The Genesis of the acid/base 2stage method

I have been aware that the question of "Who" thought of the 2 stage acid/base procedure has been in dispute.

Blind Freddie can see that Kevin and Alek’s process are very similar, and my question has always been “who thought of it first” and who gets the honour and squillions of dollars?.

I didn’t realize it, but there is a whole lot of information available about this very question on the Yahoo Biodiesel Forum at:
http://groups.yahoo.com/group/biodiesel/

I have spent quite a few hours reading entries and found a fascinating story unfold.

Things really started to get active in late 2000. Alecks had just developed his 2 stage base/base method and was trying to find a method where he could use high FFA oil and still get an acceptable yield.
He was experimenting with using a one or 2 stage base technique and then acidifying the glycerine to recover the biodiesel tied up with the soap. He had also discovered an Irish Base/acid method which was discussed.

On Nov 3 2000 Alan Portello wrote on post 623:

Here's a question for you, Aleks. Since the acid method is good for converting FFA's but is inefficient at making biodiesel, and the alkali method is efficient at making biodiesel but has trouble with FFA's, might it be good to use a two step method for production, with the first step being the acid method, which would presumably convert most of the FFA's, and the second step being the alkali method?

On Nov 6, post number 635 Aleks replied to him: “Different experiments are running as we speak.
Thanks anyway.
Aleks “

One peerson says this reply from Aleks meant he had already thought of acid first then base and had "acid/base experiments running", but his later postings do not support this conclusion and indeed seem to mean just what he said, "Different"( not acid first) experiments are running because
9 days days later on Nov 15 in Post no. 648 Aleks tells us what these experiments are:
“Hello folks!
For the past two weeks I've been trying to work something out on our soap problem. The easyest thing I've come up with is soap decomposition by acid.
With the two stage system (Ed Note: Base/Base 2 stage) it works like this: first stage is always ok, since it does not contain enough water nor lye to form a measurable ammount of soap. At the secaond stage with some types of grease I'm having problems - it does not split (too little lye) or it forms soap (too much lye). So I kept the original high ammount of lye and just let the soap to form.

Now, to put yields back on the old tracks,(-more than 90% is usual single stage yield-) I've decomposed the soaps into FFA's and Na ions.
This is done by putting a more than neutral ammount of acid (I used strong vinegar again) at the end of the sec. stage mix time and mixing for another 1/2 hour. Since vinegar contains a lot of water, the glycerine gets diluted.
I made a huge mistake then and washed everything togehter, figuring that the glyc will dilute furthermore.
Mistake. I haven't got a big enough washing vessel, so I wash twice.The first half washed so nice, that after settling time the fuel was
so clear that I didn't even bother to dry. But the second half (with the dissolved glyc) just turned into glyc soap. Of course I decomposed that with strong sulph acid, but don't try that at home.
It stinks like hell and it bubbles so much, that it covered half of bathroom-bd workshop with soap bubbles. If I come up with something more foolproof, I'll inform you.
If someone knows how much FFA in the fuel is acceptable for the engine, please let me know (otherwise I'll have to do thet damn
Fisher reaction - FFA+MetOH to ester, which is difficult and would be the third stage).

Cheers, Aleks”

Then on 6 Dec post number 824 Aleks says:

Hello, friends!
I have something for you to chew on. As I'm experimenting on my two stage process (Ed note Base/Base) I made some BD last weekend which caused some strange effects... The fuel was made with a "three" stage process with less lye and a final acid stage. It gave "runny" glyc in the first two stages and something at the third stage. What that was I don't know, because I
made it IN WATER…
Cheers, Aleks

But on 8 Dec aleks says on post no. 824:

“P.S.: I'm working on a modified first stage, which will hopefully esterify FFAs, so less lye will be needed for further transesterification.
Less lye should mean easyer washing, less dangerous Methoxide.Your "joke" about the fourth stage is near my "foolprof" recipe, as I
dicovered that some BD processes involve as much as six stages -without counting washing.”

So finally over a month after Alan Potrillo suggests using acid first Aleks says he has started working on that idea.

I wondered what had caused this seeming complete change in direction between the 6 to the 8 Dec, but could not find anything on the Yahoo biodiesel list that gave clue.

BUT, I might have found it on the Journey to forever List message 1514 DEC 7 when Kevin replied to Aleks,,

From: "Kevin " <ktidball@o...>
Date: Thu Dec 7, 2000 4:31 pm
Subject: Re: FFA@h... NOT?

What about small quantities of H2SO4 (0.1 to 0.2%) to reduce the FFA
in animal fat so that less soap is formed.

Our experiments look promising, (using the NaOH/H2O titration
method),titration values have reduced in the order of, from 4.0 ml to
2.6 ml using an initial acid + methanol reaction.

After the acid reaction we perform a BCT to create the tallow esters.

To date, experimental yields have been good with a lot less soap
produced. Tallow ester yields between 70 - 85% have been obtained so
far.

When stable and repeatable results have been achieved we will post a
recipe."

To which Aleks replied 13 minutes later in post 1515:
"Come again? What reduction of FFA? Sulph acid does the opposite - It can
for instance split soap into FFA and ionic rest,so it increases FFA levels."
This is certainly a clear indication that at this posting on 7 Dec Aleks had come to the conclusion that acid first would INCREASE FFA and it would be very unlikely that he had done any experiments with reference acid/base.

As well, something really important had happened on the Infopop forum on 29 Nov when Kevin posted his first acid/ base experiments as follows:

H2SO4 / NaOH 2 stage process Kevin, Melb. Member posted 29 November 00[/b]

Experimental success rate to date 3 from 5 batches. Aim to process animal fat with a high yield and low gel point. Process (best results)Heat fat to 125 C to remove all water, when all water is boiled off temp with rise quickly.

Stage 1, Initial Titration 3.6ml2000 ml fat,
400 ml methanol,
4 ml H2SO4
Held fat temp between 48/54 C stirred for 1 hour.
Titration at end 1.8ml

Stage 2,
Mixture was let stand for 2 days,
Titration had risen to 2.6ml (?)
375 ml Methanol, 12gm NaOH addedHeld Stage 1 product temp between 48/54 C stirred for 1 hour.
Result - approx 82% yield with very little soap, good clear colour, density approx 0.86,Gel point lower than the normal 10 C for Tallow Esters (approx 5 C).
Other tests were performed using different amounts of methanol and H2SO4 Thanks to Michael for chemistry ideas and suggestions. Aims - get the methanol usage down, control the drop in FFA, repeatable process. Could the rise in titration be excess H2SO4 working further during the standing time? If so, can the acid be neutralised between stage 1 and 2? If any one tries the experiment please let the group know the results."

So WHY did Aleks seem to totally change direction in his experiments between his Dec 6 post and Dec 8 post? MIGHT it have been Kevins posting on the JTF list on 7 Dec when he told Aleks about the success he had had with his Acid/base experiments?

I have an idea that the "Penny dropped" for Kevin on 3 Nov when Alan Potrillo suggest acid then base, and it was a fair bit later for Alecks (perhaps 7 dec 2000).
As late as 6 Dec, a week after Kevin posted the first acid/base procedure on Infopop, and a day BEFORE Kevin posted his Acid/Base experiments on the JTF List,Alecks was working on something entirely different AND thought using acid in the first step would INCREASE FFA.

16 Dec 2000 Kevin Tidball posts the Definitive FATTA method developed by him and Michael Fox.

8 Feb 2001 Aleks Kac posts his "Foolproof" method to the JTF site with the glowing header: The FOOLPROOF way to make biodiesel
NEW standard method
By Aleks Kac
Free fatty acid to ester conversion
This is a FOOLPROOF way to make biodiesel. No titration is required, and no extra equipment -- thermometer optional, and NO pH meter!

This is a two-stage procedure, acid first-stage, base second-stage.
It is based on the highest FFA content found in used oil, but it can be used with any waste vegetable/animal oil or fat (WVO), whether or not it has a high FFA content.
The process increases yields dramatically.
Use it as your standard method.

I think Alan Portillo should get credit for the acid/base idea (Pat Pend).

Tilly SBC/IBA

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

I have been testing a four stage process which produces exceedingly pure,almost colourless ester from used cottonseed feedstock.
The first stage is standard base trans. as per the book.
The second stage is the same proportion of catalyst meth used in the first stage applied cold to the ester but at 5-8%/ volume and blended.
The third stage is a water wash of the resultant(clear ester)which produces white soap with no seperation.
The fourth stage is to apply strong acid (sulpuric,or phosphoric) until seperation occures,result produces a crystal clear very light ester with clear water below?(observable).
All glyc has been removed at stages 1 and 2.
All very well ,however I dont really believe that you need to go to all this trouble to run a car on this highly refined product as to date I have experienced no problems on running my vehicles on the product produced of the first stage.Nor has there been reports of engine or injection degradation with running on SVO.
Of interest however I will do some gel and freeze experiments on this prdouct and report the result

Hintertech

Basically there is a choice between having FFA and soap in the product. If you add acid you turn soap into FFA. Soap washes out, FFA does not. Of course yields will be higher if you add acid because you keep the FFA in the product but is that what you really want? FFA may corrode steel parts but soap will not.

You have removed the glycerine before adding acid so the BD won't contain much FFA but there will be some. How about doing a titration on the product?

It is my experience that perfectly good results, including easy separation and easy washing, can be obtained in a single stage provided you do a titration and add 4.5 g NaOH plus titration. So why add a second base stage?

[This message was edited by neutral on 03 January 2003 at 08:37 AM.]

Neutral
As you say the first stage produces satsifactory results and I wouldnt run my car on anything else.Who needs Acid in an Engine!
However there is something to be said for clarity of the product and I suspect colour tending towards clear.My second stage produced very clear ester.and the following "wash and balance" lightened the yellowing and maintained the clarity.Tending towards ester processed from olive oil.I cant see there would have been much in the way of FFA after the second base stage.Would not the Soap be a result of the high concentration of KOH Salt in solution with water bound by the ester ?I am only working here with well settled ,clear ester no Glyc.?
What would the clarification and colouration issues be indicitive of?
Gell point is 4C ,Its solid at 0 C.

HIntertech

The way I see it is that the location of the soap (and there would be virtually no FFA after the second base stage) is purely a function of the relative affinities of the upper and lower layers for the soap. No matter how little soap you produce there will always be some in the upper layer. So there is always some which can be converted to FFA when you add acid. You could easily find out how much by doing a titration on the product and comparing with BD which had not had acid added. That would be an interesting observation to report.

Regarding the reduction in colour there are compounds in nature which act like pH indicators. I have noticed that the glycerine layer changes colour sometimes when acidified, though this seems to depend on the source of the oil. These coloured compounds must be intensely coloured as they can be present only in minute amounts.

Regarding clarity, it is hard to wash out the last traces of soap as again it is a question of the relative affinity of the BD and water for the soap. When we feel it is washed enough there will still be a trace of soap in the BD, but if you add acid there will be none, it will be FFA.

I think this last trace of soap only makes the BD cloudy if it is wet so drying will produce perfectly clear product. Small amounts of dry soap will be in true solution whereas wet soap, no matter how little, will be present at least partly as an emulsion which interferes with the transmission of light.

from acidifying the glycerine as a 3rd stage to a base/base Transesterfication to Acid/Base experiments?

Perhaps the following entries on 7 Dec 2000, posts 1514, 1515 on the Biofuels Journey to forever list provide a clue

Post 1514 from Kevin to Aleks

What about small quantities of H2SO4 (0.1 to 0.2%) to reduce the FFA in animal fat so that less soap is formed.

Our experiments look promising, (using the NaOH/H2O titration method),titration values have reduced in the order of, from 4.0 ml to 2.6 ml using an initial acid + methanol reaction.

After the acid reaction we perform a BCT to create the tallow esters.

To date, experimental yields have been good with a lot less soap
produced. Tallow ester yields between 70 - 85% have been obtained so far.

When stable and repeatable results have been achieved we will post a
recipe.

Kevin

Aleks responded a few hours later in post 1515:

Hy Kevin,


[Kevin's original message]- What about small quantities of H2SO4 (0.1 to 0.2%) to reduce the FFA in animal fat so that less soap is formed.

Aleks Reply:
Come again? What reduction of FFA? Sulph acid does the opposite - It can for instance split soap into FFA and ionic rest,so it increases FFA levels.

[Kevins original message]: Our experiments look promising, (using the NaOH/H2O titration
method),titration values have reduced in the order of, from 4.0 ml to2.6 ml using an initial acid + methanol reaction.

Aleks Reply: Bah?

[Kevins original messag: After the acid reaction we perform a BCT to create the tallow esters.

Aleks Reply: What's a BCT?

Cheers, Aleks"

I have adjusted my original entry to take account of these new discoveries.

BCT=Base Catalysed Transesterfication.

On 5 Feb 01 Keith
announces the "foolproof Method" to the world on his list post 2533.
Tilly SBC/IBA

[This message was edited by tILLY on 07 January 2003 at 07:24 AM.]

Tilly
For the record you are probably correct in your research ,but what is the point in splitting hairs? is it an attempt to challenge the respect of Mr A for highlighting on the world famous resourse a slight inconsistancy in the time line of famous biofuels discoveries?This does not do you Justice if this is the case.But its good to know someone is watching all the same ;>
Neutral
here I am a little confused.
Quote
"The way I see it is that the location of
the soap (and there would be virtually no
FFA after the second base stage) is
purely a function of the relative affinities
of the upper and lower layers for the
soap. No matter how little soap you
produce there will always be some in the
upper layer. So there is always some
which can be converted to FFA"
There is a lot of soap in emoltion with water ,granted over time the layers do seperate (2 weeks)No fatty acid -No gly\c settling yet lots of white soap .
Forgive my ignorance here but by doing a titration on this FFA free ester (which gave results to suggest the ph was high )but Im not sure if I do good titrations!(give me a good process please)
As you suggest the glyc layer does lighten with when acidified ,however I am convinced that this is not relevant at this level as there is no furthur glyc settling over time from the ester layer so no reaction is possible with compounds existing at this level.
Quote
"Regarding clarity, it is hard to wash out
the last traces of soap as again it is a
question of the relative affinity of the BD
and water for the soap. When we feel it
is washed enough there will still be a
trace of soap in the BD, but if you add
acid there will be none, it will be FFA"
Wouldnt the level of clarity and light colour suggest that the FFA have balanced the ascopic tendancies of the ester.Therefore the clearer and lighter the ester the lower the level of Free Fatty Acid or soap or water .giving weight to your last comment.
Quote
"I think this last trace of soap only makes
the BD cloudy if it is wet so drying will
produce perfectly clear product. Small
amounts of dry soap will be in true
solution whereas wet soap, no matter
how little, will be present at least partly
as an emulsion which interferes with the
transmission of light. "
Im not sure how you mean when you speak of dry and wet soap?
One interesting observation however is when the ester is clear if you add drops of water they sink right through with no seperation and gather at the lowest point without amalgamating ,The same test done on cloudy ester and the drops disapate,however this could be a visual illusion .

[This message was edited by hintertech on 08 January 2003 at 11:36 PM.]

HIntertech

In response to my remark "No matter how little soap you produce there will always be some in the upper layer. So there is always some which can be converted to FFA" you said:

>"There is a lot of soap in emulsion with water, granted over time the layers do seperate (2 weeks) ..."

This suggest that you are not getting a good conversion. Diglycerides make soap a lot harder to handle. If you use plenty of methanol and 4.5g or 5g NaOH plus titration, separation should be minutes or hours, not days or weeks.

You also said "the clearer and lighter the ester the lower the level of Free Fatty Acid or soap or water..."

After treating the oil with NaOH/methanol there can be no FFA present. Even if FFA were present you could not see it as it is totally soluble in biodiesel. But what you said about soap and water is right, excess soap and water will create haze.

>"I'm not sure how you mean when you speak of dry and wet soap?"

Neither am I. It is reasonable to believe however that if you added a little water to BD containing some soap in solution that the soap would absorb some of the water and become visible as haze, as it would no longer be soluble in the oil layer. On drying the haze would disappear again.

Acid/Base Experiments Kevin Tidball, Michale Fox, Aleks Kac

The development of the Acid/Base method of making biodiesel is actually well chronicled on three different discussion forums:
Infopop biodiesel discussion forum
Yahoo Biodiesel
Yahoo Biofuel

I have spent quite a few hours reading entries and found a fascinating story unfold.

Kevin Tidball, an Engineer and Michael Fox, a chemist, worked together on the project. They were both from Australia.
Aleks Kac, a chemist's assistant appeared to be working independently. Aleks is from Ljubljana Slovenija

Things really started to get active in late 2000. Aleks had just developed his 2 stage base/base method and was trying to find a “Foolproof” method that would allow him to use high FFA oil and still get an acceptable yield.
He was experimenting with using a one or 2 stage base technique and then acidifying the glycerine to recover the biodiesel tied up with the soap. He had also discovered an Irish Base/acid method which was discussed.

3 Nov 2000 Alan Portello posted “Since the acid method is good for converting FFA's but inefficent at making biodiesel, and the alkal might it be good to use a two step method for production, with the first step being the acid method, which would presumably convert most of the FFA's, and the second stage being the alkali method?"

6 Nov 2000 Aleks Kac thanks Alan for the suggestion but says “Different experiments are running as we speak”

15 Nov 2000 Aleks Kac posts that for the last two weeks he had been working on “soap decomposition by acid”

29 Nov 2000 Kevin Tidball Posts onto the Infopop Forum the successful results of an Acid/Base experiment he has conducted.

6 Dec 2000 Aleks Kac says he has been working on a Base/Base/ Acid procedure

6 Dec 2000 Keith Addison posts a message from ‘Dave uk’ which says “FFA can probably be acid catalysed. I've not tried this, but the basic recipe has been looked at by an analytical chemist who thinks it should work."

6 Dec 2000 Aleks Kac responds to Keith’s message: “FFA @ home- Not a chance! That is time and material lost. In oreder to get any result at all, the Methanol overdose has to be 5 to 7 fold the stoichiometric value. That one is tried out.”

7 Dec 2000 Kevin Tidball says to Aleks: "What about small quantities of H2SO4 (0.1 to 0.2%) to reduce the FFA in animal fat so that less soap is formed.
Our experiments look promising… titration values have reduced in the order of, from 4.0 ml to 2.6 ml using an initial acid + methanol reaction.
After the acid reaction we perform a BCT to create the tallow esters.
To date, experimental yields have been good with a lot less soap produced. Tallow ester yields between 70 - 85% have been obtained so far.
When stable and repeatable results have been achieved we will post a recipe."

7 Dec 2000 Aleks Kac immediately responds to Kevin by saying “Come again? What reduction of FFA? Sulph acid does the opposite - It can for instance split soap into FFA andionic rest, so it increases FFA levels. Bah?"

7 Dec 2000 Keith Addison responds to Kevin's offer of the recipe “Yes, Please!”

8 Dec 2000 Aleks Kac say: “I'm working on a modified first stage, which will hopefully esterify FFAs, so less lye will be needed for further transesterification.”

11 Dec 2000 Aleks Kac posts: "Teagscs idea is in fact a bit dangerous (the one with the acid stage as a second stage.), because acid is a bit difficult to wash out and nutralization with water and lye is out of the question. I'm having engine toruble after trying out the Teagasc "recipe"

11 Dec Kevin Tidball posts to Aleks: “Alek, The acid reaction I quoted in my previous posting was 1ml H2SO4 and 200 ml methanol to 1 litre of fat. This was processed at 50c for 2 hours to produce the titration listed.
What's the Bah for?”

11 Dec 2000 Aleks Kac replies to Kevin: “Kevin, Acid catalyzed ESTERIFICATION of FFAs requires 1-2% sulph acid to methanol concentrations. TRANSESTERFICATION using acid catalysys on the other hand, is not fesable because it takes 55 times Time and MetOH But never the less,you have intuitively reached the right path."

16 Dec 2000 Kevin Tidball Posts his Acid/Base “Recipe” on the Infopop Forum:

The FATTA method - Development by Kevin Tidball and Michael Fox

First stage acid catalyst (to esterify the FFA)
Oil 1000ml (1 litre)
CH3OH 100m (Methanol)
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

6 Feb 2001 Keith Addison posts: The FOOLPROOF way to make biodiesel

Good news - no need to bother about FFAs, titration, pH meters and all that stuff, just do it this way, no fuss, very high yields. You saw it here first folks!
The FOOLPROOF way to make biodiesel
NEW standard method
By Aleks Kac

Below is the Original Foolproof Recipe
1 litre Oil
100 ml Methanol
1ml concentrated H2SO4 (95%)
Heat to 55deg c
Mix. After 50 minutes turn off heat. Mix for total 1.5 to 2 hours. Oils/fats that are liquid at room temperature will be done in an hour or so, fats that are solid at room temperature will take up to 2 hours.
Allow to settle for 6 to 12 hours

Mix 3.1g NaOH in 100ml Methanol to make methoxide.
Heat oil to 55 deg c.
Remove any glycerine which may be on the bottom.
Add methoxide and stir for one hour
Settle for 6 to 12 hours.

Rev Tilly KE

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

The Foolproof Method Prevails

When Aleks Kac posted his Foolproof Method, Kevin Tidball and Michael Fox thought it resembled their FAATA method quite closely.
Not surprisingly, when the apparent similarity between the two methods were pointed out by Kevin, Keith could see no similarity at all.

6 Feb 2001 Kevin Tidball posts to Keith:
“Well as for first!
Check out,
http://www.mauibiodiesel.org/discussionforums.htm
Under the acid estification section.
The Alek's recipe proportions look very similar the ones posted at the mauidiesel site.”

6 Feb 2001 “skaar” posts to Kevin:
“maybe cause it's close to perfect and they are similar cause both stumbled on the same basic process because they were looking for the best process, course somebody could have gotten inspiration from the other”

6 Feb 2001 Keith Addison replies to Kevin:
“Hi Kevin

Indeed, they're both acid-base 2-stage processes (and not the only ones); you use 1-2 ml sulphuric acid per 100 ml methanol and 1000 ml WVO, Aleks uses 1 ml sulphuric acid per 100 ml methanol and 1000 ml WVO, and that's where the similarity ends.

You use 98% plus sulphuric acid, which is expensive, Aleks uses 95%, which is much cheaper.

You seem to mix the sulphuric acid with the methanol first, Aleks mixes the methanol with the WVO and then adds the sulphuric acid, which has a quite different effect.

You're metering the first-stage process down to a titration of 2.6, Aleks doesn't do any titration at all.

You're then using at least 6.4 grams of sodium hydroxide, depending on titration, Aleks uses 3.1 grams total, regardless of titration.

You're left with glycerine and soaps, which may have to be filtered. Aleks doesn't have any soaps.

Your method is for high FFA oil or animal fat, Aleks's is for any oil or fat - it's one standard process, it doesn't use any titration, it cuts the lye amounts by more than half, it's reliable. Your method states: "This is not for those who don't like failed batches; the proportions and process methods are still under experimentation."

Aleks and I knew you'd posted your method on the Maui board in December, but it didn't seem any different to what you'd posted to the biofuel list earlier that month following a quite lengthy discussion of it on the list with Aleks (see "Re: FFA@home-Why NOT?",
7 Dec 2000, etc). Aleks was working with high FFAs and sulphuric acid well before that anyway.
Best wishes
Keith

6 Feb 2001 Keith Addison replies to “Skaar”
“Not similar, very different. Kevin's wrong.”

At this point it will be interesting to go through Mr Addisons list of “differences” and check if the two methods are “Not similar, very different” as Mr Addison claimed.


You use 98% plus sulphuric acid, which is expensive, Aleks uses 95%, which is much cheaper.
Cost of the chemical is irrelevant as to the differences in the procedures. Aleks does say you can uses H2SO4 which is 3% less pure than Kevin and Michael were using. This makes no meaningful difference to the reaction. FALSE

You seem to mix the sulphuric acid with the methanol first, Aleks mixes the methanol with the WVO and then adds the sulphuric acid, which has a quite different effect.
While the order of mixture is not specifically spelled out in the Tidball/Fox method, in fact all the chemists who have ever commented on this have said that they can find no valid argument that the order the chemicals are added has any relevance to the procedure. They are inclined to suggest that “carefully” adding the H2SO4 to the methanol first is preferable.
FALSE

You're metering the first-stage process down to a titration of 2.6, Aleks doesn't do any titration at all.
TRUE

You're then using at least 6.4 grams of sodium hydroxide, depending on titration, Aleks uses 3.1 grams total, regardless of titration.
TRUE

You're left with glycerine and soaps, which may have to be filtered. Aleks doesn't have any soaps.
Both methods should produce identical amounts of glycerine. This is just a red Hearing Keith has tossed in.
Filtering Glycerine and soap is not a standard procedure when making biodiesel if the biodiesel is washed.
Aleks never showed any proof that the Foolproof method does not make soap. He did make a totally unsubstantiated claim that it didn’t. In fact, most of Aleks’ claims were unsubstantiated.
FALSE

Your method is for high FFA oil or animal fat, Aleks's is for any oil or fat - it's one standard process,
Again, “Claims” have no bearing on the mechanics of the procedure. Whether it washes Whiter than White and Brighter than Bright is totally irrelevant to the actual mechanics of the procedure
FALSE

it doesn't use any titration, it cuts the lye amounts by more than half,
TRUE

it's reliable.
This claim has nothing to do with the similarities and differences between the procedure and as it turns out is a false claim in any case.
FALSE


Your method states: "This is not for those who don't like failed batches; the proportions and process methods are still under experimentation."
Again, claims have no meaning when comparing procedures. As it turned out the Foolproof method was soon going to be modified too.
FALSE

Aleks and I knew you'd posted your method on the Maui board in December, but it didn't seem any different to what you'd posted to the biofuel list earlier that month following a quite lengthy discussion of it on the list with Aleks (see "Re: FFA@home-Why NOT?",
7 Dec 2000, etc.
Again, this has no relevance to comparing the two methods other than to show that Aleks and Keith were both well aware of Kevin and Michaels FATTA Acid/Base procedure on the Infopop Forum.
FALSE

Aleks was working with high FFAs and sulphuric acid
However Aleks was NOT working on an Acid Esterfication first stage. This seems to be just another “Red Hearing” Keith has tossed in to confuse the issue.
FALSE

So, under closer examination, we can say that, other than the fact that Aleks’ Foolproof method never Titrates and uses less NaOH, For all practical purposes the original Foolproof Method by Aleks Kac is identical to the FATTA method developed by Kevin Tidball and Michael Fox.
As we will see latter, this omission of the titration steps and the reduction in NaOH made a HUGE DIFFERENCE, and sadly not for the better.

So, without going into all the gory details, the fact that Keith and Aleks were prepared to vigorously deny any connection between the Foolproof method and Kevin and Michaels FATTA Method at every turn, and The Foolproof method was prominently displayed on Keith’s Journey to Forever site with glowing claims that any “Fool” could now make high quality Biodiesel with no titration and no knowledge, the over simplified “Foolproof method” became the pre-eminent acid base method.

And Kevin and Michaels much more scientifically accurate FATTA Acid/Base Method languished in the Dusty archives on the Infopop Forum for several years.


Rev Tilly KE

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

So the Fatally flawed Foolproof method became the Premier Acid/Base method for home brewers. And immediately the problems began.
Within 2 weeks there was an extra step added to take care of a newly invented phenomena, backsplitting.
According to Aleks Kac, Backsplitting is “Sulphuric acid is a powerfull decomposer. It looks after the 'week link' in organic compounds and splits them there. The ester bond seems to be this kind of week link. So, if acid can split the link between glycerine and a fatty acid it will do the same with a methyl group and a fatty acid.”
According to Todd Swearingen backsplitting is once maximum conversion has occurred “there would be some minor flip-flopping or "back-cracking," what most call an equilibrium state with a slight exchange back and forth.
HOWEVER,
The chemist Neutral (PhD over 20 years biodiesel research) says:
‘If "back splitting" means that the reaction will go in reverse, then there is no basis for the idea. All equilibrium reactions proceed ever more slowly toward equilibrium, never really getting there. Just another bit of unscientific mythology. If it proves that holding the acid reaction too long is detrimental then it has to be because some other unwanted side reaction is occurring.’

And then the Foolproof Failures began in ernest.

“> I have not been able to have a successful conversion using the so called fool proof acid base method, which claims to be titration free. Has anybody actually had any success with this?”

>” acid/base two stage process
I tried the process Aleks described. I started with 17.4 FFA waste restaurant grease which had been dried and filtered to remove contaminants.
I used 1 liter of oil + 100 ml of methanol and 1 ml of 95-98% sulfuric acid. After mixing for 90 minutes at 55C, I went through the second syep as described and settled for 12 hrs. The FFA level only dropped to 14.2. Obviously some FFA`s have combined with the methanol to make methyl esters but not all of it. What am I doing wrong ?? any thoughts ??”
>”I've tried the "foolproof method" with lightly used oil. I got dark coloured water retentive biodiesel that the car hated. I also had to run a second base stage because for my oil the recipe used too little NaOH.”

>”acid/base two stage process
I tried the process Aleks described. I started with 17.4 FFA waste restaurant grease which had been dried and filtered to remove contaminants.I used 1 liter of oil + 100 ml of methanol and 1 ml of 95-98% sulfuric acid. After mixing for 90 minutes at 55C, I went through the second step as described and settled for 12 hrs. The FFA level only dropped to 14.2. Obviously some FFA`s have combined with the methanol to make methyl esters but not all of it. What am I doing wrong ?? any thoughts ??Your help would be appreciated.”

>Having lots of animal fat available, and a failed batch(I've had no failures using vegetable oil) I decided to try the acid esterfication method. All went well until I added the acid - an explosion which shattered the medicine glass from which I was pouring the acid, and sulphuric acid everywhere. Fortunately the only damage apart from paint being stripped was a burnt out thermostat.....

>“Welcome fat man Trust you have a lot of success with the acid / base case...... After you make it work please explain to the rest of us who have read and re-read the instructions and tried it and tried it and tried it, how to make this work every time with any oil.. Titrations aren't any trouble......”

>”......When I read Alek's acid/base recipe I thought it sounded great -and the yields were claimed to be much higher than the traditional
method of single stage base treatment. I have tried it a couple of times on small batches and it doesn't seem to work. It certainly isn't foolproof. I have gone back to the single stage method. It works reliably and is simple. My yields are low (<65%). That is what everyone else seems to use as well.”

>” The foolproof method sounds good but if you read to the bottom there is a comment from Alek that although he has good results it may not work for everyone. I believe he has a consistant supply of oil and worked his formula out using this. You may also have to do the same.
"I'VE TRIED THIS METHOD ONCE OR TWICE BUT WITHOUT SUCCESS."

>“I am aware there has been an update to the Foolproof method and hopefully It is now more reliable. It would be hard for it to be worse than the original one!”

Actually , other than one or two people who said that they got the original Foolproof Method to work with new oil, NOT ONE posting that I read from a reliable person concerning the original Foolproof ever reported a success using it.

After pointing out a time or two to Keith Addison that no one seemed to be able to make biodiesel using the Foolproof method, I Finally posted on 2 April 2002, to Keith Addison “Keith, if you know someone that has gotten the Foolproof Method to work at home, will you have them go over to the Maui board and explain to everyone how they did it. Noone over there seems to have been able to make it work.”

Well, Keith never exactly answered this, but the very next posting was the first (Of Many) from Todd Swearingen who had obvously shown up to “Run Me Outa Dodge”, demanding to see all these heretical postings I had been making. But that is another story.

And 4 days later Keith Announced a Major update of the Foolproof Method which changed many things, except as it turned out, its ability to make biodiesel.

Rev Tilly KE