Foolproof Method, Science or Magic?

This discussion was originally started in the Making Biodiesel list but should have been started here.
Therefore, for ease of location in the future I thought it sensible to give a quick rundown over here and a hyper link.

Below is a Brief description. For the full story click on the link above

Because so many people have reported failure when trying to use the "Foolproof" method I decided to run a series of tests to see if there was really a problem. I followed the "Foolproof" method EXACTLY AS WRITTEN
and I watched the titration numbers closely to see how the reaction was actually progressing.
Just a reminder, properly made biodiesel should have NO titration number in the titration procedure we use.

TEST 1 WITH OIL TITRATING AT 6.4

The first "Foolproof" batch I attempted was with some very used black oil titrating at 6.4
At the end of the Acid mixing stage the oil titrated at 5.6
The Next morning at the beginning of the Base mixing stage the oil titrated at 4.4
Needles to say, with the "Foolproof" methods instructions of using only 3.1g NaOH in this stage there was never any likelyhood of a success.
After stiring the base stage for 3 hours the oil titrated at 3.
No Biodiesel Here

TEST 2 OIL TITRATING AT 4.7
I made three batches:
FOOLPROOF
SINGLE STAGE
FATTA ACID BASE using titration and using amounts of NaOH as required by the titration number.

Foolproof Batch
Starting titration 4.7
Titration at end of Acid Mix 4
Titration at beginning of base stage mix 3.7
Titration at end of 2 hrs mixing 1
No Biodiesel Here

Single stage
Used 9g NaOH.
Had good seperation but had to add 50ml extra methanol to break gel

FATTA Acid/Base Method
Initial titration 4.7
titration at beginning of base stage mix 2.2
Used 7g NaOH in the base stage and got good seperation

Viscosity test showed that the Single Stage and Acid/Base biodiesel were of nearly identical quality

TEST 3 OIL TITRATION 3.3

FOOLPROOF METHOD
Initial oil titration 3.3
At end of acid stage mixing oil titrated 3.3
At beginning of base stage mix titration 2.2
This batch made a very low quality "biodiesel".
Viscosity tests showed this batch contains in excess of 40% unreacted oil.
If I recall correctly ASTM and DIN allow something like 2%.

FATTA ACID/BASE BATCH
Initial titration 3.3
Titration at beginning of Base Stage 1.6
Used 7g NaOH in base stage and made excellent biodiesel.

SINGLE STAGE BATCH
Used 8g NaOH and made excellent biodiesel.

Viscosity of the Acid/Base and Single Stage biodiesel were nearly identical with the viscosity of the "Foolproof Batch much thicker.

TEST 4 OIL TITRATING 0.3

I made a "Foolproof" batch and a single stage batch to compare it to.

FOOLPROOF BATCH
Initial Titration of oil 0.3
At the end of Acid Mixing stage titration was 0.6
At the beginning of Base Stage mixing titration was 0.9
This batch made a low quality of biodiesel containing in excess of 16% unreacted oil

SINGLE STAGE BATCH
Used 5.5g NaOH and made excellent biodiesel.
Viscosity Run-times were about 6 seconds quicker than the runtimes for the "Foolproof" biodiesel.

MM Legend

[This message was edited by Mickey Mouse on 18 March 2004 at 03:44 AM.]

This message has been edited. Last edited by: Mickey Mouse,

Us Fellows born in Michigan are always one step ahead

I find it amusing to see the "Foolproof" instructions keep morfing.

As you recall they have just recently added to the very beginning:
NOTE: The two-stage biodiesel processes are advanced methods, not for novices -- learn the basics thoroughly first. The single-stage base method is the place to start. Start here.

And now I notice they have added in the box beside these instructions since the last time I looked:
In two professional biodiesel fuel analyses, two years apart, home-brewed biodiesel made by this method met the German DIN 51606 biodiesel standards. This means the fuel is suitable for warranty repair by VW for all their vehicles made from 1996 till today. You can make DIN and ASTM-compliant fuel just by carefully following the instructions. See National standards for biodiesel

The last time I read it it said:
In laboratory tests the product has tested at Spec. grav. (density) 886g/l, Kin. visc. 4.7 mm2/sec, CFPP –9 deg C, and with an IR spectrum equal to control samples from commercial producers in Austria -- very good fuel!

I wonder if that assurance makes the fuel any better.

Oh well...

MM Legend

[This message was edited by Mickey Mouse on 17 March 2004 at 08:42 PM.]

Tilly

You said in the other page that you agree that the glycerine settles very differently in appearance and speed in a Foolproof reaction compared with base-only.

How about the comparison of settling between a base-only reaction and a properly done acid/base?

How about yield comparison between all three methods?

Tilly has had to race off to india again
It seems Tomas Asta is in a bit of trouble.

I will do what I can but my yield measuring equipment is pretty rudimentary so they will not be terribly accurate.

MM Legend

Mr Addison made an interesting post a couple of nights after you posted this at Yahoo Biodiesel.
He said:
But now I can't find any bad oil! Some people are never happy, eh?
LOL! Well, I do some things that work nicely with good oil, but I'd like to test them with bad oil to see how far it goes or how it would
have to be adapted. I'm not exactly losing sleep over it, not urgent, everything at our website's been thoroughly tested with very bad oil anyway.

The thing I found most interesting was that this was something he just posted spontanously. Noone was questioning any of the procedures on JTF.
They wouldn't dare.
Perhaps a Freudian Slip?

LL

The results are in. The "Foolproof" method is grossly inadequate!

Made three batches:
1. FOOLPROOF
2. FATTA ACID/BASE
3. SINGLE STAGE

Oil titrated at 2.

SINGLE STAGE BATCH
Oil Titration 2
Yield After Washing about 910ml
Used 7ml NaOH in 200 ml methanol
Viscosity run times:
2min 14.56sec
2min 14.63sec

FATTA ACID/BASE BATCH
Oil titration 2
Yield After Washing about 945ml
Used only 1/2 ml H2SO4 because of low titration
Titration after 2 hr 1.8
Titration after another 2 hrs 1.5
Titration at commencement of Base stage 1.3
Base stage reacted with 6.5g NaOH
Viscosity Run Times:
2min 15.97sec
2min 16.00sec

FOOLPROOF BATCH
Yield after washing ?
Initial titration 2
Titratioon at the end of 2 hour mix 2.1
Titration at commencement of Base mix 1.8
VISCOSITY RUN TIMES
2min 26.72sec
2min 26.62sec
The Foolproof viscosity is the equivelent of adding about 300ml of unreacte oil to a litre of the Acid/Base Batch.
OR to put it another way, the Foolproof method contains in excess of 23% unreacted oil.


SOME OBSERVATIONS
I started the Acid stages yesterday and allowed the Foolproof batch about 12 hrs te set before starting the base stage.

FOOLPROOF OBSERVATIONS
When I added the base stage the oil stayed the same light colour.
After mixing for 30 minutes I put it on a shelf and watched it settle and glycerine started slowly building on the bottom the way a single stage does.
Recommenced mixing.
Batch very slowly darkened.
20 min later I again set on counter to observe and this time No glycerine build up but rather the biodiesel line started decending but without a similar build up of glycerine at the bottom, as if the biodiesel were being released from the more opaque bottom layer.
Mixing for two hours total.
Settled quite slowly with a translucent layer of biodiesel on top of a gradual shrinking and darkening opaque layer on the bottom.
Started washing two hours after last mix. Major emulsion problems which caused a loss of product so no output figure.

FATTA ACID/BASE OBSERVATIONS
On adding the base stage the oil immediatly went the same darker colour as the original oil, just a matter of seconds and much quicker that single stage darkens.
The colour seemed to be "Brighter" more transluscent than the Single stage batch.
Acted very similar to a base stage batch.
Started washing 45min after last mix.
Washed easy with no emulsions.

SINGLE STAGE OBSERVATIONS
Typical single stage reaction. Washing started about 45min after final mix. Washed quick and easy.

I just cannot believe that the people who are Pushing this method down every ones throat and who immediatly vicously attack anyone who says the process has major problems have ever used the method.
The Foolproof Method is just so obvously totally inadequate.
Yes BioGod, I think you had better locate some BAD oil soon and give it a try. Of course bad seems to be anything titrating above 0.1 for the Foolproof method.
Major "Loosing of Face" happening here!
And it does not even pretend to pass the Shake test that you put so much store on over at Yahoo.
Foolproof + water= Massive emulsion problems everytime!

I wonder how long it will take for the instructions to change from 3.1gNaOH to 6.5gNaOH in the base method? It'll be pretty quick I bet.

MM Legend

[This message was edited by Mickey Mouse on 19 March 2004 at 02:06 AM.]

This message has been edited. Last edited by: Mickey Mouse,

...Tilly, 'Mickey' Neutral, et al, nothing is "Fool-proof"...fools are incredibly ingenious...

Incidently, I tried it when I was at the bottom-end of my learning-curve, - and stayed there until I titrated, measured, and used the Single Stage Proceedure correctly...

Bongo Said
Incidently, I tried it (Foolproof Method) when I was at the bottom-end of my learning-curve, - and stayed there until I titrated, measured, and used the Single Stage Proceedure correctly...

And that is Exactly the problem with this whole sad Foolproof Saga
It is presented in the Premier Biodiesel website as the truth and being the best thing since mothers milk.
Anyone who questions Keith and his Foul-Mouthed Offsider are immediatly attacked.
And the truth is, the Foolproof Method is a catastrophy of the first order. Much worse than the two-stage base/base method.

Pushing this Foolproof Method down everyones throat has done incalculable damage to biodiesel.
How many newbies would have had a number of failures using the Foolproof Method and just given up.
I have no doubt at all that by Jamming the Fullproof Method down everyones throat, Acid/Base experimentation has been set back two years.

All for the greater glory of Biogod and Ester.

Rev Tilly

[This message was edited by Tilly on 19 March 2004 at 08:06 PM.]

This message has been edited. Last edited by: guest@@,

guest@@ I am checking it two or three times a day for just that occurance

MM Legend

Another Foolproof Disaster

Me and the boys have been hard at work here and have just finished another "Foolproof" test.
In prevous tests, we have determined that while the Foolproof method does NOT achieve seperation from oil with a titration of 4.7 it will seperate and make a very low quality fuel with oil titrating at 3.3.

Because some people seem to think if there is a bit of glycerine on the bottom of the reactor they have made good biodiesel, me and the boys are trying to see how high a titration oil will give a bit of seperation.

With that in mind we have just finished a test series using oil titrating at 3.8
We made two batches
Foolproof
FATTA Acid/Base

The Tests

Foolproof Method
This test was done following all directions precisely as per the instructions on JTF.
As Mr Addison often points out, these are not suggestions they are instructions. Apparently if you follow the instructions exactly you cannot fail (Foolproof)

WVO initial titration 3.8
Poured 80ml methonal into litre WVO and mixed for 5 min.
Put 1ml 98% H2SO4 in to reactor.
Stirred Acid Stage for an hour at 35deg c
Stirred for another hour with heat turned off.
Titration at end of stirring in Acid Stage 4.4
Allowed to sit unheated overnight-12 hours
Titration at the beginning of base stage 3.0
Mixed 120ml methanol with 3.1g NaOH.
Put half in oil and mixed for 5 min
Heated oil to 55deg c and put other half of methoxide in.
Stirred for 2.5 hrs.
Allowed to set for 3 hrs
NO SEPERATION
N0 BIODIESEL
FAILED BATCH TITRATED AT 0.6

FATTA ACID/BASE BATCH
Initial titration 3.8
Added 1ml H2SO4 to 55deg c WVO and mixed for 1 minute
Titration went to 5.1
Added 100ml methanol and stirred for a minute .
Titration went to 4.6
Mixed off and oi for two hours at 55deg c
Titration 4
Mixed an additionat two hours at 55deg c
Titration 3.5
Mixed an aditional 2 hours at 55deg c
Titration 3.2
Allowed to sit overnight
Titration 2.1 at beginning of Base Stage.
Mixed 7g NaOH into 100ml methanol
Heated oil to 55deg c and mixed for two hours.
Good quick seperation occured.
Allowed to settle for 1 hour and then washed
Wash was quick and easy with NO emulsions at anytime.
Yield after washing 950ml
Viscosity times:
2min 17.06sec
2min 16.71sec

Well, at least now we know that 3.8 is too high a titration for the Foolproof Method to handle.

To date we have attempted to make biodiesel 6 times using the Foolproof Method (Pats Pend) exactly as presented on JTF.
Three of these attempts made NO biodiesel
The three attempts which did make biodiesel made a fuel of such low quality that most people would not consider putting it in their car.

More tests to come

MM Legend

PS A quick up-date
I mixed 4g NaOH in 50ml methanol, heated the failed Foolproof Batch to 55deg c, poured in the methoxide, shook off and on for an hour, and I now have a litre of biodiesel. MM

[This message was edited by Mickey Mouse on 25 March 2004 at 07:07 AM.]

This message has been edited. Last edited by: Mickey Mouse,

Hey, don't knock the Foolproof mkethod too much! It did neutralise your FFA content enough for 4g NaOH to work.

H

http://groups.msn.com/Pinzgauerdiscussiongroup/homepage

HCR, you forgot about the initial 3.1g that went in at the start of the base stage for a total of 7.1g NaOH in the base stage.

Actually the "Foolproof" method as written on JTF is ABSOLUTE CRAP It is just a tragedy that it is still available and being pushed on the internet.

But this post makes me realize that the titration was 3 at the beginning of the Base stage which means I should have used an additional 5g NaOH, not 4.
I have just started washing the batch after 3 or 5 hrs sitting and I am presently having emulsion problems.
HCR, thanks for jogging my brain on this. More tests results as they come to hand.

MM Legend

[This message was edited by Mickey Mouse on 25 March 2004 at 07:29 AM.]

quote:

---

Originally posted by Mickey Mouse:
_HCR, you forgot about the initial 3.1g that went in at the start of the base stage for a total of 7.1g NaOH in the base stage._

---

Sorry, I was being facetious. What I was trying to say was that after all that all you had was a good starting point for some good old single stage production.

H

http://groups.msn.com/Pinzgauerdiscussiongroup/homepage

HCR, Now I understand!

Unfortunatly facetious comments are something which mice are notoriously poor comprehenders of.
You are right. The acid stage of the Foolproof method reduced the titration by a whoppping 0.8. Not exactly something to write home about.

But I did go ahead and test the salvaged Foolproof batch with interesting results.
As I mentioned above, your post made me realize that I should have used 5g NaOH, not 4, so I washed and tested the batch.
It formed a lot of emulsion durring washing and was a nusance to wash.
After eventually getting it washed with a bit of emulsion down the drain I did a viscosimeter check.
Because I have calabrated the Viscosimeter at 23deg c for checking slight differences between batches, I did the viscosity tests at 23detg c.

FATTA Acid/Base Batch
2min 24.65sec
2min 24.37sec

Salvaged Foolproof Batch
2min 25.45sec
2min 25.62sec

This difference in viscosity is consistent with an increase in un-reacted oil in the salvaged Foolproof batch of between 1% and 2% over the FATTA Acid/Base batch.
And there was more methanol in the salvaged Foolproof batch whisc seems to indicate it was the NaOH which caused the increase in quality.

It just goes to show that how something looks is not a very good indication as to it's quality.

This will be something interesting to study further at a later date.

MM Legend

This message has been edited. Last edited by: Mickey Mouse,

Over 12 hours ago one of Yahoo biofuel's trusted members (Non Censored) posted the following:

Subject: Can I please get some help ?
Hi all.
Yesterday and today I made my first batch of BD using the foolproof method.
Neither in the acid stage, nor in the second stage any separation occured.
The methanol is floating on the top and the whole lot looks like coffee with
too much milk in it.
At the bottom I find some salt, which is probably NaOH.
The oil I used is a very good quality, almost SVO.
What have I done wrong ?
I couln't get the temperature higher than 35° C.
I have tried to do it exactly as Aleks Kac writes on the site."

This fellow has been successfully making biodiesel for a nuber of years, but was recently "attacked" for asking why he should use the Foolproof method.

And what happened in his attempt is just about what always happens.

12 hours later still no answer.

Rev Tilly

Finally the Great Biogod answered this call for help which I now post for your amusement

"This is very puzzling.
I can't imagine how you achieved such a result. We've used the acid-base method with all kinds of oils in all kinds of conditions, good and bad, and considerably tortured the method as well, but we never got it not to work.
This is both the current version and the previous version, which works well, but we prefer the revised version. Actually we don't use either of them as standard, we use quite a severe adaptation, for various reasons, but it's based entirely on the Foolproof method, and if that wasn't reliable this wouldn't work at all.
We also regularly do a batch the regular way, as it's written, without any problems. Quality's always high, yields high, no wash problems. Certainly never any methanol floating on top, and it always splits well at the beginning of the second stage.

Anyway, you haven't provided much information. You do have a strange way of making biodiesel by the single-stage base method - we established it still contains unreacted material, as well as various impurities because you don't wash it. So if you want us to
troubleshoot your acid-base tests, we really need details rather than taking anything for granted.

So. How much oil did you use - was this a small test batch? I hope so. How did you heat it and how did you agitate it? How did you mix the methoxide? - I can't imagine anything that would separate the NaOH unless you didn't mix it thoroughly in the first place. Acid
would separate it from the glycerine by-product cocktail, but it would need more acid to do that than the amount of sulphuric acid
specified, which should have been more than neutralised by the methoxide anyway. How much sulphuric acid did you use? What was the purity? What proportion of the total amount of methanol is floating on top? For how long did you process each stage? How long did it settle in between? And how come the low second-stage temperature?
Beste
Keith"

I must admit, I just about died laughing when I read this reply.
Let me interpret Keith's reply for you:

Even though I personally do not use the Foolproof method it is a fine procedure and makes great fuel. Of course in keeping with the Foolproof tradition I will not post any test results which verify this.

But just to check that the magic is still working, I regularly do a foolproof batch.
I do not like the way you make your base only biodiesel so i will intimate that your work is careless and sloppy.
Even though you have said you followed the Foolproof method exactly as written, you have provided me no information.
And while you have been making biodiesel successfully for years I will imply you did not mix your methoxide properly.
I will also toss in another red hearing because you were unable to get the Base stage up to 55deg c.

And Girl Mark, I understand you are on thin ice over there, but I was very disappointed with your response.
These tests Mickey has been doing lately clearly shows that the reason there is usually no seperation in the base stage of the Foolproof method is insufficent NaOH.
Surely you could have told him to just add 4g NaOH to 50ml methanol for every litre WVO in the reaction and he would problably achieve seperation.

Rev Tilly

Hi,
I’m new to the biodiesel world and I am particularly interested in doing some experimentation with the acid/base method, which from what I’ve read, seems to be the method which yields the highest yields and best results.

I intend to use the FATTA method (below) as proposed by Kevin Tidball and Michael Fox but I have some queries which somebody may be kind enough to help me with.

1. What is the break-off point at which it is necessary to do an acid/base rathed than just a straight base transesterification? In other words if the titration takes less than say 3 grams NaOH is it worth bothering with the acid stage at all?

2. Assuming it is necessary to do the acid/base esterification/transesterification is it always 1ml of sulphuric acid you add? It says in the instructions 1-2 ml. How do you know how much acid to add?

3. The third question is probably related to the second. I don’t understand the part of the method that says “Greater levels of acid will raise the titration end point.” Does it mean that if you use greater than 1 or 2 ml of acid that you reach the desired end point of 2.6ml titration more quickly?

4. I don’t understand where he gets the 6.4g of NaOH from. Surely if the titration is 2.6 ml then you just add the 2.6 to the 3.5 and get 6.1 g. Why does he add 2.9 to the 3.5?

5. Has anybody tried this method in batches of say 200 litres and does the first stage only take around 2 hours as stated for the 1000ml sample below or is it necessary to leave the mixture settle overnight before commencing the base stage?

6. After the acid stage is it advisable to separate and remove the glycerol from the bottom if there is any?

7. Is there a detailed recipe anywhere on this acid/base method?

Thanking you in advance if you can help me with these queries.

Regards

Dermot Donnelly

The FATTA method - Development by Kevin Tidball and Michael Fox

First stage acid catalyst (to esterify the FFA)
Oil 1000ml
CH3OH 100ml
H2SO4 (conc. 98% 18M) 1-2ml
React at 48- 54C until titration falls to a minimum hopefully 2.6 ml could take longer than 2 hours. Greater levels of acid will raise the titration end point.

Second stage alkali catalyst (transesterification of the oil)
100ml methanol
6.4grams of NaOH
(3.5grams for catalyst + 2.9 grams for acid neutralisation if titration of 2.6ml achieved)
React at 48- 54C for 1 hour.
Settle and separate.

Many of your questions have been answered in this thread.

If you are new to biodiesel, and not a chemist, Acid/Base is not the place to start. Kind of in the same fashion that you would not learn to fly in an F16.
Learn how to titrate. May I recommend the World Famous Chopstick Titration Technique (Pat Pend).
Then do some single stage batches to see how things work. May I recommend the World Famous Dr Pepper Technique (Pat Pend)

Also be aware that while it only takes an hour to make a batch of biodiesel using the single stage method, the acid/base method takes longer and makes no better fuel.
You have to determine what is best in your situation.

For some answers to your questions.

2. No. For now experimentation I guess.

3. The more H2SO4 you put in the reaction, the more that will need to be nutralised in the base stage. This means that your end point titration will be higher. This means more NaOH will be needed in the base stage.

4. Tests have shown that 3.5g NaOH is not enough when using 200ml methanol in the reaction.
Different people have different ideas.
It probably should be 5g NaOH + titration.

5. The first stage takes as long as it takes. When the titration is the same in two consecutive hours it is probably finished.
Mickey found that the reaction always went well beyond 2 hours
You can then go straight into the base stage, no need to wait.

6. The only place I have seen glycerine settle out after the first stage is on the JTF website.
The picture there looks NOTHING like what really happens.
Following in the finest traditions of the Foolproof Method, I believe that picture to be a phony.

7. Yes have a read through all the acid/base threads here on this forum.
What Mickey was doing above certainly worked well and was pretty much exactly what Kevin and Michael were doing.
It is not rocket science.

The three rules of the Acid/Base procedure:
Titrate titrate titrate.

Rev Tilly

This message has been edited. Last edited by: Tilly,

Rev Tilly,

Thank you very much for your very informative reply. I appreciate your taking the time to answer my queries.

Regards
Dermot