Petter and the Angry BioGods

Once upon a time, in a tiny kingdom far away, there lived a businessman named Petter. Every morning Petter would get up early and work hard all day long.
Although Petter was very busy running his business, he found time to make biodiesel. Petter had made biodiesel successfully for over two years using the “Single Stage” method.
Petter was very happy with his biodiesel and had travelled 141,000 carefree km in his car using it.

One day Petter heard about an exciting new method of making biodiesel which took weeks to do. It was called the “Fuelpoof Method”
So Petter wrote a letter to the BioGod’s in charge of the Fuelpoof Method and explained how he made his biodiesel and how he was having so much success. Petter then asked, “What would be the main reason to change to the fuelpoof method? I am very willing to learn, so I hope nobody reads this as if the fuelpoof method would not be better. I just do not know why it would be better.”

This enraged the biogods. The fat Biogod started talking gibberish and saying strange things to Petter like “People do not have problems until they have problems and some people have heart attacks”. Next the Fat BioGod said that Petter was ruining his engine and destroying the environment because he was too lazy to use the Fuelpoof Method of making biodiesel.
Finally the fat Biogod started talking about Hummers and left.

Next, Old Biogod came and attacked Petter telling him how foolish he was. Old BioGod said that Petter made his biodiesel in a stupid way and could not even follow simple instructions.
Old Biogod told Petter he was a stupid fellow who knew almost nothing about making biodiesel and now he had the nerve to ask how the Fuelpoof Method was better.

Petter was shocked. Petter could not understand why the BioGods had attacked him so violently for asking for information. So, apologising over and over, Petter said that he would try the Fuelpoof Method the next time he made biodiesel.

About 6 weeks later Petter decided to make more biodiesel. Petter copied the directions for the Fuelpoof Method from the internet and followed them very carefully .
And at the end of the very long process there was NO biodiesel. Just 699 litres of Waste oil with methanol sitting on top. Petter was stunned. The Fuelpoof method was supposed to always work. What had gone wrong?

So Petter went back to the BioGods and said “Can I please get some help? I have tried to make biodiesel using the Fuelpoof Method and it did not work. I followed the directions exactly”.

And the BioGods did not answer Petter for a very long time.

Fortunately, a Kindly Elf had been watching all of this and knew that the BioGods were just playing a big joke on Petter.

So the Kindly Elf said to Petter, “This is just a big joke the BioGods are playing on you Petter. The Fuelpoof Method almost never makes biodiesel.” The Kindly Elf then directed Petter to some tests which a very Famous Mouse had recently done that showed that the Fuelpoof Method of making biodiesel was a big joke. The Kindly Elf told Petter he needed to mix another 4g NaOH in some methanol for every litre of WVO and add it to the reactor. That should make biodiesel.

Finally, after about a day, the Old BioGod told Petter (With a quick wink to the Fat BioGod) “This is very puzzling. I can't imagine how you achieved such a result.” Then the old BioGod told Petter that he personally did not use the Fuelpoof Method.
The old BioGod said that the problem was probably because Petter was careless and made his single stage biodiesel in a silly way. Old BioGod then said that because Petter had not supplied any information about how he had made the biodiesel he could not help Petter.

Petter decided to do some tests and found that the Kindly Elf was correct. An extra 4g NaOH for each litre of WVO would fix the problem just like the Kindly Elf had said.

Petter was very happy and told the BioGods that he had solved the problem by adding an extra 4g NaOH to each litre of WVO.

The Old BioGod was Furious at this information. He said what a silly fellow Petter had been for trying to make such a big batch of biodiesel using the Fuelpoof Method. Old BioGod told Petter exciting stories of many people who had had failures using the Fuelpoof Method. Old BioGod said one failed attempt had even exploded. Old BioGod said that he himself did not use the Fuelpoof method.
While Talking in Tongues, Old BioGod babbled on about many strange and wonderful things which had no connection to Petter's problems with the Fuelpoof Method

Then, in an incoherent rage, Old BioGod told Petter that he knew the Kindly Elf had helped Petter solve the problem and that was the very cause of the problem. Old BioGod said that because the Kindly Elf had helped Petter fix the problem that had caused the problem (BioGods are Notoriously short on logic).

The Kindly Elf just smiled to himself.

Strangely, the Fat BioGod never pretended to try and help Petter at all.
He was out in his Hummer “Bush Bashing” and racing up and down the sand dunes, far too busy having fun to worry about Petter.

Petter went back to making biodiesel using the single stage method and had years and years of carefree Biodiesel driving.
And the Kindly Elf helped many more people save their Failed batches from the Fuelpoof joke.

Rev Tilly

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

Another Foolproof Joke

Mickey had another foolproof Failure today

The experiment
WVO titration 3.5
Mixed Acid Stage exactly as per Foolproof instructions on JTF
At the end of 2 hour mix titration 3.7
Divided the litre of WVO into two 500ml batches and processed one batch exactly as per the instructions on JTF and processed the other Batch as per the Tidball/Fox FATTA Acid/Base method

For the base stage 3.1g NaOH was mixed in 120ml methanol. When it was thoroughly mixed this was divided into 2 equal 60ml batches

Foolproof Batch
After allowing to settle for 6 hrs the titration had fallen to 3.3
Added one of the batches of methoxide and mixed ofr 2 hours
No change in colour, no seperation
Titration 1
NO BIODIESEL HERE!

Tidball/Fox FATTA batch
Continued to mix for 6 hrs at 54deg c
Titration at start of base stage 2.6
Added additional 2g NaOH to the other 60ml batch of methoxide for a total of 3.05g NaOH
Added methoxide to Oil
40 good shakes.
Oil immediatly changed colour and seperation started within 10 minutes.

4 hours later the Foolproof batch was still just oil while the FATTA batch was biodiesel.

This foolproof method is a bigger joke than I had ever imagined.

Rev Tilly KE
PS after the experiment 2g NaOH was added to 30ml methanol and added to the Foolproof method and given 40 good shakes.
The colour changed immediatly and seperation commenced within 10 minutes

Another Foolproof Test

As you are probably aware, most people have struggled to make biodiesel using the Foolproof method since it was posted onto Journey To Forever over three years ago.
During this period neither Aleks or Keith have seen fit to post any meaningful test results concerning the "Foolproof" method.
Indeed, the Few tests which people have posted to different forums have shown that the Foolproof Method has major problems.

Over the last month or so my good friend Mickey has done a number of tests which have shown that the Foolproof Method is even worse than expected.

In the latest test, Mickey decided to see how the "Foolproof" method handled NEW OIL.

THE TEST
A two litre bottle of generic brand "Coles Farmland Blended Vegetable Oil" was used to make two- 1 litre batches of biodiesel.
One batch was made using the Foolproof Method exactly as written on Journey To Forever
The other batch was a single stage batch made for a comparison using 250ml methanol and 5g NaOH as per Neutral's instrucitons on how to make a high quality batch of biodiesel.

Both batches were then washed, dried and run through the World Famous Dr Pepper Viscosimeter (Pat Pend) to compare their viscosities.

As you probably know, if you do not have access to GC testing, an accurate viscosimeter is an excellent piece of test gear for comparing completion between two batches of well washed biodiesel made from identical oil.
The batch that has the longer "Run-Time" through the Viscosimeter contains more partially reacted and un-reacted material (Glycerides).
All viscosities taken at 23deg c.

FOOLPROOF VISCOSIMETER RUN-TIMES
2min 26.25sec
2min 26.25sec

HIGH QUALITY SINGLE STAGE RUN-TIMES
2min 18.56sec
2min 18.41swc

THIS SHOWED THAT THE FOOLPROOF BATCH CONTAINS AT LEAST 12% MORE UN-REACTED AND PARTIALLY REACTED MATERIAL (GLYCERIDES) THAN THE HIGH QUALITY SINGLE STAGE BATCH

While it is true that one can not say with certainty what the actual amount of Glycerides present are, I found that I had to add 100ml of New Oil (Triglycerides) to 800ml of the High quality Single Stage Batch to achieve the same viscosity as the "Foolproof" batch This was an addition of 12% triglycerides.

Of course things are not quite as simple as that because as the Chemist Neutral once explained to me:
"In badly made biodiesel the amount of diglyceride is approximately equal to the amount of triglyceride remaining. We can assume that the diglyceride has a lower viscosity than the triglyceride as it is a substantially smaller molecule.
Therefore your method of adding triglyceride to reach the same viscosity will somewhat underestimate the amount of unreacted and partly reacted material... but the amount of monoglyceride does not vary much, varying only from about 3 to 4%."

Rev Tilly KE

wasn't that 0.3 to 0.4%?

I coppied it from here

If it is 0.3 to 0.4% I will change it.

Rev Tilly KE

Tilly you are quite right. I had forgotten we were talking about "badly made biodiesel".

The Fourth act of Magic?

I am glad Keith reminded me about Professor Allen's work with the Acid/Base method. I have spent some time reading all of his postings.
I am afraid I did not spend a great deal of time over on Yahoo Biofuels-Biz in the past.

In the Foolproof Method posting on JTF, Picture number 7 shows some cloudy biodiesel sitting on top of a thick layer of Glycerine and is labeled "First Stage Glycerine"
I know other people have questioned the validity of this picture in the past. If I am not mistaken, I believe it was Squarepega and Provo. Keith reassured them that Aleks said it was a genuine picture.
I have to add, that at the end of the Acid Esterfication Stage my oil looks Nothing like Aleks picture number 7, it always looks more like picture number 6.
Anyway, on Sept 11 2002 Paddy said "with the feedstock that I have been using the 'foolproof' method does not yield glycerine that can be collected. To which Prof Allen Replied, "the esterification of FFA cannot produce glycerol(it produces water instead)"

I find that quite interestion. Prof Allen says the esterfication stage will produce NO glycerine, yet Aleks shows a jar containing a thick layer of "First Stage Glycerine" with biodiesel already on top of it.

I know the Chemist Neutral says that the Foolproof Method is based on three Acts of Magic.
Perhaps the magical apearance of a thick layer of glycerine AND biodiesel after the esterfication stage of the Foolproof Method is the Fourth act of magic?

Rev Tilly KE

Well spotted Tilly. I haven't seen the posting on JTF, but to suggest that esterifying FFA produces glycerine is a bit silly. Where would it come from? FFA stands for free fatty acid, in other words it is no longer a glyeride.

I suppose it may be possible that some transesterification does take place, but I would have thought that this would be to avery limited degree (if at all) and therefore any glycerine produced will be minimal.

H

What a REAL chemist thinks about the Foolproof method

As you might recall, Keith Addison pointed out in his recent Psychotic rant telling what a terrible person I am that:
"Prof. Michael Allen is a real chemist with a rather illustrious record,...He's been working with biodiesel since the early 1980s.
I think you know that he was working in Thailand developing a method that villagers could use to process crude palm oil into biodiesel for local distribution...
Michael adapted the Foolproof method to process CPO, but he had to adapt it a lot - more acid at certain levels, higher temperatures, and, yes, titration, but prior titration, not following the acid step."

About 10 months ago Professor Allen posted the following directions to a person who had asked about using the Foolproof Method with CPO.

"You will need to carry out a titration of this oil and any other vegetable oils you may use because the amount of mineral acid and hydroxide you will need will vary tremendously between batches.
Indeed, I don't see how you can produce a consistent product unless you titrate each batch of oil.
It doesn't matter much which strong acid you add. The amount you add may depend on
1) which acid you use,
2) What the titrated acid value is at the end of the esterification.
But if you used mineral acid in the first process (esterification), you must neutralise it (or remove it) before transesterification otherwise it will use up all your NaOH/KOH catalyst.
You will need to titrate the oil to find out precisely how much NaOH/KOH you need to neutralise the strong acid you added.
Then you need some excess for the transesterification to work."

It makes me wonder which Real Professor Michael Allen it was that told Keith you do not need to titrate at the end of the acid stage.
But in all fairness to Keith, It is common knowledge that reading the English language has been a weak point in his otherwise illusterous biodiesel career.

Rev Tilly Ke

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

I think you are being a bit rough here. The first stage of the acid/base process does produce glycerol. If you run it long enough and hot enough and don't use too much methanol there will be a bottom layer after long settling. This layer will contain a little glycerol (from transesterification, not from esterification of course), water (from esterification) and most of the surplus methanol and most of the sulphuric acid. If you use a lot of methanol this layer will float but will still contain a little glycerol.

Neutral, It has been my understanding that a small amount of Transesterfication MIGHT happen in the first stage of the Foolproof Method

However, both Michael and Aleks seemed to think that for this to happen you needed to use between 5 and 8 times stoichemetric methanol.
Also 35deg c for the first hour, then stir for one more hour and then leave to settle 8 hours or over night does not even take care of the FFA's in mickeys experience.
Girl Mark must be doing a bit of acid transesterfication ala Dr Van Gerpen (Whom Keith seems to have decided does not know what he is talking about), at least that is what Mark seemed to say in some of her posts.
She said that until she developed better methanol recovery equipment it was using too much methanol to do it on a large scale.

I must admit I do find it very difficult to not be hard on someone who has been responsible for so much inaccurate information about biodiesel being posted.

Rev Tilly KE
PS that puts us back to 3 acts of magic and one miracle.

I quite agree that after a couple of hours at 35 deg there will be no significant glycerine however that is not the issue.

You said: "Prof Allen Replied, "the esterification of FFA cannot produce glycerol(it produces water instead)"

I find that quite interesting. Prof Allen says the esterfication stage will produce NO glycerine, "

You have misquoted Prof Allen. There is a difference between "esterification" and "esterification stage" which you have slipped over.

Neutral, this is the relevant question from Paddy, biofues-biz fromPaddy 10 sept 2002 post 1568
"on the subject of FFA's, with the feedstock that I have been using the 'foolproof' method does not yield glycerine that can be collected. Common sense says to me that if you don't remove the product of the reaction it will simply go into reverse when the base catalyst is used."


This is the answer from Prof Allen Biofuels-biz entry 1578 Date: Wed Sep 11, 2002
"Paddy: While the esterification of FFA cannot produce glycerol(it produces water instead), the TRANSesterification of just about any vegetable or animal oil must produce glycerol as a by product. So sadly : "No glycerol ..... no TRANSesterification!"

Rev Tilly KE

Tilly

I too agree that photograph 7 doesn't look right. Alec doesn't say that this is biodiesel however but you say he does. There is plenty wrong with the foolproof method as we both know but going over the it again with a fine tooth comb could easily lead you into errors. The main faults of the process have been well discussed in the past.

Paddy is wrong when he asserts that the reaction will go in reverse when the base is added. You are wrong when you imply that no glycerol is released in the acid stage.

Neutral, I did not say that Aleks said the oil on top ofthe glycerine was biodiesel
That was my observation after looking at the oil in the picture and realizing that with such a large amount of glycerine on the bottom of the bottle the oil on top would be biodiesel.

Dr Allen seemed to be implying that there is no glycerine released during the acid stage. Mickey also never observed any glycerine production during the acid stage using either the Foolproof or FATTA Acid/Base method.

Rev Tilly KE

What Dr Allen said was that esterification produces no glycerol. That is perfectly correct. But the acid stage does produce glycerol. If you don't do it properly of course there may not be enough to see. That doesn't mean it is not happening.

Neutral, et al

I did find it interesting that Pofessor Allen says: "It doesn't matter much which strong acid you add".

Which other acids besides H2SO4 can be used?

Rev Tilly KE

Does this include Nitric acid ??
dva

Tilly

Hydrochloric acid (dry) in methanol is used in small scale preparations for analysis. I've never heard of this method being used in large scale work. Perhaps this reagent cannot be prepared cheaply enough. Perhaps it only works if methanol is used in large excess.

One of the advantages of using sulphuric acid is that it is a powerful dehydrating agent. This helps to move the reaction in the desired direction because it mops up the water produced by the esterification reaction. That is the rationale behind the idea of titrating for FFA before doing the acid step, so that the amount of acid used will be proportional to the water produced.

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

Recently posted success getting my wvo titration from 14 to 6 (Making Biodiesel). I now have it to 5 . Today i started it on single stage using 9g/l , but after reading the previous posts realize i have failed to neutralize the sulfuric acid content.

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