Planning to use B100 in 2009 Jetta

[Harvieux]

For what it's worth, ZDDP is an extreme-pressure additive, a "last resort" lubricant that takes effect during starting (by sticking to the metal) and in situations where the hydrodynamic lubrication fails (insufficient oil pressure, insufficient relative speed between the surfaces to maintain an oil film, extreme-pressure line-contact situations at drive gears and between camshafts and flat lifters, etc).

That's an interesting explanation of the biodiesel-dilution situation, and it makes sense although I'm no chemist. One thing of note is that the amount of ZDDP in oil has been going down because either the zinc or the phosphate parts of it (or both?) are bad for catalytic converters. Being no oil chemist, I could see this going in a few different directions. Either the amount of ZDDP is being trimmed without substituting anything else (in which case any amount of "substitution" by biodiesel could dramatically reduce its effectiveness), or ZDDP is being replaced by some other compound that is polar (same situation as described in the article could still occur), or it is being replaced by a non-polar substance (but I doubt it, because it is the polar nature of these molecules that holds them "stuck" to the surface of the metal).

I wonder out loud if oil analysis would show this. I tend to suspect not. The ZDDP is still there, but its effect on the metals is being displaced.

Fabulous input here, Brian. This may be a stupid question but, I too am far from a chemist. Would it be possible to reduce the methyl esters in the bioD to a point where the reduction of ZDDP in the newer oils will be less of a factor? Later!

 

[GoFaster]

Sure. You ditch the transesterification process that home-brewers are fans of, and you substitute the BTL (biomass-to-liquid) synthesis process that VW and others are developing, because BTL produces hydrocarbons that are indistinguishable from normal petrodiesel hydrocarbons!

Transesterification inherently produces methyl esters; the entire product is methyl esters. If you substitute ethyl alcohol (more difficult process from what I understand) then the product is ethyl esters, although I have no idea whether this would change the end result. If they behave in the same way with ZDDP then it doesn't accomplish anything.

 

[kwantam]

Transesterification inherently produces methyl esters; the entire product is methyl esters. If you substitute ethyl alcohol (more difficult process from what I understand) then the product is ethyl esters, although I have no idea whether this would change the end result. If they behave in the same way with ZDDP then it doesn't accomplish anything.

By no means proof, but the dipole moment of methanol is 2.76, whereas ethanol is 1.76. Larger dipole moment implies "more polar," so one might optimistically surmise that ethyl esters should be less likely to displace ZDDP than methyl esters.

 

[Harvieux]

By no means proof, but the dipole moment of methanol is 2.76, whereas ethanol is 1.76. Larger dipole moment implies "more polar," so one might optimistically surmise that ethyl esters should be less likely to displace ZDDP than methyl esters.

How can we find out the dipole of ZDDP? Later!

 

[rodneyh1]

This is a very interesting paper from MIT comparing ULSD and B100. Engine wear looks the same even though ZDDP functionality decreases more for B100 (just how important is the stuff?). PM is lower for B100 and should be better for DPF.

Rod


http://www1.eere.energy.gov/vehiclesandfuels/pdfs/deer_2007/session5/deer07_sappok.pdf

 

[jvance]

How can we find out the dipole of ZDDP? Later!

I'm not a chemist, but I did (as Blue Hen TDI pointed out) spend the night at a Holiday Inn.

Looks like the dipole moment for ZDDP is about 1.2 - 1.4. The dipole moment of methanol isn't the dipole moment of biodiesel - it's a big lipid molecule with an alkyl group hanging off at some point (my A in Chem 121 and 122 from 27 years ago aren't helping me out at all ) IIRC you need the molecule geometry so you can sum up all the vectors. Maybe with larger molecules there's a "local" moment. Boy, I'm talking out my rear here, so I'll just stop.

One of these days I should crack an Organic Chemistry textbook.

 

[kwantam]

Looks like the dipole moment for ZDDP is about 1.2 - 1.4. The dipole moment of methanol isn't the dipole moment of biodiesel - it's a big lipid molecule with an alkyl group hanging off at some point (my A in Chem 121 and 122 from 27 years ago aren't helping me out at all ) IIRC you need the molecule geometry so you can sum up all the vectors. Maybe with larger molecules there's a "local" moment. Boy, I'm talking out my rear here, so I'll just stop.

If the rest of the molecule is neutral, and if the covalent bond between the alkyl group and the rest doesn't affect the charge cloud too much (unfortunately this is completely untrue), then the dipole moment doesn't change much because it is only measured as the charge times the distance; large pieces of neutral molecule do nothing as long as they don't stand in the way.

http://en.wikipedia.org/wiki/Fatty_acid_methyl_ester is a good picture of what's happening when you make biodiesel. It's clear from this picture that the dipole moment is changing a whole lot.

 

[MBoni]

Fabulous input here, Brian. This may be a stupid question but, I too am far from a chemist. Would it be possible to reduce the methyl esters in the bioD to a point where the reduction of ZDDP in the newer oils will be less of a factor? Later!

That's one way to approach the problem, but take a look at the last paragraph of the Biodiesel Magazine article (emphasis added):

Even though for years biodiesel has been heralded as a lubricity additive helping keep fuel system components like the moving parts inside fuel injection systems operating smoothly, the bitter irony here is that, when post-injected, it tends to dilute engine oil and interacts with additives and increases the possibility of engine wear. Much work remains developing viscosity improving, anti-wear, dispersant and detergent additive packages in which adverse reactions with biodiesel are significantly reduced.

The other approach is to change the additive package to be more bio friendly. This sounds like a more likely path to success, but it'll take some top quality chemists to get it right.

 

[Harvieux]

What's that, a bird?, a plane?, no, it's most of the detailed chemistry explanations going right over my head. Actually, some of this stuff is coming back from my very limited chemistry exposure in college but, trust me, not enough to contribute at this point, know whadda mean! Later!

 

[Harvieux]

I'm not a chemist, but I did (as Blue Hen TDI pointed out) spend the night at a Holiday Inn.

Looks like the dipole moment for ZDDP is about 1.2 - 1.4. The dipole moment of methanol isn't the dipole moment of biodiesel - it's a big lipid molecule with an alkyl group hanging off at some point (my A in Chem 121 and 122 from 27 years ago aren't helping me out at all ) IIRC you need the molecule geometry so you can sum up all the vectors. Maybe with larger molecules there's a "local" moment. Boy, I'm talking out my rear here, so I'll just stop.

One of these days I should crack an Organic Chemistry textbook.

LOL! BTW, that's Holiday Inn Express. Later!

 

[kwantam]

The other approach is to change the additive package to be more bio friendly. This sounds like a more likely path to success, but it'll take some top quality chemists to get it right.

Good point. First it really does have to be established that the bio has real-world implications for wear. The presentation rodneyh1 linked above implies that this may not be the case.

 

[jvance]

If the rest of the molecule is neutral

Derr - I useded to know sum chemistry. And math.

and if the covalent bond between the alkyl group and the rest doesn't affect the charge cloud too much (unfortunately this is completely untrue), then the dipole moment doesn't change much because it is only measured as the charge times the distance; large pieces of neutral molecule do nothing as long as they don't stand in the way.

http://en.wikipedia.org/wiki/Fatty_acid_methyl_ester is a good picture of what's happening when you make biodiesel. It's clear from this picture that the dipole moment is changing a whole lot.

Thank you! This is why I post half-baked analyses - in the hopes that someone who actually knows what they're talking about will correct me.

 

[Harvieux]

That's one way to approach the problem, but take a look at the last paragraph of the Biodiesel Magazine article (emphasis added):

The other approach is to change the additive package to be more bio friendly. This sounds like a more likely path to success, but it'll take some top quality chemists to get it right.

In that case, what would be cheaper? Manufacturing a downstream DPF injection system or the R&D and production cost necessary to produce a more compatible oil? Then the question remains if this manufacturing of or developement of these remedies actually makes sense monetarily with bioD being such a non-factor in overall world demand. Darn, this stuff gets complicated, eh? At this point, I think the BTL fuel makes better sense for the future but then again, *** do I know, eh? Later!

 

[kwantam]

At this point, I think the BTL fuel makes better sense for the future

...with nuclear power to supply all the energy that BTL processing uses, one hopes.

 

[Harvieux]

This is a very interesting paper from MIT comparing ULSD and B100. Engine wear looks the same even though ZDDP functionality decreases more for B100 (just how important is the stuff?). PM is lower for B100 and should be better for DPF.

Rod


http://www1.eere.energy.gov/vehiclesandfuels/pdfs/deer_2007/session5/deer07_sappok.pdf

Rod, Great find, man! Can someone decifer from this presentation if this particular Cummins engine incorporates the post-injection process that the new VW CR has or is it the conventional CR injection process? Later!

 

[Harvieux]

Uh Oh! We had better stop this experiment immediately because if BMW says so, VW............. Later!

This image was stolen from another thread authored by club member, tditom.

 

[rodneyh1]

Cummins uses a urea injection in Europe on their ISB-XXX engines, but I don't know about the comparable US models. The fuel dilution part of the presentation that I linked to was artifitially done (I think) for both the ULSD and the B100 to ensure a constant dilution percentage. Still no good info on how much dilution you get with B100 compared to ULSD. Please let me know if you have something.

I'm sure glad VW didn't think to put that label on my gas (oops, fuel) cap, or I never would have started this whacky experiment.

 

[MBoni]

Still no good info on how much dilution you get with B100 compared to ULSD. Please let me know if you have something.

rodneyh1, again quoting from the Biodiesel Magazine article:

Volkswagen is using post-injection for regeneration and according to Stuart Johnson with the Engineering and Environmental Office of Volkswagen Group of America, the issue of oil dilution from biodiesel is a real concern for the automakers. “We can tolerate up to 50 percent fuel mix in the oil but no more,” he said at the 2008 National Biodiesel Conference.

Volkswagen tests using B5 and post-injection showed 45 percent oil dilution after 10,000 miles, but surprisingly no engine damage was evident upon inspection. “Using B10 at 10,000 miles surpasses that 50 percent threshold—and that is unacceptable,”

....

“Using post-injection you will generally see elevated levels of fuel dilution regardless of what fuel you’re using,” Sappok says. Because biodiesel has a higher distillation temperature and boiling point, when it’s present in the post-injected fuel it tends to dilute the oil on a level disproportionate to its blend ratio in the fuel. Fang says this is just now becoming understood.

Through his work at Cummins, Fang has developed a new algorithm to predict the amount of fuel dilution when running on various blend ratios of biodiesel.

So it does appear that biodiesel will end up contaminating the oil more than standard diesel will. It doesn't vaporize quite as quickly, so more of it stays within the cylinder. We've also got two reference points for B5 and B10 at 10k miles, but not a whole curve.

It looks like Mr Fang has done some work trying to establish a real curve, all we have to do is find where he published his results.

 

[shizzler]

guys, here are two of his papers availible at sae.org for purchase.

Biodiesel Impact on Wear Protection of Engine Oils

Document Number: 2007-01-4141
Date Published: October 2007
Author(s):
Howard L. Fang - Cummins, Inc.
Shawn D. Whitacre - Cummins, Inc.
Elaine S. Yamaguchi - Chevron Oronite
Maarten Boons - Chevron Oronite
Abstract:
Pure biodiesel fuel (B100) is typically made of fatty acid methyl esters (FAME). FAME has different physical properties as compared to mineral diesel such as higher surface tension, lower volatility and higher specific gravity. These differences lead to a larger droplet size and thus more wall impingement of the fuel during injection in the combustion chamber. This results in higher levels of fuel dilution as the oil is scraped down into the crankcase by the scraper ring. The lower volatility also makes biodiesel more difficult to evaporate once it enters the crankcase. For these reasons, levels of fuel dilution in biodiesel-fueled engines are likely to be higher compared to mineral diesel-fueled engines. When in-cylinder dosing is applied to raise the exhaust temperature required for the regeneration of Diesel Particulate Filters (DPF's), biodiesel dilution in the engine oil may be elevated to high levels. Besides changing the viscometric properties of the lubricant, biodiesel and its degradation products could also interact with the lubricant additives and impact their performance. The partially oxidized biodiesel components may compete with ZDDP antiwear additives on metal surfaces. In this study, the wear characteristics of the biodiesel-contaminated oil are evaluated by Electrical Contact Resistance (ECR), High Frequency Reciprocating Rig (HFRR) and four-ball tests. The formation of a complex between oxidized biodiesel components and ZDDP is studied with FTIR and \u3\u1P-NMR techniques. Based on wear bench test and model compound studies, it is concluded that biodiesel fuel can lead to increased engine wear caused by the interaction of oxidized biodiesel compounds and ZDDPs.
File Size: 158K
Product Status: In Stock

Biodiesel on Fuel Dilution of Engine Oil

Document Number: 2007-01-4036
Date Published: October 2007
Author(s):
Morgan M. Andreae - Cummins Inc.
Howard L. Fang - Cummins Inc.
Kirtan Bhandary - Cummins Inc.
Abstract:
In this work fuel dilution of engine oil, and the impact of biodiesel fuel on dilution, were examined. New emissions requirements have driven the adoption of a range of aftertreatment systems for diesel engines. These aftertreatment devices in many cases have specific requirements for exhaust composition and temperature. Meeting these requirements can lead to fuel dilution of the engine oil. Measurement of fuel dilution of engine oil can be challenging, and in this study a new strategy for utilizing Fourier Transform Infrared Spectroscopy (FTIR) was examined. A synthetic component of aviation oil, pentaerythritol ester (PE), was found to be a very useful tracer for measuring dilution with ultra-low-sulfur diesel (ULSD), but not useful for measuring dilution with B20. Fuel dilution and evaporation rates were measured for both ULSD and for a blend of biodiesel and ULSD (B20). Fuel dilution rates were found to be higher for B20 as compared to ULSD due to the higher distillation temperatures of methyl ester.
File Size: 106K
Product Status: In Stock

 

[SnowCub]

Looks like PCMag picked up this story as well... lot's of good stuff. More exposure is important to suss out the facts:
http://www.technoride.com/2008/09/volkswagen_not_supporting_high.php

 

[markeckley@yahoo.com]

Fang appears to have an axe to grind.
Did he look at 'loss of ZDDP' from the cylinder surface?
Did he look at cylinder damage?
Nope.

>In this study, the wear characteristics of the biodiesel-contaminated oil are evaluated by Electrical Contact Resistance (ECR), High Frequency Reciprocating Rig (HFRR) and four-ball tests.<

Why ask the question you're trying to answer when you can infer so much from the four-ball test? I'll be watching this guy.

He's selling a pig in a poke, and I'm out to show it.
ttyl

 

[markeckley@yahoo.com]

Friction-enhancing properties of ZDDP antiwear additive: Part I-friction and morphology of ZDDP reaction films(C)
Tribology Transactions, Jul 2003 by Taylor, L J, Spikes, H A


Many phosphorus-based antiwear films, including those formed by zinc dialkyl dithiophosphates (ZDDP), cause a significant increase in friction in thin film, high-pressure, lubricated contacts.

ZDDP itself doesn't sound like a picnic.

 

[nicklockard]

ZDDP is a really ooooooool skool high pressure additive that has largely been bypassed and minimized in modern formulations. It's cheap and that's why some oils still use it, though in moderation compared to yesteryear.

Purchase oils which don't lean heavily on cheap, old skool additives. My $0.02

 

[jvance]

ZDDP is a really ooooooool skool high pressure additive that has largely been bypassed and minimized in modern formulations. It's cheap and that's why some oils still use it, though in moderation compared to yesteryear.

Purchase oils which don't lean heavily on cheap, old skool additives. My $0.02

Hmmm. So I wonder if this high-zoot 8 buck a quart 507.00 oil even contains ZDDP.

 

[maktas]

Fang appears to have an axe to grind.
Did he look at 'loss of ZDDP' from the cylinder surface?
Did he look at cylinder damage?
Nope.

>In this study, the wear characteristics of the biodiesel-contaminated oil are evaluated by Electrical Contact Resistance (ECR), High Frequency Reciprocating Rig (HFRR) and four-ball tests.<

Why ask the question you're trying to answer when you can infer so much from the four-ball test? I'll be watching this guy.

He's selling a pig in a poke, and I'm out to show it.
ttyl

The paper doesn't even address the effect of the dilution, it just studies rates.... big deal. The issue is that there is no evidence of abnormal engine wear just by using high % blends of bio-D

 

[markeckley@yahoo.com]

from Biodiesel magazine article
>>“We can tolerate up to 50 percent fuel mix in the oil but no more,” he said at the 2008 National Biodiesel Conference.

Volkswagen tests using B5 and post-injection showed 45 percent oil dilution after 10,000 miles, but surprisingly no engine damage was evident upon inspection.
<<

The rest of the article focuses on Fang and his made-up arguments about biodiesel displacing oil additives. BD is unacceptable to VW, but no evidence of engine wear has been shown.

Anyways, good luck to neurot. I bet your Jetta will run like a champ on B99 and you'll make and sell better fuel as a result of your commitment to the fuel itself.
I'll be driving down to Austin next summer and I'll buy some of your product then.
Take care.

 

[Neurot]

my question is, how is "oil dilution" measured? My initial thought would be relative volume of each liquid. 45% dilution sounds like the total volume is 55% oil and 45% Biodiesel. At that level, the oil wojld be pouring out the dipstick tube.

Is there any info about exactlyhow oil dilution is calculated?

 

[CentralFloridaTDIguy]

crankcase full or...

my question is, how is "oil dilution" measured? My initial thought would be relative volume of each liquid. 45% dilution sounds like the total volume is 55% oil and 45% Biodiesel. At that level, the oil wojld be pouring out the dipstick tube.

Is there any info about exactlyhow oil dilution is calculated?

so does the amount of oil remain same and BioD adds and over flows crankcase?

or does the BIoD replace the oil and the oil gets burnt?

 

[vwrobert51]

funny how this thread has fallen silent, perhaps some problem has happened???? no ones talking???

 

[DPM]

How often would you prefer the OP added data, Robert? It aint going to die in a week. This is a long-term experiment and no change= good news...