The Imsides method

[tillyfromparadise Senior Member Find all posts View Profile Close tillyfromparadise]

Re: Reduced oil temperature in reactor ?

Moving the Imisidies procedure discussion over here where it belongs

Hi Wesley,

You are right Smithy. What Dr. Mark's process is is adding an excess of inorganic base, Calcium oxide, magnesium oxide and other bases. The catalyst KOH in normal amounts might act to cause the dried vegetable oil to become biodiesel. But neutralising the free fatty acids is done by mostly other bases present which may be calcium (di) hydroxide and magnesium (di) hydroxide.

Let me see if I understand what you are saying.
According to you, the FFA's are neutralized by whatever was in the cement and the 15g of KOH that is added for every litre of WVO has very little to do with neutralizing the FFA's but is just there as a catalyst.

Do you really believe this???
Have you done any research or experimentation that supports this idea or are you just guessing?

[WesleyB Donating Member Find all posts View Profile Close WesleyB]

Re: The Imsides method

Acid plus base yields salt and water. I do not know the relative reaction rates between calcium hydroxide , magnesium hydroxide and the catalyst caustic (potassium or sodium hydroxide). Dr. mark said swamp it with base from cement. I'm wondering how the aparatus works in processing with cement present. Even if the cement is only used to prepare the methoxide solution, there is often water present in the oil. That's a problem. I'm not guessing. The quantity of cement and its composition were not specified also.

[tillyfromparadise Senior Member Find all posts View Profile Close tillyfromparadise]

Re: The Imsides method

Hi wesley.

Dr. mark said swamp it with base from cement. .

Rubbish!
Mark has made no such claim. Mark said: "If you knew any chemistry at all, you'd understand that the whole point of my method is that the vast excess of base swamps any residual FFA acidity."
Mark is talking about the huge amount of KOH he uses- 15g KOH per litre of WVO.
The only claim Mark has ever made for the cement is that it removes water. That is it!!! Mark has never claimed that the cement has any part in the neutrlization of the FFA's.
There is nothing magical about the cement or in fact this whole procedure.

Please stop making silly guesses about what might be going on and then presenting them as fact because you have made a few test litres of biodiesel.

Let us please stick to the real world

[WesleyB Donating Member Find all posts View Profile Close WesleyB]

Re: The Imsides method

Cement was presented as a source of calcium oxide to dry methoxide solution. I worked once in a cement factory stacking 80 pound bags of cement as they came down a conveyor belt. Ground or powdered rock of some type was passed through a natural gas fire in a turning tube about 3 feet diameter. So calcium oxide is part of the product. So water plus calcium oxide yields calcium di hydroxide , an inorganic base that can react with free fatty acids to produce calcium soap. Magnesium may also be present with a valence of 2. So magnesium oxide (a base) reacts with water probably to form magnesium di hydroxide an other base to react at some rate with free fatty acids. Acid plus base yields salt plus water. The salt is soap (calcium di octadecanoic acid ester and magnesium di octadecanoate both are soaps). I'm not guessing what I don't know mainly is how quickly the soaps form.

[tillyfromparadise Senior Member Find all posts View Profile Close tillyfromparadise]

Re: The Imsides method

Hi Wesley,

Cement was presented as a source of calcium oxide to dry methoxide solution.

And that is all the cement was presented as doing, drying the methoide solution. That is it. The cement dries the methoxide! Finished!

So calcium oxide is part of the product. So water plus calcium oxide yields calcium di hydroxide , an inorganic base that can react with free fatty acids to produce calcium soap. Magnesium may also be present with a valence of 2. So magnesium oxide (a base) reacts with water probably to form magnesium di hydroxide an other base to react at some rate with free fatty acids. Acid plus base yields salt plus water. The salt is soap (calcium di octadecanoic acid ester and magnesium di octadecanoate both are soaps). I'm not guessing what I don't know mainly is how quickly the soaps form.

And in this part you are just making wild guesses as to what MIGHT be happening in the reaction. You have no idea what is happening.
How much of these inorganic bases are present in the drying phase of the methoxide?
How much water is there in the methoxide?
How did these inorgnic bases get from the methoxide drying phase to reaction?

You are just making wild guesses. Your claim that "...neutralising the free fatty acids is done by mostly other bases present which may be calcium (di) hydroxide and magnesium (di) hydroxide." is absoute nonsense.
I do not understand why you sometimes say such silly things.

[WesleyB Donating Member Find all posts View Profile Close WesleyB]

Re: The Imsides method

"Cement-Wikipedia, This cement is made by heating limestone (calcium carbonate CaCO3) with other materials (such as clay) to 1450 degrees celcius in a kiln in a process known as calcination, whereby a molecule of carbon dioxide CO2 is liberated from the calcium carbonate CaCO3 to form calcium oxide CaO, or quicklime. " Calcium oxide CaO accepts a molecule of water H2O to form calcium (di) hydroxide Ca(OH)2. Maybe that's a guess. I don't have a reference on that on hand. Then acid plus base yields salt plus water. Calcium hydroxide (the base) reacts with (slowly) free fatty acids in the vegetable oil to form soaps like calcium (di) octadecanoic acid ester (a salt ,an unwanted soap). Getting the soap out of the biodiesel is a problem due to polarity. Polarity of a molecule is due to electronegativity differences between atoms bonded to each other in the molecule and bond angles in the molecule. The soap is like biodiesel in its' polarity. Like dissolves like relative to solubility. Sorry if I lost anyone in this description.

[smithy Senior Member Find all posts View Profile Close smithy]

Re: The Imsides method

Wesley, I think you are getting mixed up with two quite separate reactions here. After the CaO has done its job removing water from the reaction it takes no further part in the neutralisation reaction, nor does any Ca(OH)2 formed. These 2 chemicals have to be settled in the dried methoxide, so they take no further part in any further reactions.

The problem I had when testing this method some years ago was totally my own fault. I was not careful enough when decanting the methoxide and got some unreacted CaO into the mix, hence the calcuim soaps formed. When i tried it a few weeks ago I was more careful and so the resultant bio was bright and clear, no calcuim soaps.

[DavidS Junior Member Find all posts View Profile Close DavidS]

Re: The Imsides method

Wesley, I think you are getting mixed up with two quite separate reactions here. After the CaO has done its job removing water from the reaction it takes no further part in the neutralisation reaction, nor does any Ca(OH)2 formed. These 2 chemicals have to be settled in the dried methoxide, so they take no further part in any further reactions.

The problem I had when testing this method some years ago was totally my own fault. I was not careful enough when decanting the methoxide and got some unreacted CaO into the mix, hence the calcuim soaps formed. When i tried it a few weeks ago I was more careful and so the resultant bio was bright and clear, no calcuim soaps.

To which I would add that I also got cloudy bio when doing a 200litre batch, which like Dave, I pit down to my carelessness when decanting the "dried" methodise from the quicklime. The slightest turbulence when pouring off, and the fines get whipped up like a whirlwind.

When I did further testing using plastic soda bottles (I tested quicklime, cement and control), all the bio was bright and clear, in fact exceptionally so.

[tillyfromparadise Senior Member Find all posts View Profile Close tillyfromparadise]

Re: The Imsides method

Hi everyone,

Our latest foolproof method that is also titrationless.

Over the years, this "foolproof" claim has been made several times. If ”foolproof” means the procedure always makes biodiesel, invariably they are not ”foolproof”
The claim of being foolproof is a good indication that the author has performed very little actual testing and has a limited understanding of the reaction.
Also the procedure requires at least one magic step.

This ”foolproof” procedure is said to work because the cement dries the methoxide and therefor there is no water in the reaction. Then the addition of “the vast excess of base”-15g KOH per litre of WVO, has magical qualities that “swamps any residual FFA acidity.”

The author of this procedure is apparently unaware that, as smithy pointed out, neutralization of the FFA's produces water and this ”foolproof” procedure does not remove any of the water produced by neutralizing FFA's. In fact it is this water, the water produced neutralizing the FFA's, that causes the most problems with the reaction.
If you have ever used NaOH in the reaction and tried to react high titration WVO, you know that once the titration starts getting around 10 NaOH you are much more likely to form a complete gel due to the large amount of soap produced.

I am currently testing the procedure and will post the results as they come to hand

[WesleyB Donating Member Find all posts View Profile Close WesleyB]

Re: The Imsides method

A book titled "A Text-Book of Practical Organic Chemistry Including Qualitative Organic Analysis" by Vogel , Published by Longman Group Limited , London , Third edition 1970 , gives on page 166 "absolute ethyl alcohol" , dehydration of rectified spirit by quicklime. Rectified spirit is the 95.6 per cent ethanol that carries water with it across a fractionation column in a still head. It's the 190 proof strongest alcohol in a liquor store. My point in bringing this up is reaction rate, the time and temperature it takes to dry alcohol using calcium oxide (quicklime). "The contents of one Winchester bottle of rectified spirit (2-2.25 litres) are poured into a 3-4 litre round-bottom Pyrex flask, about 500 grams of freshly- burnt quicklime are introduced, and the flask fitted with a double surface condenser carrying a drying tube on top. The mixture is gently refluxed on a water bath for 6 hours, and allowed to stand overnight. " Then in a dry still the 199 proof ethyl alcohol is distilled away from the calcium (di) hydroxide which holds the water back. In this Imisides room temperature method of making biodiesel the methoxide solution must be in contact with the calcium oxide for maybe 16 hours at even elevated temperature for the calcium oxide to do its' job at drying the alcohol. It's not a fast drying agent based on reading this proceedure from the grail of organic chemistry fact. A fly in the ointment is what if the vegetable oil is wet? Then the effects of carefully drying the methoxide-methanol solution is quickly undone. I put about 500 milliliters of new corn oil, fresh from a grocery store into a 1000 milliliter beaker, then began heating and magnetic stirring. At around 100 degrees centigrade and up I got boiling . I expect it was water boiling off from new oil. So new oil is not entirely dry (anhydrous). But I did not capture condense and test what was boiling off. It might have been radon, francium, uranium, who might guess what boils off from oil at 100 degrees and up? Tests are needed. Even new oil probably has water in it. Used oil probably has more, that's a guess.

[tillyfromparadise Senior Member Find all posts View Profile Close tillyfromparadise]

Re: The Imsides method


TESTING----------TESTING----------TESTING----------TESTING

Hi everyone,

Before even sillier claims are made for this procedure, I thought it would be a good idea if some meaningful tests were actually performed and do away with all the navel gazing that has been going on up to this point.

Do be mindful that the author of this procedure has states on several occasions that the 3/27 test is not importance. I am pretty sure his definition of making biodiesel is that there is separation of by-product on the bottom and biodiesel on the top.
That is the main judgement I will use in these tests to determine whether biodiesel has been produced and I will not do any 3/27 testing

If you knew any chemistry at all, you'd understand that the whole point of my method is that the vast excess of base swamps any residual FFA acidity.

I am not sure where you live, but in the world where I live that is not an accurate statement.
Where I live, the 15g KOH per litre of WVO you require for your reaction, would, at the very best, only neutralize all the FFA's in one litre of WVO titrating up to 15 KOH. Then the KOH will be all used up and if the WVO titrated more than 15 KOH no further neutralizing of FFA's and no further catalyzing will occur.

But if you want to take the bet bring along your "WVO titrating 15KOH or above" oil and I'll demonstrate it for you.

Cheers mate, but no worries. Everything is sweet. I have the testing under control


THE PROCEDURE

Early Saturday morning I went to the local hardware and asked for a bag of their finest magical General Purpose Grey Cement.
I stressed that the magical qualities were very important. The salesman assured me that the bag of cement I bought for the princely sum of $6.50 was considered first quality magical grade

So I took my prized bag of cement home and made up enough methoxide to the required formula so that I could perform a number of tests when the obligatory 2 day settling period was over.

Meanwhile the hunt was on for high titration oil. I did know I had some but it took a while to locate it.
The WVO I finally located titrated about 18 KOH

This morning, as the end of the 2 day settling period approached I heated several litres of the high titration WVO to remove any water present.
I heated it well past the measuring ability of my thermometer and continued to heat until all bubbling had stopped.
When The oil had cooled to around 40C I re-checked the titration and it was still around 18 KOH
I then proceeded with

TEST ONE

I decanted one litre of 40 deg C WVO into a 2 litre Dr Pepper bottle, added the required methoxide, screwed the top down hard and shook mightily. I shook for an initial 30 seconds and then off and on frequently for the next hour.
After an hour of shaking I left the oil to sit for another hour and there was no separation.
I then performed a titration on the contents of the bottle and found that it titrated 5 KOH.

Why am I not surprised

Conclusion
15 g KOH is not sufficient to neutralize all the FFA's in a litre of WVO titrating 18 KOH and no biodiesel was produced.

More test results to follow as they come to hand

[WesleyB Donating Member Find all posts View Profile Close WesleyB]

Re: The Imsides method

If the calcium oxide is present when the transesterification is done on the vegetable oil, it might work. I treated new corn oil with magnesol, magnesium silicate, then boiled what was probably water out of it with heating and magnetic stirring. When I tested for free fatty acids with phenolpthalein and isopropyl alcohol, I got a pink color with one drop of the sodium hydroxide (weak) solution. A minimal amount of ffa's were present. This low temperature method seems to have worked with vegetable oil that had little free fatty acids. That's good work Tilly on your titration 18 vegetable oil test.

[tillyfromparadise Senior Member Find all posts View Profile Close tillyfromparadise]

Re: The Imsides method

TEST 2- “Apple Sauce”

Hi everyone
My second test used the same oil titrating 18 KOH as the first test.

My concern was that because I had actually performed the first test at 40C there may have been a complaint that the magic involved with this procedure is specific to cold WVO and by using warm WVO in the reaction I had possibly damaged the magic.

Keeping with the spirit of having fair testing, I felt I should repeat the test using room temperature WVO (25C).

Using oil from the same pot as I used for the first test I did the second test at room temperature.
The WVO turned to “ Apple Sauce” almost immediately and no matter how much I shook it stayed Apple Sauce.

An explanation of "Apple Sauce"

When you react WVO, in the first few minutes the oil goes through a transition where the viscosity of the oil first increases and then suddenly decreases.
I have noticed that the higher the titration of the oil, the more viscous the oil becomes before suddenly reducing viscosity.

Over my years of testing I have experienced on several occasions that, if you are using insufficient caustic in the reaction, the oil will “hang up” at the increased viscosity and the reaction will go no further. No matter how hard you shake.
In this increased viscosity state it looks very much like Apple Sauce so I call it Apple Sauce
It will stay Apple Sauce until you add more caustic to the reaction.. Then the reaction usually continues where it left off.

A day after performing this latest experiment the oil in the bottle still looks like Apple Sauce.
Later today I will add more Caustic (Mixed in methanol) to the reaction to see if the reaction will continue.

I did check the titration of the Apple Sauce and to my surprise it titrates 5 KOH, just like the first batch

If you knew any chemistry at all, you'd understand that the whole point of my method is that the vast excess of base swamps any residual FFA acidity.

When should I expect this "swamping" phenomena to occur

CONCLUSSION


As my very first test showed, this procedure is not "foolproof"
No magical qualities detected anywhere

Methoxide containing 15g KOH is not sufficient to produce biodiesel from WVO titrating 18 KOH. In fact methoxide containing 15g KOH is not sufficient to neutralize all the FFA's in WVO titrating 18 KOH


More test results as they come to hand

[smithy Senior Member Find all posts View Profile Close smithy]

Re: The Imsides method

Apple sauce is probably due to the water liberated from neutralisation. As there is insufficient catalyst for any transesterification to proceed the water will be held in suspension instead of being absorbed by glycerol (not present as the reaction cannot proceed that far)

[WesleyB Donating Member Find all posts View Profile Close WesleyB]

Re: The Imsides method

Maybe there is a misunderstanding of the term "swamping" with base. Sawamping to me means a great excess, like a tidal wave swamping an area of land. So excess cement adsorbing water from the materials forms excess base calcium (di) hydroxide that makes the ffa's neutralised. The excess base over powers present weak acids . But the proceedure whre the hydrolyzed cement is removed prior to neutralizing the ffa's requires the caustic catalyst to neutralize the free fatty acids. The catalyst is show to be deficient in quantity to neutralize the free fatty acids and remain in adequate concentration to produce (transesterifiy) the biodiesel. The no titration proceedure is incorrect, but it works with vegetable oil with no ffa's present. I have not tested my low temperature imisides method (biodiesel) for soap content yet. I did get a transparent product and glycerine fall out.