A few years ago I released my first new method for base-catalysed biodiesel manufacture ( Imisides-Pyne ) using a heterogenous catalyst. Due to the cost and logistical difficulties involved in the use of a heterogenous catalyst, however, I never actually used that method and went on to develop another new method using a homogenous catalyst.
Having now used this method for a couple of years, and decided that it has no commercial value (as it will never replace the commercial acid/base process), I now release it for public consumption.
This method has two advantages over the conventional base-catalysed transesterification process:
1. It is foolproof (no titration required)
2. It proceeds at room temperature.
In principle, this differs from the conventional method in that it modifies the methoxide solution by the addition of a drying agent (calcium oxide, or Quicklime). This removes water and pulls the equilibrium to the right, thus resulting in a far higher concentration of methoxide, which speeds up the reaction kinetics such that heating is not required.
Here are the reactions:
1. MeOH + OH- ↔ MeO- + H2O
2. H2O + CaO → Ca(OH)2
Adding the two reactions together we get
3. MeOH + OH- + CaO → MeO- + Ca(OH)2
Note that reaction 1 is an equilibrium. The addition of the CaO removes the water, thus pulling the equilibrium to the right and greatly increasing the methoxide concentration. The obvious implication of this is that since you no longer need to worry about forming emulsions from water in your reaction mixture, you can add as much base catalyst as you want.
Dissolve about 10% w/v KOH in methanol – for example, 2kg KOH in 20L MeOH. Caution – depending on how quickly you add it, this may get hot enough to momentarily boil the MeOH – make sure there are no naked flames in the vicinity.
Now, add the CaO and stir vigorously for several minutes. Since this process is heterogenous (the CaO doesn’t dissolve), vigorous stirring is required to allow as much contact as possible with the water in solution. I generally stir for a good 5 minutes.
Now allow it to settle. Most of it will settle out quickly, but the fines take a lot longer. I generally allow two days for it to settle. How much CaO do you use? I generally use about two shovels full in 20L so that when it settled it was about an inch thick on the bottom.
Now just add the methoxide solution to the WVO in your normal quantities at room temperature. I generally use a mixing ratio of 100:15. Depending on how cold it is and your stirring setup you may need to heat the oil a little to thin it out enough for your stirrer to stir it adequately. The reaction is mildly exothermic and the temperature should increase by about 6°C. The reaction appears to go to completion in 10 minutes but I generally let it react for an hour. Let it settle for a day and tap off the sludge in the bottom that contains the glycerol, KOH and fatty acid salts.
After the initial reaction and settling period, a small amount of reaction products remain in the biodiesel due to residual methanol. When the methanol is removed, they fall to the bottom and may be isolated. There are probably several ways to do this, but due to the highly alkaline nature of the reaction mixture, water washing is not one of them.
I use air purification and just use a small aquarium pump to bubble air through the product for several weeks before using it (there is plenty of information around on other air washing setups). Against the biodiesel background, methanol has a characteristic acrid odour that you can quickly train yourself to recognize, and so a smell test can help work out whether the product is ready or not. The surest result, however, is if you just allow plenty of time for the MeOH to evaporate.
1. Quicklime is not easy to get your hands on, unlike hydrated lime, or Ca(OH)2 – don’t get the two mixed up. Although it’s made and used by the truckload in cement factories, since it has no common domestic use it is generally not sold in hardware stores or chemical suppliers. Ideally, you’re looking for a cement factory that has a retail shop, but they aren’t that common. For those of you in Melbourne it’s easy – just go for a drive up to the Unimin factory in Lilydale on a Saturday morning and you can buy it over the counter. For those of us here in WA, Cockburn Cement don’t retail to the public, but I found a mob up in the northern suburbs (Susac Lime) who said they could get some of the Cockburn product for me.
Note – Quicklime does not store well. It is very dry and will absorb water on storage. The best way to store it is to transfer it to a sealed container where it can be isolated from atmospheric moisture.
2. The methoxide solution is unstable (presumably due to carbonation) and must be freshly made for each batch
3. This method is not optimized. The initial recipe that I tried worked immediately so I didn’t bother experimenting with it further. It may be possible, for example, to get away with a lower concentration of KOH or less lime.
4. By publishing this method on the web it is now in the public domain, so you are free to redistribute it wherever you wish. My only request is that you ensure that my name is attached to the method.
Simple schematic for a pump and heater control with a high limit
Sensor for the biodiesel/glycerin layer
Interesting; thanks for sharing.
There's lots of talk about different types of lime here lately. Did you check out this thread? http://biodiesel.infopop.cc/ev...9605551/m/3397000933 You might have some interesting viewpoints or experience to contribute there as well.
I wasn't able to access any of the articles, but it appears that they are using hydrated lime as a heterogenous catalyst.
The reason for this is pretty easy to understand - hydrated lime is a very common industrial base and is much cheaper than NaOH. It is used in preference to NaOH in the waste management sector, not only because it's cheaper, but because it also adds weight to any settled flocs that you're trying to create.
It also has the advantages that as a heterogenous catalyst it will probably sop up some of the water that is formed (by adsorption) and also adds weight to the settling phase (glycerol).
Chemically, it wouldn't work as well as potassium carbonate (my first method) as the K2CO3 avoids the creation of water completely, but the lime would probably work well enough and would be a lot cheaper.
Heterogenous catalysis has a lot going for it - the glycerol sticks to the catalyst like glue, resulting in very fast separation - the only problem is engineering - how you get the settled catalyst/glycerol mass out of the bottom of the reactor.
But of course, they have to be heated. The room temperature method that I have presented here is so simple that you could make it in a big plastic bucket.
Now that the cold has settled here in the northern hemisphere we can think about next seasons bio batches.
1. If the methoxy is allowed to settle before adding to the reaction wouldn't most of the CaO sludge be left behind in the methoxy container? Decant the methoxy needed for the Biodiesel reaction from the top. This would leave some fines in the bio/gly but that could be drained with the glycerol via a GL1 setup.
2. Could whole batch demething be performed on the above biodiesel/glycerol/residual CaO fines mix before draining without releasing the water from the CaO into the bio?
3. Can the CaO sludge remaining in the bottom of the methoxy container be used over again?
4. Wouldn't the amount of CaO needed equal the number of moles of base used to make the methoxy?
Saint Paul, Mn.
Here is a thread on this Failed Miracle method of Dr.Egotrips.
The guy that did all the testing and wrote the report is a very close friend of mine.
If he told me little green men had landed in the back yard I wouldn't even check before going to get my camera and a gun.
No one would like to find a shortcut to the bio making process more than my mate, hence why he went to the trouble of doing the tests.
I guarantee if he can't make it work, it will take a miracle for anyone else to.
Contrary to the above, readers might be interested in the following paper which reviews recent investigations of solid catalysts and notes CaO, aka. quicklime, as a good candidate to be used ALONE in making biodiesel.
metal oxide catalysts
Also this other article
which notes how Ca(OH)2 forms a Ca-methoxide on its surface, kind of explains how a solid catalyst which does not dissolve into the methanol still has a chemical effect.
treatment of hydrated lime with methanol
Very interesting. I hadn't thought of that (but probably should've). The highly basic nature of the CaO would serve exactly the same function as the KOH. It's rather similar to the heterogeneous method that I developed using K2CO3. Problem with these methods, however, is that they still require heat, which is why I developed this method.
One problem with it, however, is the availability of CaO. When I first developed the method I was living in Melbourne, and you could just drive up to the cement factory and buy the CaO over the counter. Now that I'm in Perth, however, I'm finding it rather hard to come by, and it is only sold in industrial bulk quantities.
So I've been investigating alternative dehydrating agents that are more readily available. I've found a couple, and am now just testing them to see which of them works the better. I'll post results when available (along with a vid). BTW - can vids be added directly to this site, or do I have to upload to YouTube and post up a link?
I'm curious to know why you are using insulting language.
I suppose your friend has simply proved that nothing is ever really foolproof, no matter how simple it is. Tell him to send me an email to firstname.lastname@example.org and I'll sort out his problem, whatever it is. It's probably just a simple mistake where he's either misread something, or my instructions weren't as clear as they could have been.
In answer (sorry I don't know how to cut and quote):
Yes, the only difference is the addition of the dehydrating agent. This removes the interfering effect of the water, and creates a higher methoxide concentration, which lowers the activation energy of the process and allows it to proceed at room temp.
1. You don't need to titrate because since there is no water in the system, the concentration of FFAs no longer matters.
2. Obviously your shovel is bigger than mine. Rough rule of thumb is that the settled lime occupies about 10% of the vessel by volume.
Note, owing to the difficulty in getting quicklime, I have now modified this method and, if anything, it works better.
Mr. Imisides; What's the advantage of your process when compared to using sodium methylate in anhydrous methanol, for the transesterification reaction? Maybe the sodium methylate is more difficult or dangerous?
Hi Wes, I'm not sure which method you're referring to - can you post some details? In principle, it sounds the same though, except I don't think that sodium methylate (if you're referring to the sodium methoxide formed from the reaction of NaOH and MeOH) is as soluble in the MeOH as the potassium salt, and since it is the higher catalyst concentration that (by definition) lowers the activation energy and allows it to proceed at RT, you may need the K salt.
But if you comixed the dehydrating agent with the NaOH, you may eliminate a common ion effect that could be limiting the NaOH solubility (and therefore NaOMe conc), and you may get enough NaOMe into the MeOH to achieve the same effect as I have with the KOH.
I actually thought of trying that myself, but since the KOH was only a little more exy than the NaOH I just took the simplest approach.
Mr. Imisides; Sodium Methylate-DuPont; The compound is made by reacting elemental sodium with methyl alcohol. The catalyst contains no water and is shipped in a methanol solution. DuPont provides sodium methylate in 25% and 30% solutions.
Very interesting. Yes, in principle that is the same as my method. It may be the case, however, that the sodium salt of the methoxide is not as active as the potassium salt that my method generates. I don't know why that would be, as in theory the cation is only a spectator ion, but it is certainly the case if you use my other (heterogenous) method - potassium carbonate works but sodium carbonate doesn't. Go figure.
But I'm curious to know what they do with the hydrogen they generate by this process:
2Na + 2MeOH = 2NaOme + H2
Perhaps they sell it to BMW for their hydrogen cars?
for the last few weeks I have been trying this method. Drying the potassium methoxide with quicklime (CaO)
The method produced around 2/3 of the normal amount of glycerol (16 litres from 24litres of added methoxide) and the yield was noticeably higher, producing 208 litres of biodiesel after de-mething from 200 litres of oil.
In this respect this method worked extremely well. However, I found one large drawback, the process produces some calcium soaps. Not a great deal, but they are very difficult to remove.
They are virtually insoluble in water, so cannot be washed out. They are, or seem to be a very similar density to the bio, so a centrifuge will not remove them. I also tried magnesol to no effect.
The only way I found to remove them was to filter through oak chips several times. OK, I suppose if you are set up to do that.
I probably overdosed the methoxide with lime in the initial drying in an attempt to really get the methoxide dry, producing an excess of calcium methoxide.
A 104% yield using 12% methanol is pretty remarkable.
Are you sure you have not forgotten to mention some chemicals used?
Perhaps a glycerine prewash or two?
Did you do this in 45 minutes at room temperature like you normally do?
The calcium soaps are likely heavier than the methoxide solution and might settle out of the methoxide if given enough time.
The calcium that reacted with the water to slaked lime Ca(OH)2
set in the bottom of the cubie. The excess CaO portion that didn't react was indeed settled above the reacted lime, however I think that even if I hadn't overdosed the methoxide the addition of the lime would still produce some calcium methoxide.
It is not so much that the lime settles in the methoxide but that the calcium soaps remain in suspension in the biodiesel.
Mark Imisides reports in his first post on here that the reaction products fall when the methanol has been removed and I realise this is usually the case, but I found this didn't happen with the calcium soaps and in my opinion they are a problem to this method.
The amount of water formed when KOH is added to methanol is 320gms per kilo of KOH and requires also 1 kilo of CaO to absorb this water. I probably overdid the CaO addition and added well over 1 kilo, which didn't help.
Since this first process I did a second using 25% of the dried methoxide and 75% ASM as the catalyst and although the calcium soaps were very much reduced, they were still evident and the batch still had to be passed through woodchips to remove them.
It would be much simpler to just use ASM only, however the drawback is the solid glycerol which makes pre-treatments difficult.
Mr Imisides; I admire your knowledge of chemistry. It cost me a lot to get mine. I do not believe a room temperature causing an appreciable reaction rate. I do not say it is impossible. Increasing the density of methoxide in solution will not lower the activation energy as you claimed. It would increase the reaction rate at temperature. You might be on to something here.
Many people have performed the reaction at room temperature.
Testing I have performed shows that as long as everything remains liquid and increased mixing time is available, temperature is not a limiting factor to the quality of the biodiesel produced as long as you have adequately mixing.
The rule of thumb is that at 50C with an adequate reactor, a single stage reaction finishes in about an hour.
For every 10C the temperature reduces, mixing time doubles. A good place to start is:
50C= 1 hr mixing
40C= 2 hr mixing
30C= 4 hr mixing
20c= 8 hr mixing
All he is doing is removing the water produced by mixing NaOH/ KOH with methanol.
You need to weigh up the increased cost and extra time spent performing this method against what people achieve not using it.
I personally do not see value for money or time spent.
Of course you have Dgs who just claimed he is achieving 104% yield using a mere 12% methanol.
If that was actually true it would be an amazing accomplishment.
Unfortunately, Dgs makes many incredible claims that are not reproducible so I tend to disregard most of them.
There were earlier trials into this in 2011 and 2012.
Use "find" to search for "new process for making biodiesel" started by The Quiet Dan.
(Which includes my post of course the process does produce bio but
the suspended calcium soaps are too sticky to deal with.
Reminds me of what happens within our arteries.
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