Polymerization in WVO

For discussing the modifications needed for diesel vehicles to run with 2 tank veggie oil conversions.

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Postby Burbarian » Sun Mar 16, 2008 8:24 pm

Experiment as noted here:
http://biodiesel.infopop.cc/eve/forums/ ... 1921086832

Samples 1 through 10 counting from left to right.

Samples have 40% distilled water by volume added to the initial mix together with 10 grams of powdered brass mill trailings, placed in disposable plastic cups with an aquarium air pump bubbling air through a porous stone at the bottom. SVO used is new corn oil.

Image

After 2 weeks, the uniformly creamy continuously emulsified and air agitated contents were decanted into individually labeled centrifuge tubes. Not owning a working specimen centrifuge, zip-tying them to the spokes of an electrical exercise bicycle laid on its side worked splendidly.

#1 100% diesel - Diesel clear, water murky. On close examination, water was in the form of tiny 'water bubbles'. Water droplets encased in a skin of diesel oil. There is a noticeable foamy crud layer in both the diesel/water interface and the diesel/air interface.

#2 50% diesel, 50% svo - fuel slightly cloudy, water cloudy.
#3 25% diesel, 75% svo - fuel slightly cloudy, water slightly cloudy.
#4 10% diesel, 90% svo - fuel slightly cloudy, water clear. Some contaminants.
#5 5% diesel, 95% svo - fuel slightly cloudy, water cloudy. More contaminants.

In 2 to 5 we get increasing cloudiness of the fuel mix and increasingly thick svo/water and svo/air interface layers. The water layer goes from segregated into individual oil filmed bubbles packed together to increasing aggregation and larger bubble sizes. By #4 the water is has merged into a single homogeneous layer with no internal oil interfaces. #5 is likewise homogeneous but cloudy. Contaminants in 4 and 5 are filaments rising from the oil/water interface and descending from the oil/air interface.

#6 100% svo - fuel murky, water cloudy. The svo has floating contamination in the form of strands and filaments and small black particles. Also has a much thicker fuel/water crud layer but about the same fuel/air layer as #5.

Once I get that order of 1 micron filter pads in, I shall put silica gel into each tube to dessicate the samples, then see how long it takes each sample to filter through the 1 micron pad, and how much oil made it through the filter media.

The amount of byproduct (Polymerization? Bacterial?) is too small in the samples to measure directly with good accuracy, so I will compare the flow rate and post-filter fuel volume with clean unoxidized samples of the same diesel/svo ratio.

#7 90% svo / 10% water with silica gel. The gel soaks up the water and swells. The oil is clear and a small sample tests dry on a hot pan test. The silica appears to have either prevented or drastically reduced polymerization.

Unexpected results are the best kind.

#8 90% svo / 10% mineral spirit - Fuel slightly cloudy, water clear. No other visible signs of polymerization. On shaking the sample tube into an emulsion, it separates rapidly and the water separates clear. Will try this again with smaller ratios. This looks promising. Perhaps it is an effective biocide.

#9 90% svo / 10% WD40 - WD40 is supposed to be a water repeller. It in fact makes a pretty good emulsifier and air entrainer. I thought it would outperform diesel, but that was not to be. I have no idea if it promoted or prevented polymerization.

#10 90% svo / 10% Power Service diesel fuel supplement (white bottle winter formula) - This was a solid air entrained emulsion through and through. Even 10 minutes on the makeshift exercycle-centrifuge couldn't budge it. I know many people add DFS to their WVO to improve cetane and in the belief that it improves cold flow antigel as it does with diesel. That may yet still be the case. But apparently it also acts as a powerful emulsifier and air entrainer. Sample was also highly viscous.

Comments and criticism welcome.
Last edited by Burbarian on Thu Mar 27, 2008 8:49 am, edited 1 time in total.
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Postby John Galt » Sun Mar 16, 2008 8:42 pm

Interesting results so far. The Brits have used 'white spirit', 'mineral spirits', 'paint thinner', 'turps', etc. for thinning their VO for some time now with generally good success. Their kerosene is dyed and if the dye shows up in their tank they can be fined, so it's not often used to thin VO.
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Postby SunWizard » Sun Mar 16, 2008 10:04 pm

Interesting science project. You didn't do a sample of 100% VO with no water? #7 is sort of that. Poly would not be visible, it is clear to amber color which blends right into the VO. Viscosity tests with a visgage (pics on my post on page 1) would be a good way to measure it. Filter pads may give some indication of it but also include bacterial.

Temperature during the test? Oxidation doubles with every 10C increase.

Keep up the good work!
YVORMV - Your veg. oil results may vary.
95 Dodge Cummins 4x4 SVO WVO conversion.
81 Mercedes 300D- stock and happy on V80/D20 blend.
Low fossil net zero house- 100% solar power and heat.
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Postby Burbarian » Mon Mar 17, 2008 8:28 am

SunWizard wrote: You didn't do a sample of 100% VO with no water? #7 is sort of that.


I assume that as well, considering that the desiccant quite rapidly dried the oil. Considering 1. Its apparent stability. 2. Effectiveness. 3. Low cost. 4. That water is the bogeyman of VO fuels. 5. That condensation can form in fuel tanks and contaminate otherwise painstakingly dried fuel. I think I will add a simple screened coolant heated pipe full of silica gel just prior to the fuel filter in my setup. It is cheap insurance.

Poly would not be visible, it is clear to amber color which blends right into the VO. Viscosity tests with a visgage (pics on my post on page 1) would be a good way to measure it. Filter pads may give some indication of it but also include bacterial.


Ahh, good info for empirical testing. Perhaps I can replicate the function with a glass syringe, a fine hypodermic needle, mount it vertically and use a standard weight on top of the plunger in conjunction with a stopwatch.

Any ideas on how to eliminate bacterial contamination and proliferation as a factor while not affecting regular oxidation/polymerization testing?

Temperature during the test? Oxidation doubles with every 10C increase.


Test was run in the workshop. It is only sporadically heated, but fairly well insulated. Temperature goes between 50F and 65F depending on whether I am present and running the stove and/or generator.

Update: Immersed the sample tubes in a pail of hot water overnight.

All the samples except #9 lost their oil/air interface crud layer, and the oil looks clearer.

#9 Showed better separation. Emulsified stuff on top, cloudy water below.
#10 Finally broke the emulsion, and there was partial separation. Cloudy oil on top, emulsified water below.
The two look like mirror opposites.
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Postby SunWizard » Mon Mar 17, 2008 8:37 am

You could make a visgage easily. Its just 2 ball bearings rolling within 2 clear pipes 8" long. Roughly 1/4" pipe with 3/16" balls. And in 1 pipe is a reference oil, which in your case could be the original unused VO, the other pipe is the test sample. There is a scale drawn between the 2 pipes, and you tilt it and once 1 ball reaches the end, you read viscosity off the scale. 2 different scales, 1 next to each pipe, depending on which ball hits the end first.
YVORMV - Your veg. oil results may vary.
95 Dodge Cummins 4x4 SVO WVO conversion.
81 Mercedes 300D- stock and happy on V80/D20 blend.
Low fossil net zero house- 100% solar power and heat.
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Postby SkySkiJason » Sat Mar 22, 2008 6:01 pm

Sunwizard, you are spot-on with your first 2 posts, very well put.

Richard, I wish I had a rice bran oil source(s) like that! I shoulda tried harder to hook up w/you while I was in SoCal at the end of last year!

Ok, bringing my poly... thoughts here from the dewatering thread. :wink:

I don't understand why our Aussie friend is not making mountains of chicken skin?? In the VO lab, they make oil polymerize by heating it and bubbling air/oxygen thru it.

What is it that is different about what he's doing? He is 'exposing' the oil to large amounts of oxygen, right?

I said this in the dewatering thread, but to add to Sun's original posts, VO is breaking down from the time it is pressed. As it breaks down, the 'free radicals' begin cruising around damaging other molecules and creating more free radicals. The bits these free rads knock off like to stick together, forming long chains - polymerization. This process is ACCELERATED by the presence of oxidents, oxygen and heat.

I agree w/Sun's suggestion that eliminating or mitigating the presence of those ingredients does SLOW the poly... process, but it continues on regardless. Without the TBHQ and anti-oxidents added to the VO we ALL use, it would have never lasted long enough for us to get it.

I'm gonna ask the VO 'chemist' who tried to explain this process to me to join this group. He was posting on another forum, but I think he tired of the 'parrot talkers' arguing facts w/fear mongering and blatantly un-scientific data. The personal attacks were uncalled for as well. I hope this forum is able to avoid the various 'camps' of belief 'taking sides' and bashing each others ideas.
2001 F-350, DRW, 4x4, XLT Crew Cab, flat bed, 7.3, 6 spd, Dipricol Optix gauges, DP tunes - Single-Shot injectors! Vegistroke-style WVO conversion, 55,000 VO miles so far - 190 deg VO before the heads
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Postby coachgeo » Sat Mar 22, 2008 8:43 pm

SkySkiJason wrote:....tired of the 'parrot talkers' arguing facts w/fear mongering and blatantly un-scientific data. The personal attacks were uncalled for as well. I hope this forum is able to avoid the various 'camps' of belief 'taking sides' and bashing each others ideas.
We can avoid the bashing and this camp verses that camp stuff you speak of by us just putting out all the information on the table and let readers decide on their own after review of the information. Let the info stand its own merits. No need in calling any one out personaly over a different view cause that just mucks up the good info.

So if you see something in one thread that you have a different take on.. please do mention it!!!! If that mention starts a lot of new discussion then take it to a new thread so not to clutter up someone elses. Of course add a link into the orginal thread so folk can easily find the new discussion.
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Postby David » Sat Mar 22, 2008 9:21 pm

SkySkiJason wrote:]

I don't understand why our Aussie friend is not making mountains of chicken skin?? In the VO lab, they make oil polymerize by heating it and bubbling air/oxygen thru it.

What is it that is different about what he's doing? He is 'exposing' the oil to large amounts of oxygen, right?


Hi Jason,

I can make mountains of chicken skin on command and it requires no effort, machinery or energy input.
Get a 200L drum and stand it on its end. Pour a layer of water on it to cover the surface about 1cm deep. Then, add some WVO to also cover the entire surface. Walk away leaving it outside for a week and come back and you will have something between Glad wrap and silly Putty. It's that simple. I did some accidentally just this week and the stuff was actually impressive. I couldn't help but think if you refined this to an industrial level, there would probably be a bunch of uses for it. I reckon you could dry and harden this up a bit more and use it like a, self amalgamating waterproof wrap/ sealant.

In MY experience, water seems to be a required factor in making poly. I do not get poly inside my fuel drums ( And I have a ship load!) or inside the dryer. The outside of the dryer is covered in it from spills and splashes but the inside where the oil is in contact in the drying process is spotlessly clean as it was from day 1. Spills on the outside of the drums get very sticky and attract dirt like a magnet. Drum washing is an ongoing and time consuming part of supplying my friends oil.

I can only guess the reason the oil does not poly the way I dry it is because either the resident time in the drum ( Typically 3 hours but has been over 24) is not long enough or that the oil is not in contact with the water long enough, OR, that the constant motion of the water in the oil being pounded into submission somehow upsets the process. I have read of situations where all these elements are present where poly occurs so......?

My oil is typically cottonseed with god knows what mixed in depending on where I collect the drums that randomly go into that batch. I get small amounts of canola, Peanut, sesame and " Blended oils from Malaysia that probably contain palm and whatever else.

You have given me an idea for an experiment I'll go set up later today.
I will get 3 20L steel tins and set them on end in a place where they are exposed to the weather but under shelter from rain.

I will get some dried oil and put it directly on the end of tin 1.
On tin 2, I'll put a layer of water and then the dryed oil and on tin 3, I'll put a sample of "As collected oil. Unfortunately all I have ATM is probably good to better than average stuff ( what a thing to complain about!) but should be interesting to see how that goes.

My predictions:
Dry oil in contact with steel will do nothing at all except attract bugs and flies.
Dry oil with water will chicken skin but I'm leaning towards little if any rust on steel surface.
For "Raw oil, I'm predicting chicken skin and some rust of drum although not much as I know this oil is probably a hell of a lot dryer than what a lot of people happily put in their tank.

I take shots and post up the results.
_____________________

I don't give a damn about what might or could happen until a significant group of people can tell me it HAS happened to them.
Until then, it's just more endless gloom and doom Veg folk law.
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Postby SkySkiJason » Sat Mar 22, 2008 10:37 pm

David wrote:I take shots and post up the results.


You are the man! Hope you don't think I was 'calling you out'. I beleive you, it is just 'breaking the rules' if you will. I was making fun of your toilets for flushing the wrong way though :D , it just ain't right! :roll:

Don't worry Coach, my heart really is in the right place, you'll see. I guess I see how that could've been taken the wrong way. I have the ability to dissagree w/someone and still go have a beer when we're done. David and I will have to have a virtual beer on account of our proximity to one another. We can crack on my Kiwi friends together... :lol:

The only poly I've seen, aside from outside, hot places, is on the water heater elements that have been in service for awhile. I prolly could not make a handful after 2yrs and 1000's of gallons.

Most of that dewatering was done in an un-lined 80 gal water heater (140F then off for 12-24 hours and drain bottom). I too have 55 gal drums w/no paint and had oil in them for 2 yrs now. No poly, no smell. But they are un-processed. These are black drums in full south sun all day. Full to the tippy top, though. I actually forgot about one until I was on my way here and was scrambling for oil (thats a whole thread there - boil out sucks!). I held my breath when I opened it, I thought it was gonna stink. Nope, some of the cleanest oil I've processed!! Ah, the power of time...

I wonder if you could spray the VO until it polymerizes? How hot is it when yer spraying it?
2001 F-350, DRW, 4x4, XLT Crew Cab, flat bed, 7.3, 6 spd, Dipricol Optix gauges, DP tunes - Single-Shot injectors! Vegistroke-style WVO conversion, 55,000 VO miles so far - 190 deg VO before the heads
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Postby David » Sat Mar 22, 2008 11:35 pm

SkySkiJason wrote:You are the man! Hope you don't think I was 'calling you out'. I beleive you, it is just 'breaking the rules' if you will.


Hi Jason,

No, that never even ocoured to me.
What I was thinking of was all the stuff I have heard about WVO reacting with steel. We had a guy here some time back that was pumping straight out of dumpsters into his fuel tank and when it all polyed up and everything else, everyone went off on an idiotic tangent that the WVO was reacting with the steel. Now there are a whole mindset of people running round telling everyone they have to have their steel tanks coated or the WVO reacts! :roll:

I'd like to have a crack at dispelling that myth as well as trying out my belief of the presence of water being a component of Poly forming.
I'm sure whatever the results people will start with the far fetched theroys and question the results with with claims of the type of oil not being right or the altitude the test was conducted at being wrong or wanting to know the phase of the moon etc but the rest of us may just be interested in the results for what they are. :D

And BTW, Our toilets work fine, Yours flush the wrong way? That must get awful smelly havin that comin back up at ya!! :shock:
_____________________

I don't give a damn about what might or could happen until a significant group of people can tell me it HAS happened to them.
Until then, it's just more endless gloom and doom Veg folk law.
David
 
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Joined: Thu Mar 06, 2008 4:12 am
Location: Sydney Australia

Postby coachgeo » Sun Mar 23, 2008 1:33 am

Yall sound like you see water having alot to do with it. Dana Linscott has been saying that for some time too.

intresting stuff. Look forward to more on this.
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Postby Welder » Sun Mar 23, 2008 2:03 am

coachgeo wrote:Yall sound like you see water having alot to do with it. Dana Linscott has been saying that for some time too.

intresting stuff. Look forward to more on this.


Dana Linscott, who's Dana Linscott?
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Postby Welder » Sun Mar 23, 2008 2:10 am

David wrote:
SkySkiJason wrote:
I don't understand why our Aussie friend is not making mountains of chicken skin?? In the VO lab, they make oil polymerize by heating it and bubbling air/oxygen thru it.

What is it that is different about what he's doing? He is 'exposing' the oil to large amounts of oxygen, right?


Hi Jason,

I can make mountains of chicken skin on command and it requires no effort, machinery or energy input.
Get a 200L drum and stand it on its end. Pour a layer of water on it to cover the surface about 1cm deep. Then, add some WVO to also cover the entire surface. Walk away leaving it outside for a week and come back and you will have something between Glad wrap and silly Putty. It's that simple. I did some accidentally just this week and the stuff was actually impressive. I couldn't help but think if you refined this to an industrial level, there would probably be a bunch of uses for it. I reckon you could dry and harden this up a bit more and use it like a, self amalgamating waterproof wrap/ sealant.

In MY experience, water seems to be a required factor in making poly. I do not get poly inside my fuel drums ( And I have a ship load!) or inside the dryer. The outside of the dryer is covered in it from spills and splashes but the inside where the oil is in contact in the drying process is spotlessly clean as it was from day 1. Spills on the outside of the drums get very sticky and attract dirt like a magnet. Drum washing is an ongoing and time consuming part of supplying my friends oil.

I can only guess the reason the oil does not poly the way I dry it is because either the resident time in the drum ( Typically 3 hours but has been over 24) is not long enough or that the oil is not in contact with the water long enough, OR, that the constant motion of the water in the oil being pounded into submission somehow upsets the process. I have read of situations where all these elements are present where poly occurs so......?

My oil is typically cottonseed with god knows what mixed in depending on where I collect the drums that randomly go into that batch. I get small amounts of canola, Peanut, sesame and " Blended oils from Malaysia that probably contain palm and whatever else.

You have given me an idea for an experiment I'll go set up later today.
I will get 3 20L steel tins and set them on end in a place where they are exposed to the weather but under shelter from rain.

I will get some dried oil and put it directly on the end of tin 1.
On tin 2, I'll put a layer of water and then the dryed oil and on tin 3, I'll put a sample of "As collected oil. Unfortunately all I have ATM is probably good to better than average stuff ( what a thing to complain about!) but should be interesting to see how that goes.

My predictions:
Dry oil in contact with steel will do nothing at all except attract bugs and flies.
Dry oil with water will chicken skin but I'm leaning towards little if any rust on steel surface.
For "Raw oil, I'm predicting chicken skin and some rust of drum although not much as I know this oil is probably a hell of a lot dryer than what a lot of people happily put in their tank.

I take shots and post up the results.


This post is an excellent resource. It should be posted on infopop as well.

IIRC, Dana has been saying that he has a hunch that water is somehow related to vegpoly formation. Davids input seems to corroborate that pretty significantly. To "do science" all we need is for someone in Arizona, Texas etc to follow Davids vegpoly making recipe and we'll have a physical verification of Davids obsevation here on N.A soil.

(Dave, I'm not insinuating you're a liar. I'm only requesting a time honored tradition of scientific verification through controlled peer experimentation. If the results will be the same [they will], then we'll KNOW you're right {I believe you are})
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Postby Burbarian » Sun Mar 23, 2008 4:14 am

"Chicken skin" polymerization isn't the only type, though it is the most visibly apparent. As I am still learning on this subject, Sun has informed me that poly could be completely invisible to the naked eye. It is miscible in the fuel, and the only indicators could be increased viscosity. I've not yet fabricated a visgauge, but intend to in order to test a larger batch of samples being bubbled. Too many projects, too few hours..

From what I have read, 'chicken skin' appears to form on air-exposed steel surfaces, and 'green slime' on copper/brass surfaces. With just bubbling in a plastic or plastic-lined container, or not enough residence time and high agitation in a metal container, then these poly forms may not manifest or be evident, but poly could still be present. In a metal container, one could imagine 'chicken skin' precursors too small to be naked-eye visible mixed with the oil. With no substrate to bond to, we could have free floating 'chicken skin flakes' as it were. Still, only a small amount could have formed in the short time (a few hours) that the bubbling was being done. So once the water has been removed and the oil properly stored, continued polymerization rate should be greatly reduced. This might explain David's experience.
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Postby David » Sun Mar 23, 2008 7:09 am

Hi Burb,

What you ( and sun) suggest makes perfect sense.
What occurs to me is if oil is polyed up from air drying ( or heat or anything else that people claim causes it) and goes through the fuel system and burns fine in the engine as mine does If it is polyed at all, is there anything to worry about in the first place?
_____________________

I don't give a damn about what might or could happen until a significant group of people can tell me it HAS happened to them.
Until then, it's just more endless gloom and doom Veg folk law.
David
 
Posts: 333
Joined: Thu Mar 06, 2008 4:12 am
Location: Sydney Australia

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