methyl palmitate.
>
>so 45.55 grams will need 32.04 x 45.55/256.42 = 5.69
>grams of methanol
>
>Taking 791 grams/litre as the density of methanol,
>this means that we need to have a minimum 5.69/791
>litres of methanol available for the reaction to go to
>completion.
>
>This is only 0.007 litres!
>
>So why do we add 0.08 litres of methanol per litre of
>oil as set out in "First stage para 4" of Aleksander
>Kac's
>http://journeytoforever.org/biodiesel_aleksnew.html?
>
>Well the <=> sign in the above equation is to show
>that it is reversible. That is, if we take the ester
>and add some water in the presence of a strong acid,
>we get some free fatty acid formed and some alcohol.
>(This method is actually used in the analysis of
>unknown fats and oils )
>
>The main reason we add excess methanol (about ten
>times as much as the stoichiometric amount needed) is
>to force the reaction further in the direction we want
>it go. Removing the water has the same effect so using
>concentrated sulfuric acid as the catalyst also helps
>the reaction move over to the right  because it is
>really great at dehydrating things like sugar and
>human flesh . . . . . . . . :-(
>
>But, as I suggested in my note, the excess methanol
>also dilutes whatever water is left at the end of the
>esterification reaction. (And we are going to need
>that methanol for the transesterification stage
>anyway). When we neutralise that sulfuric acid with
>sodium hydroxide, we make sodium sulfate which does
>not bond to water quite as strongly as the sulfuric
>acid so, as a consequence, I suspect that the water
>activity probably increases.
>
>Incidentally, you can make the same calculation for
>any fatty acid found in vegetable or animal oils and
>you will find that between 9 and 12 times the minimum
>stoichiometric amount of methanol is used in the
>Aleksander Kac esterification process.
>
>For similar reasons, the transesterification process
>also uses excess methanol: 0.2 litres of
>methanol/litre of oil is about 1.7 times the
>stoichiometric amount needed and 0.25 litres of
>methanol/litre of oil is about twice the minimum
>amount needed. (Aleksander Kac's two methods). You get
>slightly different results if you cover all the
>possible mono-glycerides, di-glycerides,
>tri-glycerides of all the fatty acids but the above
>figures are quoted for 

Re: [biofuels-biz] Re: hi ffa feed stocks

2002-09-01 Thread Michael Allen

Hi Keith,

In answer to your question:

Lets start with a litre of oil. 
Ours has a density of 910.9 grams/litre so a Free
Fatty Acid content of 5% on a weight basis means that
5% of that 910.9 grams is FFA

So one litre of oil with a FFA content of 5% (weight
basis) contains 45.55 gms of FFA

The chemical reaction of esterification is 

H+
R-COOH + CH3OH <=> CH3-OOC-R + H2O

In other words, 1 molecule of acid reacts with one
molecule of alcohol to give one molecule of ester plus
one molecule of water .

Using the molecular weights and choosing palmitic acid
as the predominant fatty acid, we get that 

256.42 grams of palmitic acid needs 32.04 grams of
methanol to produce 18 grams of water and 270.5 grams
of methyl palmitate.

so 45.55 grams will need 32.04 x 45.55/256.42 = 5.69
grams of methanol

Taking 791 grams/litre as the density of methanol,
this means that we need to have a minimum 5.69/791
litres of methanol available for the reaction to go to
completion.

This is only 0.007 litres!

So why do we add 0.08 litres of methanol per litre of
oil as set out in "First stage para 4" of Aleksander
Kac's
http://journeytoforever.org/biodiesel_aleksnew.html?

Well the <=> sign in the above equation is to show
that it is reversible. That is, if we take the ester
and add some water in the presence of a strong acid,
we get some free fatty acid formed and some alcohol.
(This method is actually used in the analysis of
unknown fats and oils )

The main reason we add excess methanol (about ten
times as much as the stoichiometric amount needed) is
to force the reaction further in the direction we want
it go. Removing the water has the same effect so using
concentrated sulfuric acid as the catalyst also helps
the reaction move over to the right  because it is
really great at dehydrating things like sugar and
human flesh . . . . . . . . :-(

But, as I suggested in my note, the excess methanol
also dilutes whatever water is left at the end of the
esterification reaction. (And we are going to need
that methanol for the transesterification stage
anyway). When we neutralise that sulfuric acid with
sodium hydroxide, we make sodium sulfate which does
not bond to water quite as strongly as the sulfuric
acid so, as a consequence, I suspect that the water
activity probably increases.

Incidentally, you can make the same calculation for
any fatty acid found in vegetable or animal oils and
you will find that between 9 and 12 times the minimum
stoichiometric amount of methanol is used in the
Aleksander Kac esterification process.

For similar reasons, the transesterification process
also uses excess methanol: 0.2 litres of
methanol/litre of oil is about 1.7 times the
stoichiometric amount needed and 0.25 litres of
methanol/litre of oil is about twice the minimum
amount needed. (Aleksander Kac's two methods). You get
slightly different results if you cover all the
possible mono-glycerides, di-glycerides,
tri-glycerides of all the fatty acids but the above
figures are quoted for glyceryl tri-palmitate which is
one of the major components in our oil feedstock.

This is why I feel that a condenser on the outlet of
the reactor is a useful way of saving money. And
because chemical reactions go faster at higher
temperatures, we can carry out the reaction at a
temperature closer to the boiling point of methanol
(64.6C) by refluxing all the condensed methanol back
into the reactor until the reaction is finished. At
present we use a simple copper-pipe heat exchanger and
we totally recycle the cooling water through two x 200
litre oil drums working as an evaporative cooler by
having a sprinkler over three perforated baking trays.
(I'll send you a picture and some plans if you like.)

We have assessed the advantages of a condenser with
our 100 litre reactor and, as a result, we our
currently modifying the 1 tonne reactor used for
making biodiesel from stearin. (This 1 tonne unit is
the reactor which produces biodiesel for the railway
trials)

(Sorry to be a tad pedantic and maybe a bit
long-winded but it sort of goes with the patch as a
Visiting Professor here in Thailand!)

Best wishes

Michael Allen


--- Keith Addison <[EMAIL PROTECTED]> wrote:
> Hello Michael
> 
> 
> 
> >Incidentally, with respect to the high free fatty
> acid
> >feeds, the limit to the amount of FFA possible is
> >probably related to the formation of water in
> Alek's
> >first stage esterification using sulfuric acid as
> the
> >catalyst. Thus 5%FFA in the oil means that 4mls of
> >water are produced for every litre of oil. This
> water
> >increases soap formation in the second stage (which
> is
> >catalysed by sodium hydroxide).
> 
> I know about the water, that'd be about right. But I
> don't know about this:
> 
> >Alek Kak's method
>
>(http://journeytoforever.org/biodiesel_aleksnew.html)
> >reduces this impact by using 95% pure sulfuric acid
> >which has a strong affinity for water. He also
> >recommends about 9 times the amount of methanol
> >theoreti

Re: [biofuels-biz] Re: hi ffa feed stocks

2002-08-29 Thread Keith Addison

Hello Michael



>Incidentally, with respect to the high free fatty acid
>feeds, the limit to the amount of FFA possible is
>probably related to the formation of water in Alek's
>first stage esterification using sulfuric acid as the
>catalyst. Thus 5%FFA in the oil means that 4mls of
>water are produced for every litre of oil. This water
>increases soap formation in the second stage (which is
>catalysed by sodium hydroxide).

I know about the water, that'd be about right. But I don't know about this:

>Alek Kak's method
>(http://journeytoforever.org/biodiesel_aleksnew.html)
>reduces this impact by using 95% pure sulfuric acid
>which has a strong affinity for water. He also
>recommends about 9 times the amount of methanol
>theoretically needed to react with the FFA. This also
>has the effect of reducing the water concentration.

It uses 8% methanol v/v oil for the acid stage, and 12% for the 
second stage. You're saying acid esterification of 5% FFAs needs less 
than 1% methanol?

>So, for high(er) FFA, more methanol and more sulfuric
>acid should be beneficial. However, that means more
>sodium hydroxide to neutralise the acid and some form
>of methanol recovery system. We use a simple condenser
>connected to the reactor to grab the methanol. We can
>either recycle this to the next batch or operate the
>reactor under total reflux. This makes it possible to
>operate the reactor at a higher temperature and so
>accelerate the rate of the separate reactions.

You're using Aleks's acid-base method this way? Or is that the 
one-stage transesterification you mentioned previously, for the 
train's B50?

Best

Keith


>Hope this gives you some useful ideas
>
>Regards
>
>Michael Allen
> >
> > --- In [EMAIL PROTECTED], Michael Allen
> > <[EMAIL PROTECTED]> wrote:
> > > Dear David,
> > >
> > > We did extensive work last year on heated Straight
> > > Palm Oil (SPO) in two-wheeled tractors and fishing
> > > boat motors. We had field trials by local farmers
> > of
> > > four commercial tractors and did test-bed work
> > with
> > > three others. Crude palm oil caused erosion of the
> > > pistons by late ignition but refined palm-oil (of
> > the
> > > grade used for cooking oil) worked well. But we
> > never
> > > got around to using it in a locomotive.
> > >
> > > This year we have been trying a range of reactor
> > > designs to optimise methyl ester production from
> > > refined oil. We are now moving back through
> > various
> > > forms of oil "refinement" towards the crude palm
> > oil
> > > (CPO). And yes, we are currently using the Aleks
> > Kak
> > > two-stage process. And yes it is currently at
> > > atmospheric pressure (although the reactor was
> > > designed to handle 200 kPa mainly as a safety
> > feature.
> > > Even so, some enthusiastic welders have
> > > "overpressurised" it twice now through forgetting
> > to
> > > flood (and then drain) it with water before
> > modifying
> > > the unit).
> > >
> > > The locomotive I mentioned is running on a B50
> > blend:
> > > It uses esters from a one stage
> > trans-esterification
> > > reaction of methanol with the stearin and palmitin
> > > which has separated from the CPO. This waxy stuff
> > is
> > > probably quite comparable with the good Scottish
> > lard.
> > >
> > > Lots of luck!
> > >
> > > Michael Allen
> > >
> > > --- Keith Addison <[EMAIL PROTECTED]> wrote:
> > > > >Thanks for your response, prof. Allen.  I'll
> > > > formulate an inquiry to
> > > > >Mohammed Farid as you suggest.  You mentioned
> > Thai
> > > > railway application. I
> > > > >saw somewhere that German railways are using
> > SVO in
> > > > some of their shunting
> > > > >engines.
> > > >
> > > >
> > >
> >
>http://www.wired.com/news/technology/0,1282,53591,00.html
> > > > Choo-Choo Trains on Energy Crunch
> > > >
> > > > >The encouraging part of your message is you are
> > > > reacting at 60C and that
> > > > >this is near methanol boiling point.  That
> > implies
> > > > you are succeeding at
> > > > >atmospheric pressure. Do you use conc.
> > sulphuric
> > > > acid first stage?  I agree
> > > > >meth recovery is so simple that using excess is
> > not
> > > > really a problem.
> > > > >
> > > > >David T.


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Re: [biofuels-biz] Re: hi ffa feed stocks

2002-08-29 Thread Michael Allen

Dear Marco,

I presume that you have read the
http://journeytoforever.org/biodiesel_svo.html and
their stuff on ethanol? It is an excellent place to
start and concisely sets out all the major
constraints.

Our work with agricultural engines showed that there
is a considerable difference between the injection
ports of small agricultural diesels so it might be a
bit dangerous to generalise.

Essentially though, we recommend starting and stopping
on petro-diesel (or biodiesel if available). The
exhaust pipe for the engine is taken out through a
simple one-pass heat exchanger in the palm-oil fuel
tank. After about 5 mins running on petro-diesel, the
40 litres of palm oil is warm enough to have similar
flow properties as petro-diesel. So we turn off one
fuel supply and move to the other.

We also recommend running the engine on petro-diesel
for the last five minutes of operation too. That way,
everything is left free of fatty-acid residues which
might cause corrosion (particularly if the engine is
not going to be used for a while.)

Ambient temperatures here rarely fall below 27C or
rise above 34C. As a consequence, SPO is always
liquid. This means that with some engines, you can
actually start them on palm-oil. But we don't
recommend it.  

Where are you precisely? What sort of engines do you
want to use SPO with? What operations do you want the
engines to perform (electricity generation, pumping,
transport, ploughing etc.). What are your ambient
temperatures?

I have some experience of using ethanol/methanol
blends with petroleum for spark-ignition engines. We
did this work in New Zealand about twenty years ago
and the results are well documented. However these are
highly volatile fuels with low-flash points and are
nothing like palm-oil really.

Regards

Michael


--- marcohgcardoso <[EMAIL PROTECTED]>
wrote:
> Dear Michael,
> 
> tks a lot for your help. So, we can use palm oil
> direct without 
> transes.?
> WHich motor modifications do you usually do?
> 
> Do you know how to do the sme process with Ethanol?
> Or anyone who 
> does it?
> 
> regards,
> 
> Marco
> 
> --- In [EMAIL PROTECTED], Michael Allen
> <[EMAIL PROTECTED]> wrote:
> > Dear Marco,
> > 
> > 
> > > I have plent of Palm Oil. When you mentioned
> that
> > > you used Straight 
> > > Palm Oil you hadn't transerterificate the oil?
> > 
> > That is correct. The first stage of our program
> was to
> > demonstrate that oil-palm growers could run their
> farm
> > machinery on straight palm oil (SPO)by making
> simple
> > engine modifications. The overall aim of the
> program
> > is to stabilise oil prices for oil-palm growers.
> That
> > means that we are looking at all aspects of
> palm-oil
> > use.
> > 
> > Incidentally, with respect to the high free fatty
> acid
> > feeds, the limit to the amount of FFA possible is 
> > probably related to the formation of water in
> Alek's
> > first stage esterification using sulfuric acid as
> the
> > catalyst. Thus 5%FFA in the oil means that 4mls of
> > water are produced for every litre of oil. This
> water
> > increases soap formation in the second stage
> (which is
> > catalysed by sodium hydroxide).
> > 
> > Alek Kak's method
> >
>
(http://journeytoforever.org/biodiesel_aleksnew.html)
> > reduces this impact by using 95% pure sulfuric
> acid
> > which has a strong affinity for water. He also
> > recommends about 9 times the amount of methanol
> > theoretically needed to react with the FFA. This
> also
> > has the effect of reducing the water
> concentration. 
> > 
> > So, for high(er) FFA, more methanol and more
> sulfuric
> > acid should be beneficial. However, that means
> more
> > sodium hydroxide to neutralise the acid and some
> form
> > of methanol recovery system. We use a simple
> condenser
> > connected to the reactor to grab the methanol. We
> can
> > either recycle this to the next batch or operate
> the
> > reactor under total reflux. This makes it possible
> to
> > operate the reactor at a higher temperature and so
> > accelerate the rate of the separate reactions.
> > 
> > Hope this gives you some useful ideas
> > 
> > Regards
> > 
> > Michael Allen
> > > 
> > > --- In [EMAIL PROTECTED], Michael Allen
> > > <[EMAIL PROTECTED]> wrote:
> > > > Dear David,
> > > > 
> > > > We did extensive work last year on heated
> Straight
> > > > Palm Oil (SPO) in two-wheeled tractors and
> fishing
> > > > boat motors. We had field trials by local
> farmers
> > > of
> > > > four commercial tractors and did test-bed work
> > > with
> > > > three others. Crude palm oil caused erosion of
> the
> > > > pistons by late ignition but refined palm-oil
> (of
> > > the
> > > > grade used for cooking oil) worked well. But
> we
> > > never
> > > > got around to using it in a locomotive.
> > > > 
> > > > This year we have been trying a range of
> reactor
> > > > designs to optimise methyl ester production
> from
> > > > refined oil. We are now moving back through
> > > various
> > > > forms of oil "refinement" towards th

Re: [biofuels-biz] Re: hi ffa feed stocks

2002-08-28 Thread Michael Allen

Dear Marco,


> I have plent of Palm Oil. When you mentioned that
> you used Straight 
> Palm Oil you hadn't transerterificate the oil?

That is correct. The first stage of our program was to
demonstrate that oil-palm growers could run their farm
machinery on straight palm oil (SPO)by making simple
engine modifications. The overall aim of the program
is to stabilise oil prices for oil-palm growers. That
means that we are looking at all aspects of palm-oil
use.

Incidentally, with respect to the high free fatty acid
feeds, the limit to the amount of FFA possible is 
probably related to the formation of water in Alek's
first stage esterification using sulfuric acid as the
catalyst. Thus 5%FFA in the oil means that 4mls of
water are produced for every litre of oil. This water
increases soap formation in the second stage (which is
catalysed by sodium hydroxide).

Alek Kak's method
(http://journeytoforever.org/biodiesel_aleksnew.html)
reduces this impact by using 95% pure sulfuric acid
which has a strong affinity for water. He also
recommends about 9 times the amount of methanol
theoretically needed to react with the FFA. This also
has the effect of reducing the water concentration. 

So, for high(er) FFA, more methanol and more sulfuric
acid should be beneficial. However, that means more
sodium hydroxide to neutralise the acid and some form
of methanol recovery system. We use a simple condenser
connected to the reactor to grab the methanol. We can
either recycle this to the next batch or operate the
reactor under total reflux. This makes it possible to
operate the reactor at a higher temperature and so
accelerate the rate of the separate reactions.

Hope this gives you some useful ideas

Regards

Michael Allen
> 
> --- In [EMAIL PROTECTED], Michael Allen
> <[EMAIL PROTECTED]> wrote:
> > Dear David,
> > 
> > We did extensive work last year on heated Straight
> > Palm Oil (SPO) in two-wheeled tractors and fishing
> > boat motors. We had field trials by local farmers
> of
> > four commercial tractors and did test-bed work
> with
> > three others. Crude palm oil caused erosion of the
> > pistons by late ignition but refined palm-oil (of
> the
> > grade used for cooking oil) worked well. But we
> never
> > got around to using it in a locomotive.
> > 
> > This year we have been trying a range of reactor
> > designs to optimise methyl ester production from
> > refined oil. We are now moving back through
> various
> > forms of oil "refinement" towards the crude palm
> oil
> > (CPO). And yes, we are currently using the Aleks
> Kak
> > two-stage process. And yes it is currently at
> > atmospheric pressure (although the reactor was
> > designed to handle 200 kPa mainly as a safety
> feature.
> > Even so, some enthusiastic welders have
> > "overpressurised" it twice now through forgetting
> to
> > flood (and then drain) it with water before
> modifying
> > the unit).
> > 
> > The locomotive I mentioned is running on a B50
> blend:
> > It uses esters from a one stage
> trans-esterification
> > reaction of methanol with the stearin and palmitin
> > which has separated from the CPO. This waxy stuff
> is
> > probably quite comparable with the good Scottish
> lard.
> > 
> > Lots of luck!
> > 
> > Michael Allen
> > 
> > --- Keith Addison <[EMAIL PROTECTED]> wrote:
> > > >Thanks for your response, prof. Allen.  I'll
> > > formulate an inquiry to
> > > >Mohammed Farid as you suggest.  You mentioned
> Thai
> > > railway application. I
> > > >saw somewhere that German railways are using
> SVO in
> > > some of their shunting
> > > >engines.
> > > 
> > >
> >
>
http://www.wired.com/news/technology/0,1282,53591,00.html
> > > Choo-Choo Trains on Energy Crunch
> > > 
> > > >The encouraging part of your message is you are
> > > reacting at 60C and that
> > > >this is near methanol boiling point.  That
> implies
> > > you are succeeding at
> > > >atmospheric pressure. Do you use conc.
> sulphuric
> > > acid first stage?  I agree
> > > >meth recovery is so simple that using excess is
> not
> > > really a problem.
> > > >
> > > >David T.
> > > 
> > > 
> > 
> > 
> > __
> > Do You Yahoo!?
> > Yahoo! Finance - Get real-time stock quotes
> > http://finance.yahoo.com
> 
> 


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Re: [biofuels-biz] Re: hi ffa feed stocks

2002-08-26 Thread Michael Allen

Dear David,

We did extensive work last year on heated Straight
Palm Oil (SPO) in two-wheeled tractors and fishing
boat motors. We had field trials by local farmers of
four commercial tractors and did test-bed work with
three others. Crude palm oil caused erosion of the
pistons by late ignition but refined palm-oil (of the
grade used for cooking oil) worked well. But we never
got around to using it in a locomotive.

This year we have been trying a range of reactor
designs to optimise methyl ester production from
refined oil. We are now moving back through various
forms of oil "refinement" towards the crude palm oil
(CPO). And yes, we are currently using the Aleks Kak
two-stage process. And yes it is currently at
atmospheric pressure (although the reactor was
designed to handle 200 kPa mainly as a safety feature.
Even so, some enthusiastic welders have
"overpressurised" it twice now through forgetting to
flood (and then drain) it with water before modifying
the unit).

The locomotive I mentioned is running on a B50 blend:
It uses esters from a one stage trans-esterification
reaction of methanol with the stearin and palmitin
which has separated from the CPO. This waxy stuff is
probably quite comparable with the good Scottish lard.

Lots of luck!

Michael Allen

--- Keith Addison <[EMAIL PROTECTED]> wrote:
> >Thanks for your response, prof. Allen.  I'll
> formulate an inquiry to
> >Mohammed Farid as you suggest.  You mentioned Thai
> railway application. I
> >saw somewhere that German railways are using SVO in
> some of their shunting
> >engines.
> 
>
http://www.wired.com/news/technology/0,1282,53591,00.html
> Choo-Choo Trains on Energy Crunch
> 
> >The encouraging part of your message is you are
> reacting at 60C and that
> >this is near methanol boiling point.  That implies
> you are succeeding at
> >atmospheric pressure. Do you use conc. sulphuric
> acid first stage?  I agree
> >meth recovery is so simple that using excess is not
> really a problem.
> >
> >David T.
> 
> 


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Re: [biofuels-biz] Re: hi ffa feed stocks

2002-08-22 Thread Keith Addison

>Thanks for your response, prof. Allen.  I'll formulate an inquiry to
>Mohammed Farid as you suggest.  You mentioned Thai railway application. I
>saw somewhere that German railways are using SVO in some of their shunting
>engines.

http://www.wired.com/news/technology/0,1282,53591,00.html
Choo-Choo Trains on Energy Crunch

>The encouraging part of your message is you are reacting at 60C and that
>this is near methanol boiling point.  That implies you are succeeding at
>atmospheric pressure. Do you use conc. sulphuric acid first stage?  I agree
>meth recovery is so simple that using excess is not really a problem.
>
>David T.


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Re: [biofuels-biz] Re: hi ffa feed stocks

2002-08-22 Thread David Teal

Thanks for your response, prof. Allen.  I'll formulate an inquiry to
Mohammed Farid as you suggest.  You mentioned Thai railway application. I
saw somewhere that German railways are using SVO in some of their shunting
engines.
The encouraging part of your message is you are reacting at 60C and that
this is near methanol boiling point.  That implies you are succeeding at
atmospheric pressure. Do you use conc. sulphuric acid first stage?  I agree
meth recovery is so simple that using excess is not really a problem.

David T.


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Re: [biofuels-biz] Re: hi ffa feed stocks

2002-08-22 Thread Michael Allen

Hi David,

[EMAIL PROTECTED] is running a research project
on transesterification of beef tallow. I'm not sure he
has heaps of results from his enzymatic process yet
but he certainly has references to all the literature
you need. (Mohammed is an Associate Professor of
Chemical Engineering at the University of Auckland in
New Zealand)

We are making commercial quantities (1 tonne/day)of
biodiesel by transesterifying stearin from palm oil.
Indeed, one of the Thai railways routes from Hadyai to
Sungei Golok is using a B50 blend of our stuff with
petro diesel in their 150km run every day.

At the moment I have built a 120 litre deep bed unit
for  working on a crude palm oil feedstock with the
methoxide introduced at the bottom. We have lots of
stearin and palmitin (lard!) floating in the olein
liquid (and large amounts of free fatty acids) so we
have to run the reactor at 60C. This temperature is
close enough to the boiling point of methanol that we
have to recover the excess methanol to make the
process economic. 

I imagine you would have to do the same with lard.

Lots of luck

Michael Allen
Visiting Professor
Prince of Songkla University
Thailand
--- David Teal <[EMAIL PROTECTED]> wrote:
> In Scotland, chip shops use lard (animal fat).  Last
> week I took a quantity
> of such material and tried (admittedly without much
> confidence) using the
> same procedure as for WVO (2 stage base).  Nothing
> doing, as expected.  I
> was hoping Aleks' acid/base method would be the
> answer, but from Todd's
> reply we might need HTP.  Any experience with lard
> anyone?
> 
> David T.
> 
> 


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Re: [biofuels-biz] Re: hi ffa feed stocks

2002-08-20 Thread Appal Energy

Your wastewater treatment plant ought to compensate you nicely
for taking charge of the grease trap waste. No doubt they would
be happy to pawn their grease skimmings off on you as well.

FFAs...Theoretical limit or physical limit?

I don't believe Aleks lays a claim to any exact high point of
FFAs which can be converted when following the procedure outlined
in his ambient pressure method. At ambient pressure the primary
limiting factors are reaction time and diluted catalyst.

To establish a physical limit a series of tests would have to be
conducted. Even then, the results would be dependant upon time
limit. Some would have no problem with letting the reaction
extend for a lengthy period. Others would be more inclined
towards the McDonalds' drive thru method.

Todd Swearingen

- Original Message -
From: movember <[EMAIL PROTECTED]>
To: 
Sent: Tuesday, August 20, 2002 10:14 PM
Subject: [biofuels-biz] Re: hi ffa feed stocks


> The high-ffa feedstock is from industrial food waste and grease
> traps. It doesn't smell very nice either!
>
> Out of interest, what is the upper limit of FFA that would be
suited
> to standard pressure, ~60 degrees C, Aleks-style two-stage
processing?
>
>
>
> --- In [EMAIL PROTECTED], "Appal Energy" <[EMAIL PROTECTED]> wrote:
> > Yes. HTP is required to obtain high esterification conversion
on
> > such material. I would suggest that you seek out your nearest
> > college's chemistry department head and/or chemical
engineering
> > department to determine exactly what ballpark you will be in
> > relative to pressure and temp.  They may also be willing to
> > assist you with the sampling
> >
> > 85% FFA feedstock is not derived from your run of the mill
fish
> > and chips outlet. It sounds more as if it's soap stock that
has
> > been removed during oil processing.
> >
> > Todd Swearingen
> >
> > - Original Message -
> > From: movember <[EMAIL PROTECTED]>
> > To: <[EMAIL PROTECTED]>
> > Sent: Monday, August 19, 2002 9:03 PM
> > Subject: [biofuels-biz] Re: hi ffa feed stocks
> >
> >
> > > I am able to source large quantities of the high ffa
feedstock
> > (FFA
> > > 85%), however initial miniature tests (1 litre batches
using
> > Aleks'
> > > two stage Acid/Base method) have proved unsuccessful.
> > >
> > > Would the same process, under high Temperature/Pressure, be
> > > sufficient to convert feedstocks of this type? If this may
be
> > the
> > > case, then what mini-batch experiments could be done to
test
> > the
> > > feedstock?
> > >
> > > Much apreciated.
> > >
> > >
> > > --- In [EMAIL PROTECTED], "Appal Energy" <[EMAIL PROTECTED]>
wrote:
> > > > It's a bit difficult to say that acid/base catalysis
"falls
> > > > down," whether it be the ambient procedure as presented
by
> > Aleks
> > > > Kac or a HTP industrial procedure.
> > > >
> > > > Most of what industry achieves under high pressure and
> > > > temperature can be achieved at STP by conducting the
reaction
> > > > over prolonged periods, at moderate temperature and in
> > several
> > > > stages when necessary.
> > > >
> > > > To date we have experienced repeated success with STP
> > > > esterification, simply by prolonging the esterification
> > period to
> > > > 36-48 hours, generating a complete transesterification
> > reaction
> > > > on 3.5% FFA feedstock with but 1.5 grams of KOH per liter
of
> > oil
> > > > over a 36 hour period.
> > > >
> > > > Whether a repeat cycle is used on the esterification side
or
> > not,
> > > > it is necessary to separate the feedstock from any layers
> > that
> > > > formed during the esterification prior to conducting the
> > repeat
> > > > cycle or the base stage.
> > > >
> > > > Todd Swearingen
> > > >
> > > > - Original Message -
> > > > From: goat industries <[EMAIL PROTECTED]>
> > > > To: <[EMAIL PROTECTED]>
> > > > Sent: Monday, August 19, 2002 4:19 PM
> > > > Subject: [biofuels-biz] hi ffa feed stocks
> > > >
> > > >
> > > > > Check out work done by Canakci and Van Gerpen. I'm
trying
> > out
> > > > their ideas,
> > > > > but finding it difficult to get good results. Also, an
acid
> > > > value of 1mg
> > > > > KOH/g = 0.5 % FFA. They identiified water formation in
the
> > acid
> > > > stage as the
> > > > > inhibiting part of the reaction, which is where Alek's
> > > > 'foolproof' method
> > > > > falls down (apparently).
> > > > >
> > > > >
> > > > >  Yahoo! Groups
> > > > Sponsor -~-->
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> >
> ---
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> > > > > http://journeytoforever.org/biofuel.html
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> > > > > List messages are archived at the Info-Archive at
NNYTech:
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Re: [biofuels-biz] Re: hi ffa feed stocks

2002-08-19 Thread Appal Energy

Yes. HTP is required to obtain high esterification conversion on
such material. I would suggest that you seek out your nearest
college's chemistry department head and/or chemical engineering
department to determine exactly what ballpark you will be in
relative to pressure and temp.  They may also be willing to
assist you with the sampling

85% FFA feedstock is not derived from your run of the mill fish
and chips outlet. It sounds more as if it's soap stock that has
been removed during oil processing.

Todd Swearingen

- Original Message -
From: movember <[EMAIL PROTECTED]>
To: 
Sent: Monday, August 19, 2002 9:03 PM
Subject: [biofuels-biz] Re: hi ffa feed stocks


> I am able to source large quantities of the high ffa feedstock
(FFA
> 85%), however initial miniature tests (1 litre batches using
Aleks'
> two stage Acid/Base method) have proved unsuccessful.
>
> Would the same process, under high Temperature/Pressure, be
> sufficient to convert feedstocks of this type? If this may be
the
> case, then what mini-batch experiments could be done to test
the
> feedstock?
>
> Much apreciated.
>
>
> --- In [EMAIL PROTECTED], "Appal Energy" <[EMAIL PROTECTED]> wrote:
> > It's a bit difficult to say that acid/base catalysis "falls
> > down," whether it be the ambient procedure as presented by
Aleks
> > Kac or a HTP industrial procedure.
> >
> > Most of what industry achieves under high pressure and
> > temperature can be achieved at STP by conducting the reaction
> > over prolonged periods, at moderate temperature and in
several
> > stages when necessary.
> >
> > To date we have experienced repeated success with STP
> > esterification, simply by prolonging the esterification
period to
> > 36-48 hours, generating a complete transesterification
reaction
> > on 3.5% FFA feedstock with but 1.5 grams of KOH per liter of
oil
> > over a 36 hour period.
> >
> > Whether a repeat cycle is used on the esterification side or
not,
> > it is necessary to separate the feedstock from any layers
that
> > formed during the esterification prior to conducting the
repeat
> > cycle or the base stage.
> >
> > Todd Swearingen
> >
> > - Original Message -
> > From: goat industries <[EMAIL PROTECTED]>
> > To: <[EMAIL PROTECTED]>
> > Sent: Monday, August 19, 2002 4:19 PM
> > Subject: [biofuels-biz] hi ffa feed stocks
> >
> >
> > > Check out work done by Canakci and Van Gerpen. I'm trying
out
> > their ideas,
> > > but finding it difficult to get good results. Also, an acid
> > value of 1mg
> > > KOH/g = 0.5 % FFA. They identiified water formation in the
acid
> > stage as the
> > > inhibiting part of the reaction, which is where Alek's
> > 'foolproof' method
> > > falls down (apparently).
> > >
> > >
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