The Imsides method

[Tony From West Oz Vice Chairperson of WARFA Find all posts View Profile Close Tony From West Oz]

Re: The Imsides method

Obviously, swamping does not mean that 15g/L of KOH will "swamp" an oil titrating at 18 (KOH) g/L.
Perhaps he meant 150g KOH??
I am sure that would "swamp" oil titrating at 18(KOH) easily.

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

Re: The Imsides method

Components of cement become an inorganic base upon reacting with water (drying the methoxide/ methanol solution). Calcium oxide reacting with water adds two hydrogen and one oxygen to calcium oxide , yielding two hydrogen and two oxygen and one calcium. Calcium forms two bonds (a valence of two). Hydrogen forms one bond. Oxygen forms two bonds. So with calcium in the middle single bonded to two oxygen atoms on either side of a calcium atom. Each of the two oxygen atoms are single bonded to one hydrogen atom, making two hydroxide groups (ions) on opposite sides of the calcium atom. There is more than 15 grams per litre of metal hydroxide molecules to react with ffa's if the calcium oxide/calcium di hydroxide (cement) is left in during the reaction. That would be an excess of hydroxides (swamp?). I'm not sure if that's what Dr Mark meant to say. I'm referring to tilly using 15 grams of caustic on an 18 titration used vegetable oil using this low temperature method earier in this thread.

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

Re: The Imsides method

TEST 3- WVO TITRATION 10 KOH

On this test I mixed oil to produce a lower titration oil. I was initially aiming for around 12 KOH but it came in around 10 KOH.
So I decided to give it a go and see what happened.
I did think there was a good chance this would just scrape in and have separation, but it was a toss up. I was sure WVO with a 12 KOH titration was very unlikely to achieve separation and I was trying to find the lowest titration oil that would still not achieve separation- In other words it would not make biodiesel.


THE TEST

I dried the oil the same as in the past and allowed it to cool to room temperature (25C)
I then added the methoxide, shook hard off and on for over an hour and then waited to see what happened.


RESULTS

The oil became low viscosity- no apple sauce, but after several hours of sitting there was no Separation.
I titrated the resulting oil and as soon as the indicator went in it changed colour which meant that all the FFA's had been neutralized- a titration of 0 KOH


CONCLUSION

If I were to make a guess (which I usually leave to Wesley) I would guess this batch was very close to separation.
However, we are now at three batches and no biodiesel produced yet using this “foolproof “ method.
Perhaps titration 8 KOH will the golden “foolproof” number.

More test results as they come to hand

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

Re: The Imsides method

Just a quick one, I think its gotta be a little simpler than we give it credit for.

The concept of the titration from my understanding is to find out how much extra catalyst is required to convert the oil.

common base rates used are 8 grams for KOH and 3.5 - 5 grams for NaOH.

sooooo, if you are putting in 15 grams TOTAL per litre of oil of KOH, then you are only ever going to convert oil that titrates around 7, as the first 8 grams are used up in the activity of converting the 'virgin' oil, and the remaining 7 are used up converting the FFA's created when cooking with the oil?

Now I know that explanation is laughable to you lot you have a keen understanding of the process.

I just wanted to put a lay spin on it.

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

Re: The Imsides method

Hi Cade,

The reason we titrate is to find out how much Caustic- NaOH or KOH is required to neutralize the FFA's in the oil
This is in addition to the NaOH or KOH required to catalyze the transesterification reaction that actually produces the biodiesel

Your understanding is pretty accurate- until we come to magical procedures like this one. Then the sky seems to be the limit

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

Re: The Imsides method

RE-PROCESS TITRATION 18 KOH "APPLE SAUCE" BATCH.

The results for this reprocess I found quite interesting
I mixed 10g KOH into 50ml Methanol.
The Apple Sauce was quite firm, not really liquid at all and at room temperature.
I added the methoxide and the Apple Sauce immediately went to a thin liquid and quickly changed from a light colour to a dark brown colour.
Most impressively, the whole litre of oil heated up substantially. Although I did not think to measure the temperature, I would guess easily 40C, maybe more.

No doubt about it, we were certainly back into the soap making business


RESULTS

There was no separation so the reprocess did not make biodiesel.
The reaction went further and the oil is now runny at room temperature with a titration of 0 KOH.

I do not intend on doing anything more with this litre of oil

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

Re: The Imsides method

I did the soap test on this low temperature Imisides method (titrationless) biodiesel making formula. I made maybe 100 milliliters of biodiesel from magnesol treated new corn oil at room temperature (25 degrees centigrade). I put ten grams of the biodiesel into a clean 50 milliliter beaker with an operating small magnetic stirbar. I added about 20 milliliters of 99% isopropyl alcohol at room temperature then 2 drops Bromophenol Blue Ph indicator solution. The indicator turned blue indicating basic Ph. I added 135 drops of 0.01 Normal hydrochloric acid, but the test liquid did not turn yellow (acid). About 24 drops of water is a milliliter. I'm at a loss temporarily what to do . There's residual catalyst and calcium di hydroxide and calcium oxide and soap in the liquid. The biodiesel formed but purifying it is a problem. I have a substantial glycerine layer.

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

Re: The Imsides method

Hi wesley,

There's residual catalyst and calcium di hydroxide and calcium oxide and soap in the liquid.

How did you determine there is calcium di hydroxide and calcium oxide in the liquid or are you just making wild guesses again

if you react new vegetable oil with 15g KOH! it is likely you will have a lot of soap!!

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

Re: The Imsides method

Just to stop and have a look at this.

NO TESTING has ever been posted that supports the contention that the water is being sucked out of the methanol by the cement.
Maybe the water is happier being mixed with the methanol and virtually none of the water is taken up by the cement.

The only meaningful testing that has been posted so far that I have seen is to demonstrated the procedure is not foolproof.
Other than that it is just conjecture as to what , if anything, is happening

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

Re: The Imsides method

A book I have titled "A Text-Book of Practical Organic Chemistry" by Arthur Vogel , 3rd edition , published by Longman (London) in 1970 says on page 166 and 167 that water is removed from 190 proof ethanol by quick lime . The proceedure is described on how to dry 190 proof grain spirits to 99.5% anhydrous ethanol. 0.5% of water remains. The water reacts with calcium oxide (it's sucked out) to form calcium dihydroxide. You might find this title in a University library. The name of the proceedure is "Absolute ethyl alcohol".

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

Re: The Imsides method

Hi Wesley,

What does the book say about methanol

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

Re: The Imsides method

An answer to my own question-

"Specific compounds dried with calcium hydride and analyzed for residual water content include benzene,² dioxane,² acetonitrile,^2,4 methanol,⁵ ethanol,⁵ 2-butanol⁵ and t-butyl alcohol...

Methanol and ethanol are dried to ~100 ppm residual water content,⁵ in conflict with an early recommendation against using this drying agent.⁶ Apparently, calcium hydride reacts with water considerably faster than with alcohols, making it an excellent drying agent for these compounds."

http://reag.paperplane.io/00000531.htm

So apparently calcium hydride does dry methanol

[Tony From West Oz Vice Chairperson of WARFA Find all posts View Profile Close Tony From West Oz]

Re: The Imsides method

We learn something every day. Isn't that right Tilly?

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

Re: The Imsides method

In organic reactions often a general reaction applied to a specific reaction applies to many other similar reactions. Calcium oxide adsorbing water from ethanol probably means it will absorb water from other alcohols with carbon carbon single bonds , like ethanol, propanol butanol isopropanol et cetera. So it probably adsorbs water from methanol (a similar reaction) producing calcium di hydroxide. Calcium oxide is a base. A base is a proton accepter. An acid is a proton donor. Calcium oxide, with one calcium atom and one oxygen atom accepts a hydrogen atom from water (the proton) making briefly calcium hydroxide with a positive charge, then the residual hydroxide from the acidic water losing a hydrogen atom quickly bonds with calcium hydroxide + to make calcium with two hydroxides bonded to opposite sides of the calcium atom. I did not copy that out of a book.

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

Re: The Imsides method

RE-PROCESSED TITRATION 10 KOH BATCH- ACHIEVED SEPARATION

Hi everyone,
I did a reprocess of the 10 KOH titration batch using 6 KOH mixed into 50ml methanol and achieved separation.


CONCLUSION

We finally made biodiesel.
So far I do not see any benefit in this procedure over the standard single stage method