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There is sure a lot of talk about " Le Chateleir's principle"
Is that similar to "Lady Chatterley's Lover" Wink






 
Location: ลึก ประเทศอินเดีย | Registered: March 03, 2001Reply With QuoteReport This Post
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quote:
Originally posted by Dr Chemical:
quote:
Originally posted by RickDaTech:
quote:
Originally posted by Dr Chemical:
so it is easily disposed of down the sink


Really? You may want to rethink that one.


Look at the video.



I watched the video. Interesting.

I Gotta move to Perth. In the US the government gets really upset with us if we pour highly caustic, poisonous, flammable liquids into the public sewer system. So in Perth, as long as it's thin like water, there is no problem with pouring anything in the sink. I love it.
 
Location: Cowboy Country | Registered: December 06, 2004Reply With QuoteReport This Post
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Hi Mark,

quote:
Originally posted by Mark:
Actually I reckon the biggest source of water is from the methoxide reaction:
NaOH + MeOH = NaMeO + H2O
Of course water is ONLY produced when Methoxide is actually produced. Dissolving KOH in methanol does not produce water.



quote:
It puzzles me how few people that make bio are aware of that.
Everyone I know who makes biodiesel is aware that water is produced when you make methoxide by mixing KOH or NaOH with methanol. It is common knowledge. It puzzles me why you think most people who make biodiesel were unaware of this.






 
Location: ลึก ประเทศอินเดีย | Registered: March 03, 2001Reply With QuoteReport This Post
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In the US the government gets really upset with us if we pour highly caustic, poisonous, flammable liquids into the public sewer system


Like the current pipeline oil spill near St Louis that threatens rivers and public water supplies alike?

But no, seriously, glycerol and methanol are supposed to be okay in foulwater systems.
 
Location: New Zealand | Registered: August 15, 2006Reply With QuoteReport This Post
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A common sight in downtown Perth.

http://youtu.be/lcA0C1Nf7tk






 
Location: ลึก ประเทศอินเดีย | Registered: March 03, 2001Reply With QuoteReport This Post
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Originally posted by Tilly:
There is sure a lot of talk about " Le Chateleir's principle"
Is that similar to "Lady Chatterley's Lover" Wink


Tilly,

A few years back Dr. Van Gerpen's academics claimed Le Chateleir's principle was the reason for the 6:1 molar ratio of oil to methanol. They put out a video not long ago that implied the real reason for the 6:1 molar ratio has more to do with Dalton's Law, than Le Chateleir's Principle.

Mark is claiming that Lady Chatterly's Lover Le Chateleir is the reason why overdosing the KOH lets him operate at room temperature. It's possible, but he has presented no evidence of the completeness of conversion. The commercial guys have been using the potassium methoxide premix for years and the only room temperature commercial process I've found so far is using enzymatic catalysts. Implying Mark's method may be low conversion biodiesel.

You might find this interesting, I suspect that making methoxide with the cement may let you use less KOH than simple mixing of KOH with methanol.

I'd still like to see four or five people with open minds try Mark's method (less pouring raw glycerin down the drain) and reporting back on water content of the oil and how it did in the 3/27 test and soap test. Repeatability is where that other foolproof method failed.


Rick
 
Location: Cowboy Country | Registered: December 06, 2004Reply With QuoteReport This Post



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quote:
Originally posted by RickDaTech:
quote:
Originally posted by Dr Chemical:
quote:
Originally posted by RickDaTech:
quote:
Originally posted by Dr Chemical:
so it is easily disposed of down the sink


Really? You may want to rethink that one.


Look at the video.



I watched the video. Interesting.

I Gotta move to Perth. In the US the government gets really upset with us if we pour highly caustic, poisonous, flammable liquids into the public sewer system. So in Perth, as long as it's thin like water, there is no problem with pouring anything in the sink. I love it.


I'm not sure where you live, but the laws where you are are probably the same as they are here.

As long as it's water-miscible you can dump it down the sink. If you are doing it on a regular basis, such as a food or beverage manufacturing plant, the water corp will require you to take regular samples and have them tested for BOD. According to that BOD, and therefore the load that is being placed on the system, you will then have to pay a certain amount per Kl.

I have worked in the waste management industry for years, and have been involved in several plants where we have designed a WWTP for the purpose of lowering the outfall BOD. Then it's just a numbers game. The cost of the WWTP is compared with the savings made on lowering the BOD, and then a decision is made on whether it's economically viable to build the plant.

But in the case of dumping glycerol waste down the sink, everything in it is water-miscible and biodegradable, and therefore it's perfectly legal to send it to waste,
 
Registered: September 28, 2017Reply With QuoteReport This Post
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quote:
Originally posted by Paulus:
quote:
In the US the government gets really upset with us if we pour highly caustic, poisonous, flammable liquids into the public sewer system


Like the current pipeline oil spill near St Louis that threatens rivers and public water supplies alike?

But no, seriously, glycerol and methanol are supposed to be okay in foulwater systems.


Correct. Perfectly legal. See post above.
 
Registered: September 28, 2017Reply With QuoteReport This Post
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quote:
Originally posted by Dr Chemical:
Hi Rick,

I'm afraid you don't understand the chemistry of my method.

The high methoxide concentration is nothing to do with water. In fact the unique part of my method is the dessication step - the removal of all water from the methoxide solution. This uses Le Chateleir's principle to generate very high concentrations of methoxide.

Since the methoxide is a catalyst, its role, by definition, is to lower the Ea of the reaction. This means it will proceed at ambient temperature and does not require the input of thermal energy.

And yes, I am aware that KOH is not unique to my method. The video clip, I must confess, puzzles me. I haven't read through all the comments, but there are two things that no one I have seen has commented on

1. I'm not convinced it's the same drum. There appear to be some black marks on the top of it after the reaction that weren't there beforehand. But there's possibly an innocent explanation - maybe it just got grubby sitting outside with some dust in the oil or something

2. Of more concern is the volume of glycerol. With my method, 17% methoxide by volume generates 22% glycerol by volume. In this video clip it's no more than about 10%. So at best it's a halfway reaction.

And then of course there's the obvious thing, that lots of people have commented on, about the fact that she tipped the raw product into her tank without any processing or washing.

No, I haven't done any tests on my product yet - there's no need to. It produces a low viscosity, low smoking product that runs beautifully. Before I changed the ratios from 100:15 to 100:20 it was a bit smoky in the merc until the engine warmed up, which tells me there was probably some unconverted WVO in there. But having changed the ratios it's now smokeless.

An unexpected by product of the change of ratios was very low viscosity, low-foaming glycerol. It's almost as thin as water and is easily discarded down the sink. I've added some more video clips at the link on my site

One day I'll run my product through a GCMS just for my own interest, but it's not a high priority.

And yes, it's highly possible that someone else thought of using Le Chateleir's principle to generate a high concentration of anhydrous catalyst - it's an obvious modification - but I haven't seen such a method

Mark


One more thing. I'm constantly making the mistake of assuming knowledge in others that is obvious to me, and I've done it again.

One obvious reason why I know that this process is a very high yield process is because it's based on a high concentration of catalyst. It's such a basic principle of chemical manufacturing (and physical chemistry) that there is no more certain way to obtain a high reaction yield than to increase the level of catalyst, whether it be homogenous or heterogenous, as it overcomes any variation in reaction kinetics caused by the Boltzmann distribution.
 
Registered: September 28, 2017Reply With QuoteReport This Post
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Dr Chemical; You wrote "since the methoxide is a catalyst". The methoxide is not a catalyst, it is the product of a catalyst (KOH). A catalyst regenerates itself. A methoxide molecule is consumed in the production of the ester.
 
Location: Texas | Registered: April 27, 2011Reply With QuoteReport This Post
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quote:
Originally posted by WesleyB:
Dr Chemical; You wrote "since the methoxide is a catalyst". The methoxide is not a catalyst, it is the product of a catalyst (KOH). A catalyst regenerates itself. A methoxide molecule is consumed in the production of the ester.


Correct. A technical point, but quite correct. It's more accurate to say "higher concentration of catalyst (KOH), resulting in a higher concentration of the nucleophilic intermediate (the methoxide).

But I think you've just explained something else. I've sat down and done that thing that organic chemists do, drawing arrows between atoms and bonds, to work out where the electrons go, and made a discovery that explains something I haven't been quite able to figure out.

The glycerol that this method produces is incredibly thin - essentially like water - and is easily disposed of down the sink (see video). I thought this was because of the thinning effect of the MeOH, but was never really happy with that explanation, mainly because I noticed that when I sit it in a beaker in the atmosphere for a few days it thickens into the syrup that I've observed before, without a significant change in the volume.

Here's what I think, after my scribbling exercise with arrows and stuff - the by-product of my reaction is not glycerol, but the potassium salt of the glycerol. To generate glycerol (and regenerate the KOH), the water is required that I have removed:

K3C3H5O3 + 3H2O = 3KOH + C3H8O3

So in the absence of water, I don't have glycerol at all - I have its potassium salt. And that explains why it's so thin - NO HYDROGEN BONDING. The viscosity of glycerol is wholly explained by its hydrogen bonding, and in the absence of hydrogen bonding it's as thin as water.

And that explains why it thickens upon standing - it sucks up water from the atmosphere according to the above reaction (Le Chateleirs principle again) until the mixture is composed wholly of the reaction products KOH and glycerol.

Glad I figured that out - I was never really happy with the "thinned by methanol" explanation
 
Registered: September 28, 2017Reply With QuoteReport This Post
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Originally posted by Dr Chemical:

But in the case of dumping glycerol waste down the sink, everything in it is water-miscible and biodegradable, and therefore it's perfectly legal to send it to waste,



Making assumptions about what is and is not legal can bite you really hard. Please, take the time to verify your assumptions even though it's based on your previous experiences, laws change.

Like Tilly said earlier, yield is not an indicator of quality. It is used as an economic indicator. You have put forth no evidence of quality, other than for your clarification process.

All that said, I would like to see your process be proven, with repeatable results by multiple people using multiple oil sources.


WesleyB, Would you be willing to try it on a test batch scale? You have always sounded like the open minded type. This would be experimentation for the sake of knowledge.


Anyone else interested in trying it on a test batch scale?


Rick
 
Location: Cowboy Country | Registered: December 06, 2004Reply With QuoteReport This Post



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Hi,

quote:
One more thing. I'm constantly making the mistake of assuming knowledge in others that is obvious to me, and I've done it again.
Tell me about it. This happens to me all the time! I will just forget about my superior intellect for an instant, and before I know it I will be engaged in a meaningless conversation with someone who does not even have the intellect to wipe dog poo off their shoe.

As I said to Bertrand just last week at the monthly Mensa meeting, having a superior intellect can be such a burden. People are constantly talking to you about meaningless drivel.

I now wear a badge that says:
"Unless your IQ is over 140 and you have a PhD in Physics and Mathematics,
you have nothing to say to me that I do not already know.
Go talk to someone else"






 
Location: ลึก ประเทศอินเดีย | Registered: March 03, 2001Reply With QuoteReport This Post
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To read the process may require going to another web site. I gather the process is like the Imisides cold transesterification method, using cement powder to dry regular methoxide thereby pushing the reaction to the right which increases methoxide concentration. I already did a cold process method using calcium oxide to dry the methoxide (it worked fine at 25 degrees celcius). My cold method biodiesel passed a 10/90 test with no fallout.
 
Location: Texas | Registered: April 27, 2011Reply With QuoteReport This Post
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Hi Mark,

quote:
Originally posted by Mark:
The glycerol that this method produces is incredibly thin - essentially like water - and is easily disposed of down the sink (see video). I thought this was because of the thinning effect of the MeOH, but was never really happy with that explanation... mainly because I noticed that when I sit it in a beaker in the atmosphere for a few days it thickens into the syrup that I've observed before, without a significant change in the volume.
Glad I figured that out - I was never really happy with the "thinned by methanol" explanation
There is also the fact that you are producing a large quantity of soap.
For some reason you erroneously equate a large By-Product layer (that which you refer to as glycerol) as an indication of a "full" reaction. That is not the case.
A large By-Product layer is an indication of a large amount of soap being produced.
You say you produce about 22% By-Product
Let me help you understand this.

The By-Product layer (which you call glycerol) is usually composed of four main ingredients;
Glycerol
Methanol (with KOH)
Soap
Biodiesel

It is easy to do a rough calculation of the quantities of each ingredient.

Glycerol- There is about 79ml of glycerol in every litre of oil. That means in in a full reaction, the glycerol will be about 7.9% of the total volume of oil reacted which is about 6.6% of the total content volume of your reactor keeping in mind you added 17% methanol to the oil.
Methanol- There is a rule of thumb that says that about 1/3 of the excess methanol is in the biodiesel phase and 2/3 of the excess methanol is in the By-product phase.
The Stoichiometric amount of methanol for a complete reaction is considered to be about 12% of the volume of the oil. You used 17% (170ml per litre of oil) methanol in the reaction. That means there is an excess of 5% methanol that will be divided between the biodiesel and by- product phases.
If 2/3 of this excess is in the byproduct, that is about 2.8% methanol of the total content volume in the reactor keeping in mind that you added 17% methanol to the oil.

If you produced no soap, there would be virtually nothing else in the Byproduct Layer.
In that case the By-Product Layer would be about 9.4% by volume of the total volume of the reactor..
Testing I have done shows that this is pretty accurate.

However, you say you have about 22% glycerol in the reactor
So what is the additional 12.6% By-product you are producing?
It is Soap and biodiesel
The Rule of thumb here is that for every 2 litres of soap produced it will take about 1 litre of biodiesel with it into the By- product.
So about 2/3 of the additional 12.6% by-product or about 8.4% of the total volume in the reactor is soap and about 4.2% is Biodiesel.

So your byproduct layer ,expressed as a percentage of the total volume of the contents of the reactor contains about;
Glycerol- 6.6%
Soap- 8.4%
Biodiesel- 4.2%
Methanol- 2.8%


As you can see, your by-product layer is actually only about 30% glycerol.

I hope you have found this explanation helpful and has sorted out your confusion in this matter.
Please do not hesitate to contact me if I can help clear up any other misunderstandings you have.

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






 
Location: ลึก ประเทศอินเดีย | Registered: March 03, 2001Reply With QuoteReport This Post
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Originally posted by WesleyB:
To read the process may require going to another web site. I gather the process is like the Imisides cold transesterification method, using cement powder to dry regular methoxide thereby pushing the reaction to the right which increases methoxide concentration. I already did a cold process method using calcium oxide to dry the methoxide (it worked fine at 25 degrees celcius). My cold method biodiesel passed a 10/90 test with no fallout.


Yes it works a treat. I'm just kicking myself for not working out the chemistry of the glycerol phase earlier. I never knew why my glycerol was so thin - I always assumed it just hadn't partitioned completely. But in fact it had, and all I was doing by letting it sit for so long was letting it suck up water from the atmosphere and get converted from the potassium salt to the glycerol.

Of course it's my bloody fault for being too lazy to sit down and work out the reaction stoichiometry. It was your comment about the catalyst that got me thinking, so thanks for that.

BTW, don't make the mistake of either reading or replying to every post on this site. There's a certain serial pest on this and other biofuels sites who cannot bear the thought that someone may have come up with a biodiesel method that makes his obsolete. But in fact his knowledge of chemistry could be written on the back of a postage stamp, and I stopped reading his contributions years ago.

Of course it significantly lowers the signal to noise ratio of every thread he contributes to, but as long as the site administrators allow him to post his babble there's not much we can do about it
 
Registered: September 28, 2017Reply With QuoteReport This Post
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quote:
Originally posted by RickDaTech:
quote:
Originally posted by Dr Chemical:

But in the case of dumping glycerol waste down the sink, everything in it is water-miscible and biodegradable, and therefore it's perfectly legal to send it to waste,



Making assumptions about what is and is not legal can bite you really hard. Please, take the time to verify your assumptions even though it's based on your previous experiences, laws change.

Like Tilly said earlier, yield is not an indicator of quality. It is used as an economic indicator. You have put forth no evidence of quality, other than for your clarification process.

All that said, I would like to see your process be proven, with repeatable results by multiple people using multiple oil sources.


WesleyB, Would you be willing to try it on a test batch scale? You have always sounded like the open minded type. This would be experimentation for the sake of knowledge.


Anyone else interested in trying it on a test batch scale?


Rick


There are no assumptions or guesses. Like I said, I've worked in the industry for years. And unlike some people on this site I don't guess, and then pass it off as gospel truth.

There are two things that will get you into trouble for going down your sink - stuff that is either non-miscible with water or stuff that is non-biodegradable. In the former case it's usually greases or oils, in which case you'll need to put in a greasetrap (if you're a restaurant for example) and the latter case usually refers to chlorinated solvents, although they are pretty much ancient history now.

And of course, it's because people can't put oil down the sink we that we have a source of WVO for making bio.

And in terms of repeatability of my method, the whole point about it is that it's foolproof - as long as you can follow basic instructions it's not possible to get it wrong. I've been making it by this method for about 15y now.

But just in case the vids don't convince you of the simplicity of the method, I'll be doing a public demonstration with my next batch.
 
Registered: September 28, 2017Reply With QuoteReport This Post
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quote:
Originally posted by WesleyB:
To read the process may require going to another web site. I gather the process is like the Imisides cold transesterification method, using cement powder to dry regular methoxide thereby pushing the reaction to the right which increases methoxide concentration. I already did a cold process method using calcium oxide to dry the methoxide (it worked fine at 25 degrees celcius). My cold method biodiesel passed a 10/90 test with no fallout.


WesleyB, what can you tell us about the oil you used? Titration,water content, anything else?

Rick
 
Location: Cowboy Country | Registered: December 06, 2004Reply With QuoteReport This Post



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Mark,

I'm not going to try to get you to change anything especially how you dispose of glycerin. Keep doing however you feel is appropriate.

Repeatability is at the core of the scientific method. You have done all you can. Now it is up to others to verify your method is repeatable.

Ricky
 
Location: Cowboy Country | Registered: December 06, 2004Reply With QuoteReport This Post
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RickDaTech; I used new corn oil from a grocery store. I did not want to complicate matters so I used new oil. I was researching if room temperature tranesterification proceeds at a reasonable rate. Used vegetable oil can be wet. It didn't make sense to use dried methoxide with potentially wet oil. I titrated the new corn oil once at about 0.6, it was not zero.
 
Location: Texas | Registered: April 27, 2011Reply With QuoteReport This Post
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