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Hi Its a long time since I posted here but just want to pick your collective brains. A client of mine is producing an industrial mould release agent that is an emulsion of methyl esters and water. We produce the methyl esters in the usual way and add emulsifiers plus water to get the consistency we want. More additives are added to make up the final product. If we could produce methyl esters with a higher level of soaps we would be able to reduce the emulsifiers.
The wvo we use normally titrates at 4 to 6 ml KOH and currently our resultant soap levels are around 400ppm . A soap level of 1500 - 2000ppm would allow us to dispense with emusifiers completely. but how would we achieve this level consistently?
 
Location: Lismore Ireland | Registered: November 25, 2007Reply With QuoteReport This Post
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Hi IMB, nice to see you are still active.

If adding glycerol back into your mix isn't a problem (glycerol nominally contains about 35% soap) then just add the glycerol back in until you get a titration of 0.55 based on a 1.0ml sample.

This will then give you about 1700ppm soap. Cheers, Dave.
 
Location: YORK UK | Registered: April 27, 2014Reply With QuoteReport This Post
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Hi imakebiodiesel,
quote:
Originally posted by imakebiodiesel:
If we could produce methyl esters with a higher level of soaps we would be able to reduce the emulsifiers.
The wvo we use normally titrates at 4 to 6 ml KOH and currently our resultant soap levels are around 400ppm . A soap level of 1500 - 2000ppm would allow us to dispense with emusifiers completely. but how would we achieve this level consistently?
The way you make soap when making biodiesel is to add water to the reaction.
The problem is likely to be that most of the additional soap produced by adding water to the reaction will be removed along with the byproduct/ glycerol as it settles out of the biodiesel.






 
Location: ลึก ประเทศอินเดีย | Registered: March 03, 2001Reply With QuoteReport This Post
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Hi Dgs,

quote:
Originally posted by Dgs:
(glycerol nominally contains about 35% soap)
I am not sure why you would say that.
Assuming that when you say glycerol you mean the byproduct layer of the reaction, the soap content of the byproduct is variable and is dependent to a large degree on the titration of the oil being reacted. The higher the titration, the more soap that will be produced.
If you are reacting low titration oil there will be little soap produced so there will not be much soap in the byproduct layer.






 
Location: ลึก ประเทศอินเดีย | Registered: March 03, 2001Reply With QuoteReport This Post
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quote:
Originally posted by Tilly:
Hi Dgs,

quote:
Originally posted by Dgs:
(glycerol nominally contains about 35% soap)
I am not sure why you would say that.
The higher the titration, the more soap that will be produced.
If you are reacting low titration oil there will be little soap produced so there will not be much soap in the byproduct layer.


Total rubbish Tilly.

Most of the soap produced in the reaction (assuming reasonably low titrating oil) is from the water produced in the methoxide making reaction.

Go crack yourself some glycerol derived from low titrating oil. You will see from the amount of FFA's you get just how much soap is in there.
 
Location: YORK UK | Registered: April 27, 2014Reply With QuoteReport This Post
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Hi Dgs,

quote:
Originally posted by Dgs:
]Total rubbish Tilly.
Most of the soap produced in the reaction (assuming reasonably low titrating oil) is from the water produced in the methoxide making reaction.
Exactly what I said.
If you are reacting low titration oil there will be very little soap produced because there is only a very tiny amount of water produced when you mix NaOH/KOH with methanol so there is only a tiny amount of soap produced with low titration oil.

The higher the oil titration, the more soap that is produced

The RUBBISH was when you posted that "(glycerol nominally contains about 35% soap)" Absolute rubbish!






 
Location: ลึก ประเทศอินเดีย | Registered: March 03, 2001Reply With QuoteReport This Post



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Thanks for your prompt reply and what a good idea. I was thinking along the lines of adding extra water to the veg oil before processing but in my experience too much water might stop the process or cause poor conversion.
Because there is a significant amount of water in the final product there should be no problem of the glycerol separating from the emulsion, my only concern would be possibility of smearing or staining on the moulded concrete surface. The customers for this product are very fussy and wont tolerate any staining. We can do some trials to check this out.
Many thanks
 
Location: Lismore Ireland | Registered: November 25, 2007Reply With QuoteReport This Post
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From the UK VOD forum, some years ago.



Joined: Jul 2014
Reputation: 22
RE: What's in the glyc?



I've done this before but not for a while so here goes again.

lets base this on a 100 litre batch where we have used 16% methanol in total and this batch has produced 16 litres of glycerol. The oil used titrated at 2.0

The actual glycerine in the oil was 3.1 litres (info from countrypaul)
After the 12.5 litres of methanol used in the reaction there is a residual 3.5 litres, if it really is split in the 3:1 ratio glyc/bio then there would be 2.63 litres of methanol in there.

If KOH was used at the rate of 10gms/litre of oil then the water released in the methoxide would be 420 gms (320 from the methoxide production and 100 from the 90% KOH) The water from the ffa neutralisation would be 64 gms. If trinity virgin methanol was used at (last time I tested it) 115ppm water so not significant to take into consideration.

Next an estimated 0.5 litres of tied up biodiesel.

So that gives us;

Glycerol 3.1 litres 19.4%

Methanol 2.63 litres 16.4%

Water 484mls 3.0%

Biodiesel 0.5 litres 3.1%

Whats left has to be soap at 9.3 litres 58.1%

A bit rough and ready and I've made a few assumptions like dry oil, but I don't think it will be far off.




05-12-2016, 07:30 PM Post: #7
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RE: What's in the glyc?
Tallies with my Glyc/FFA splitting.

Approx 50/50 split indicating around 50% of the by-product was soap.
 
Location: YORK UK | Registered: April 27, 2014Reply With QuoteReport This Post
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Hi Dgs,

58.1% soap- and you believe that???
Needless to say, there are some major mistakes in your both your calculations and assumptions. I will give you a hand sorting some of this out and possibly arriving at a more realistic figure
quote:
lets base this on a 100 litre batch where we have used 16% methanol in total and this batch has produced 16 litres of glycerol. The oil used titrated at 2.0
The actual glycerine in the oil was 3.1 litres (info from countrypaul)
First HUGE mistake.
There is about 79ml glycerine in each litre of oil. This makes the glycerine content of the glycerol/ by-product layer about 7.9 litres, not 3.1 litres. That is why the by-product layer is often called glyceol and not soap



quote:
After the 12.5 litres of methanol used in the reaction there is a residual 3.5 litres, if it really is split in the 3:1 ratio glyc/bio then there would be 2.63 litres of methanol in there.
The Rule of thumb is that 2/3 of the recoverable methanol is in the by-product and 1/3 in the biodiesel. Which makes it about 2.3 litres methanol in the by-product



quote:
If KOH was used at the rate of 10gms/litre of oil then the water released in the methoxide would be 420 gms (320 from the methoxide production and 100 from the 90% KOH) The water from the ffa neutralisation would be 64 gms. If trinity virgin methanol was used at (last time I tested it) 115ppm water so not significant to take into consideration.
As I have repeatedly told you, when you mix methanol and KOH, water is only formed when methoxide is actually produced. That means that there is probably not 320ml of water produced because all the methanol does not become methoxide. But I will use your numbers.



quote:
Next an estimated 0.5 litres of tied up biodiesel.
Second HUGE mistake.
I can only assume you are making wild guesses here.
The rule of thumb is that for every 1 litre of soap produced, 2 litres of biodiesel are removed with the soap into the byproduct layer.
A titration of 2 KOH gives about 1% FFA, which will become about 1 litre of soap when it is neutralized. This soap will take 2 litres of biodiesel with it when it settles out into the by-product layer



quote:
So that gives us;
Glycerol 3.1 litres 19.4%
Methanol 2.63 litres 16.4%
Water 484mls 3.0%
Biodiesel 0.5 litres 3.1%
Whats left has to be soap at 9.3 litres 58.1%
So that gives us-
Glycerol 7.9 litres 49.4%
methanol 2.3 litres 14.4%
water 484mls 3.0%
Soap from neutralizing FFA's 1 litre- 6.2%
Biodiesel removed with the Soap 2 litres- 12.5%

The remaining 2.4 litres is probably a mixture of soap and biodiesel.
If we stick with the 2/3 biodiesel- 1/3 soap rule of thumb, that makes it an additional
800 ml soap- 5%
1.6 litres biodiesel- 10%

Total soap content of the by-product/ glycerol- about 1.8 litres- 11.2%






 
Location: ลึก ประเทศอินเดีย | Registered: March 03, 2001Reply With QuoteReport This Post
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Well, that seemed to get the old juices flowing Tilly!

It was written some time ago and I realised some of the info given to me (like the glycerine) content was incorrect.

Your rule of thumb seems to be as accurate as the one you keep posting about the reaction temperature.

11.2% soap eh? giving a FFa layer of about 40% of the total when the glycerol is acidified- I don't think so.
 
Location: YORK UK | Registered: April 27, 2014Reply With QuoteReport This Post
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Hi Dgs,

quote:
Originally posted by Dgs:
It was written some time ago and I realised some of the info given to me (like the glycerine) content was incorrect.
Of course you knew that the glycerine was actually about 7.9 litres, that is why you said it was 3.1 litres.

You just keep posting meaningless drivel







 
Location: ลึก ประเทศอินเดีย | Registered: March 03, 2001Reply With QuoteReport This Post
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Another post from later in the thread:


dgs
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RE: What's in the glyc?
With Pauls modified glycerol (6.2%) we now have;

Glycerol 6.2 litres 38.8%

Methanol 2.63 litres 16.4%

Water 484mls 3%

Biodiesel 0.5 litres 3.1%

Soap 6.2 litres 38.8%
Location York.
Enhanced Glycerol pre-wash, then 1 more stage (usually)
De-meth, water wash and dry to <200ppm.
2x 2.0 HDI's both on B100.
2x ransomes mowers both on B100.
FOC Water testing by S/B or KF for forum members.
 
Location: YORK UK | Registered: April 27, 2014Reply With QuoteReport This Post



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We have made up a couple of samples of our release agent with 5% and 8% glycerol added. We reduced the emulsifier by 50%. After several weeks there is no sign of any separation which is very important. Next test will be to do some test mouldings to see is there is any deterioration in separation and smearing. Thanks very much for your input, as always, intelligent and to the point.
 
Location: Lismore Ireland | Registered: November 25, 2007Reply With QuoteReport This Post
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Hi imakebiodiesel,

quote:
Originally posted by imakebiodiesel:
..Thanks very much for your input, as always, intelligent and to the point.
It is a pleasure to help. Feel free to ask for further assistance anytime Wink






 
Location: ลึก ประเทศอินเดีย | Registered: March 03, 2001Reply With QuoteReport This Post
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No Problem John, pleased it seems to be working for you.
 
Location: YORK UK | Registered: April 27, 2014Reply With QuoteReport This Post
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imakebiodiesel; Part of what science is is being able to reproduce results hopefully in a predictable way . So make your purest biodiesel. Make your purest soap and mix them in a somewhat quantitative way. That would be reproduceable and predictable.
 
Location: Texas | Registered: April 27, 2011Reply With QuoteReport This Post
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Hi Wesley, sorry I missed your post, I dont log on to this forum very regularly. You are right the most scientific method would be to produce high quality soap and add it to good quality methyl esters but often in business clients want the most cost effective method even if its not the most scientific. Our tests have been very successful, we add a small portion of glycerol to the water, mix thoroughly and then mix with the methyl esters and we have been able to reduce the need for emulsifiers drastically. Again my thanks to DGS.
Perhaps I might pick your brain on another subject. I am helping a client develop an industrial product from glycerol by product. Our experiments have shown that pharma grade glycerine plus water plus common salt makes an ideal product but at too high a cost. We are trying to modify raw glycerol by product to be as close to this ideal product as possible.
My idea is to neutralize the glycerol with HCl which would hopefully convert the soaps into Na and KCl plus water and allow the FFAs to separate and be removed. Ive done this before with sulphuric and phosphoric acid but I have no experience with hydrochloric. Do you think it would work and have you any suggestions as to how we might calculate the correct dose. As always thanks for your scientific input.
John
 
Location: Lismore Ireland | Registered: November 25, 2007Reply With QuoteReport This Post
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I've taken homemade potassium soap with water in a beaker, added muriatic acid (hydrochloric acid), warmed the beaker some with difficult stirring with a thick glass rod, then the white free fatty acids were released. There were two layers. The white free fatty acid layer on top, with the water,glycerine, salt layer on the bottom. Figuring the quantity of hydrochloric acid to use might be difficult since each batch is different. But I would estimate/guess the amount of soap in the glycerine, add less than an equivalent amount of acid, then use phenolphthalein to show where the pH is (acid or base) in a small portion off to the side. To start. That's a tough question. A problem using muriatic acid or hydrochloric acid is knowing the initial strength. A factory here exploded after the improper addition of sulfuric acid to glycerol. Sulfuric acid would release the free fatty acids, but the acid also would react with glycerol to make an ester in an exothermic reaction. The explosion was July 17, 2009 in Chicago USA, from glycerol being mixed with sulfuric acid.
 
Location: Texas | Registered: April 27, 2011Reply With QuoteReport This Post



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Hi Wesley,

It looks like imakebiodiesel wants to hire you as a chemistry consultant.
Chemistry consultants typically make $200- $500 an hour.
That sounds like a good little earner for you Wink






 
Location: ลึก ประเทศอินเดีย | Registered: March 03, 2001Reply With QuoteReport This Post
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I was thinking along the same lines. Ive used Sulphuric acid before and it quickly heats up due to the exothermic reaction. Im going to try a one litre sample tomorrow. Ill do a rough calculation of how much HCl Ill need and divide it into 10 parts. Ill add one part , stir for 15 mins test the ph and then go again until I reach 7. That should avoid the overheating effect. thanks for the help, Ill let you know how we get on
John
 
Location: Lismore Ireland | Registered: November 25, 2007Reply With QuoteReport This Post
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