New Methods #2. The Imisides Method

[tillyfromparadise]

Re: New Methods #2. The Imisides Method

Hi Geewizztoo,

Just a minor correction Tilly, it's 10 minutes at 8 deg C.

Correction noted

I have had my small batch of 10%w/v KOH methoxide 'soaking' with CaO for two days now, so I am all set to run my side by side tests at room temperature when I get home tonight. I'll report back with my results in a day or two.

I wait to see your results

By the way Tilly, in your test why did you heat your oil? Did you ever doubt that 1ml titrating oil would fail the 3/27 test with this much KOH?

I have never really done any in-depth experimentation with KOH. By the time I started using KOH I was finished with all the testing I wanted to do (until now)
I know that using this much excess NaOH would be a disaster. I really have no experience using very limited methanol with a huge excess of caustic. I was pleasently surprised with the results.

The reason I heated the oil was because I do not believe in magic. From past experience I know that if I had performed the reaction at room temperature I would have been shaking the Dr Pepper bottle for at least 10 hours. Probably more like 12 hours.
There is a rule of thumb in chemical reactions (which seems to apply pretty well to the biodiesel reaction) that for every 10deg C the temperature is reduced reaction time is doubled.

So if the reaction takes 1.5 hour at 50deg C then it takes 3 hours at 40deg C, 6 hours at 30 deg c and 12 hours at 20deg C.
And then you add on more mixing time "Just in case"

My Thoughts
Most of my oil titrates around 1 KOH. The oil I used in this reaction was from a particurlarly lightly used batch that I got from a private school. It was probably used about once.

I will have to do some further testing. I may well change my production technique. I will call it "The World famous Dr Pepper KOH Hammer Technique (Pat Pend)"

[geewizztoo]

Re: New Methods #2. The Imisides Method

Just a minor correction Tilly, it's 10 minutes at 8 deg C.

I once made a batch at 8 degrees C (in Melbourne "room temperature" can be pretty cold) and it appeared to go to completion in about ten minutes.

I tend to agree with you, the reason Mark claims its titrationless is the substantial dose of KOH, which would probably react any of the good to moderate oils that most of us encounter. 10%w/v equates to 15g/L WVO which should take care of oil titrating up to about 7ml.

I have had my small batch of 10%w/v KOH methoxide 'soaking' with CaO for two days now, so I am all set to run my side by side tests at room temperature when I get home tonight. I'll report back with my results in a day or two.

By the way Tilly, in your test why did you heat your oil? Did you ever doubt that 1ml titrating oil would fail the 3/27 test with this much KOH?

[tillyfromparadise]

Re: New Methods #2. The Imisides Method

Just to recap the claims for this procedure,
It is foolproof (no titration required)
It proceeds at room temperature.
The process is utterly anhydrous
A complete reaction is achieved in about 10 minutes at 6 deg C
Only uses 15% methoxide.

Apparently there was no testing performed to support any of these absolutely amazing claims. A faith based procedure?

To be honest, I have a hard time believing any of the above claims other than the fact that the reaction will procede at room temperature, but certainly not to completion in 10 minutes.

I could not locate any CaO so I decided to perform a reaction using the recommended amounts of chemicals minus this magic ingredient.
In earlier experimenting when I was using NaOH, I had observed that there was a certain trade-off between the amount of Methanol and NaOH used. In other words if you increased the amount of NaOH used in the reaction you could decrease the amount of methanol and still achieve the same results as far as biodiesel quality was concerned.
The tradeoff was that increasing NaOH increased soap production and you soon produced a gelled biodiesel because of the extra NaOH soap produced.
KOH soap does not normally form a gel in biodiesel.

In my mind I thought the huge excess of KOH used in this procedure was probably more important than the CaO.
So I heated up a litre of WVO (titration probably around 1 KOH) and reacted it with 150ml methanol containing 15g KOH (A huge excess of KOH) in a 2 litre Dr Pepper bottle. After 2hours of repeated shaking I performed a 3/27 test with the biodiesel and it just passed the 3/27 test.

I am pleasantly surprised.

[geewizztoo]

Re: New Methods #2. The Imisides Method

I just look for the easiest path to travel so in saying that is there an easier way? always open minded to suggestions

Yeah, just do what you do now, except leave out the CaO.

Save a couple of days lead time, avoids the messy sedimentation, decanting and disposal of caustic slurry.

[murf]

Re: New Methods #2. The Imisides Method

Thanks Murf,

Have you ever made biodiesel by the exact same process, except omitting the CaO as a direct comparison?

With reasonable oil, heat and at this level of KOH, this recipe should make perfectly acceptable biodiesel without CaO.

I.

good question, no I haven't made BIO without the CaO

it works for me and I guess if it ain't broke don't fix it

I am no chemist or scholar just a brain challenged bloke I suffer chronic headaches and chronic neck pain so I just look for the easiest path to travel so in saying that is there an easier way? always open minded to suggestions

cheers Murf

[geewizztoo]

Re: New Methods #2. The Imisides Method

Thanks Murf,

Have you ever made biodiesel by the exact same process, except omitting the CaO as a direct comparison?

With reasonable oil, heat and at this level of KOH, this recipe should make perfectly acceptable biodiesel without CaO.

I'll have to repeat my tests at room temp to see if I can see any difference in the rate of reaction.

I've been doing more reading and it seems that CaO can absorb a maximum of 28.5% by weight of moisture and it takes several days to saturate. So if we wanted to fully dry the methoxide we would need to use about 3.5 times the weight of KOH.
Murfs method of leaving the methoxide for several days to settle would have merit to let the CaO 'soak'. Although, to maximise absorption we would need to agitate the mixture to fully expose the surface area of all the CaO particles to the methoxide.

[tillyfromparadise]

Re: New Methods #2. The Imisides Method

Hi Murf,

Did you ever do a 3/27 test?

yes in the early days and it passed no worries

That is interesting to hear.
Because you are evidently the only person to ever actually perform any testing with this procedure, Just to confirm that your fuel does pass the 3/27 test could you perform a 3/27 test on some of your biodiesel that you have in storage and report back your results.

3/27 test posted here


For years I used a similar fomula to the one you use use except I only used 6g NaOH mixed into 150ml methanol per litre of oil reacted and no CaO. That also made very nice biodiesel.

[murf]

Re: New Methods #2. The Imisides Method

Did you ever do a 3/27 test?


yes in the early days and it passed no worries

I learnt what oil did what and just go by feel now

I don't spend a lot of time making BIO compared to some, I am human and very lazy and will take the path of least resistance

I have to use my Iphone timer to keep reminding me of the steps though, I learn't that the hard way

cheers Murf

[murf]

Re: New Methods #2. The Imisides Method

Hi Murf,
Thank you for your reply.
Can you be more specific as to what tests you have performed.
Did you ever do a 3/27 test?

What formula do you use to make biodiesel?
In particular how much methanol and how much KOH and CaO do you use for each litre of oil reacted?
For instance, while Mark's instructions are a bit vague. as close as I can make out, Mark seems to recommend using 150ml methanol, 15g KOH and 30g CaO for each litre of WVO being reacted. That would work out to 15 litres of methanol per 100 litre of WVO being reacted.

I make 55lt batches of Methoxide in a 60lt home brew drum with a tap at the bottom

551t of Methanol

5.5kg of KOH, I mix in 2.5kg one day and 3kg the next, it gets too hot if I put the 3kg in first

5kg of CaO quicklime is stirred in once it has cooled down, usually the next day (a good long stir)

then after a few days settling I decant off the Methoxide into 20lt plastic Jim Beam containers, I put 17lt into these containers as only 15lt drains out when level, with the remaining 2lt I use the very scientific method of that oil looks **** so I tilt the drum and pour an extra 1lt or so of Methoxide into the reactor. the CaO settles some more in the 20lt containers.

15lt of Methoxide to 100lt of 50deg Celsius WVO I never used to heat the oil at first but just got into the habit of heating in winter and just kept heating

mix through processor for one hour

drain off by-product

pump to 205lt open top drum let settle for a few days, this drum has a stand pipe inside it so I can decant of the Bio and leave the residual by-product to be drained into a 20lt drum

gravity drain Bio to another 205lt open top drum this drum also has a stand pipe inside it so I can decant of the Bio and leave the residual by-product

Air wash the Bio with a fish tank bubbler, usually 3 to 5 days, this is the other very scientific method of a sniff soon tells you if it still has methanol in it

Pump up to 1300lt stand tank with gravity feed bowser, I keep an eye on the settlement in this tank through the bottom drain I fitted a valve to and I get very little by-product
I also have a 205lt open top drum plumbed into the processor for settling oil, it has a stand pipe inside so I can decant off the settled oil and drain out any water and chips. I pump into this from my oil trailer tanks and also empty the dregs of the 20lt drums of oil into it

I use the processor pump to fill the processor from an open top drum at knee height, I pour 20lt drums of WVO into this keeping an eye out for the rubbish on the bottom that is then poured into the oil settlement tank

oh well back to the brew room to make some BIO and run the still for some moonshine

cheers Murf

[tillyfromparadise]

Re: New Methods #2. The Imisides Method

Hi geewizztoo,
I think you are correct.
I have changed that part of my post.

Tilly, the way I read it, I think Murfs referring to 55L batches of methoxide.

[geewizztoo]

Re: New Methods #2. The Imisides Method

Thanks Murf for joining this interesting discussion.

Can you tell us your recipe and procedure? ie. specific quantities, mix ratios, times, etc?

I'm particularly interested in your methoxide mixture, I assume you put the KOH in first, then the CaO. How long do you mix the CaO and how long do you leave it settle before you use it?

Tilly, the way I read it, I think Murfs referring to 55L batches of methoxide.

Thanks Wesley, the dessicant properties of CaO in alcohols is well documented as you have discovered. It does seem to take some time to adsorb the water and perhaps the exchange of info in this thread will be able to pin down how us biodiesel homebrewers can put it to good use.

[WesleyB]

Re: New Methods #2. The Imisides Method

A book, Practical Organic Chemistry written by Vogel gives a laboratory procedure for drying 95% ethanol to 99.5% dry ethanol. It uses Calcium Oxide to pull out the water leaving almost anhydrous ethyl alcohol. 500 grams of Calcium Oxide is put into 2 litres of 95% ethanol, then 6 hour reflux, then sits overnight in a sealed flask, then the 99.5% dried ethanol is distilled off. In the book next is a procedure for making super dry ethanol. The book says methanol may also be dried using Calcium Oxide. I think it doesn't take out all the water, but it gets most of it out.

[tillyfromparadise]

Re: New Methods #2. The Imisides Method

Hi Murf,
Thank you for your reply.
Can you be more specific as to what tests you have performed.
Did you ever do a 3/27 test?
What size batches of biodiesel do you make?

What formula do you use to make biodiesel?
In particular how much methanol and how much KOH and CaO do you use for each litre of oil reacted?
For instance, while Mark's instructions are a bit vague. as close as I can make out, Mark seems to recommend using 150ml methanol, 15g KOH and 30g CaO for each litre of WVO being reacted. That would work out to 15 litres of methanol per 100 litre of WVO being reacted.

[murf]

Re: New Methods #2. The Imisides Method

Hi Murf,

With those quantities I imagine you have been very careful to document all the testing you performed and their results on each batch of biodiesel you produced.

I am sure everyone would really like to see the testing you performed and the results.

mate I did all sorts of tests I could find at the time and gave Mark a heap of questions when I first began making Bio, to be honest I now don't do any testing of any sort other than a sniff test to see how much methanol is in the bubbling tank and a quick sight test in a class jar to see how clear it is before pumping to my 1300ltr storage tank

I use one of those 60ltr home brew drums to mix the methanol and Koh then the Quicklime, I do 55ltr batches at a time,
the valve is high enough on the home brew drum with a little back slant on the drum to decant the methoxide off the top of the settled CaO into 20lt containers (17ltrs as there is 2 ltrs left at level) this is then gravity fed into my processor

I live on a 120ac property and the lime is spread over the paddocks, yep it kills the grass at first if put on in one dump but soon all is good again

this is such a KISS system and any monkey can do it as I am proof over the years (don't tell anyone as I will have a fight to keep my oil supplies )

I have no idea of what titration I have as I have never tested it ever??? some really ugly looking oil/fat will give me more by-product but who cares, I just churn it out and use it

I do heat the oil to around 50deg C I think, haven't tested it for a couple of years, I time the heater and put my hand on the tank to see if it is too hot.

the only problem I have had is the mates 80 series 1HZ injector pump rattles like a marble in a shaken tin can, he had the pump fixed for $1300 and it still did the same thing haha, a pusher pump fixed that and has since put 5000ltrs or so through it

oh and my GQ didn't like a sub zero morning running frytoll LARD once lucky I had power and a fan heater

in short you don't have to be a biochemist to do it, it is very financially rewarding, only takes up a couple of hours of my time a week and most importantly allows me to do things that I could not afford before I started making BIO (thanks again Mark )

on the negative its messy and there are literally hundreds of drums sitting around the place, I have made several oops by leaving valves open and filling the dam with a couple of hundred ltrs of BIO and WVO a couple of times (never walk away or get distracted when draining by-product or water from storage tanks)

so tied and have a screaming headache so if what I said don't make sense then there's ya answer haha

cheers Murf

[murf]

Re: New Methods #2. The Imisides Method

Quicklime - It's not a DG, so there should be no special transport or storage considerations involved. When I bought it over the counter I think I paid $12 for a 20kg bag. From memory it was a 90% purity product, with most of the rest of it being MgO

the Tamworth plant won't let me pick it up in a trailer, has to be on a truck with cages straps and tarps, awaiting transport notes and delivery price, Quicklime is $300/Tonne

cheers Murf