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Author: Subject: BIODIESEL - cheapen your gasoline
stricnine
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Increase people's daily cheese intake, so their intestines get clogged, and then :we can market glycerin as "Human Drano"!! (IN other words, as a laxative) LOL!!

[Edited on 10-11-2006 by stricnine]

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Ozone
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Well, glycerol is used as a stool softener, not a laxative per-se. Of interest, however, is that molasses (I mean blackstrap, not the stuff they sell for consumption, viz. "Steens"). This stuff has a very high ash content, including Mg/Ca citrates! A couple of spoonfulls (which I tried when I was naive, thinking it smelled delicious)...was able to hit the "eye of a needle at fifteen paces" (harsh!). I've thought of mixing it with bleached powdered cellulose and coating it with Nukol and marketing it is "all natural" "Molaxative".

I apologize for deviating from the thread, but my inner juvenile could not resist the anectdotal reference.

The composition of molasses, however, is of interest since the production of EtOH supports the production of greasle. Molasses is about the most complicated composition of *shit* and sugar imaginable, but with 30% fermentable carbohydrate is a viable (*cheap*) feedstock. Experimentally, we have been growing rapeseed ("canola") to compliment this process.

This is theoretically possible on the home-scale, at least, until the industry scoops up all of the molasses .

Best of luck to all on the homebrew,

O3

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froot
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Well glycerine could be a fuel in itself. It has a boiling point of 290 deg.C, a flashpoint of 160 deg.C and a BTU of about 97000/gallon. (reference for this: http://biodiesel.infopop.cc/eve/forums/a/tpc/f/739605551/m/1...) biodiesel having about 117000 btu/gallon.

I dont see why, with a bit of manipulation, biodiesel and glycerol cant be used as a fuel in turbine engines. With a good preheat in the combustion chamber past their respective flashpoints, they both should ignite readily when exposed to oxygen. Just think, you could go see the world and all you need is a truckload of laxative .
The safety aspects make it a rather attractive option compared to kerosene and it's eagerness to burn everything up.

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Tacho
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Burning glycerine produces acrolein, ranked as one of the most hazardous compounds (worst 10%) to ecosystems and human health.

I could not open the link you posted, maybe it shows a way to circunvent this problem. Sorry if that is the case.

Ozone, since you brought that very interesting point up, why don't you start a thread about possible uses for glycerine. Indeed, it seems that there will be lots of it available in the near future.

froot
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No, that link is just my reference for the BTU of glycerol.

Well after a bit of googling, I read that acrolein autoignites at 233 deg.C or there abouts. The temperature of the gases after combustion in a turbine engine are well above 1000 deg.C. I'm pretty sure any trace of acrolein will be decomposed by secondary combustion releasing more energy.

Ps, sorry for off topic, maybe the glycerine part split off into a new topic?

[Edited on 14-11-2006 by froot]

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Ozone
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Hello all,

The *big* problem with glycerol in an internal combustion engine is the fact that the acrolein (besides toxicity and a bunch of condensation products, viz. dioxolanes from glycerol and acrolein) will polymerize fouling the hell out of everything.

I thought a new thread would be a good idea as well! I'll try to get one up.

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Ozone
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OK everyone,

I started a new thread regarding the valorization of glycerol!

See you there,

O3

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DrP
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Hi,

I wasn't sure if I should start a new thread for this question or not, so, I'll put it here.

Does anyone know anything about the antifreeze used in diesel? I'm presuming it is more sophisticated than simple ethylene glycol! So - What chemical is used as antifreeze in diesel fuel for engines?

Thanks!
Ozone
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Depending on the weather, up to 10% EtOH can be added to (or left in!) the biodiesel; this helps to prevent gelation (without fuel warmers).

O3

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tito-o-mac
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do hydrogen fuel cells work just as well as biodiesel?
Centimeter
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I think a lot of people confuse hydrogen as a source of energy. In truth it is looked at as more of an energy bank for transferring energy to a car where it can be mobile. If memory serves me correctly, hydrogen is the most efficient energy vector that we know of. The energy that produces the hydrogen gas comes from a different source, currently fossil fuels. It poses an interesting solution in particular if nuclear power becomes more widely used. As you can imagine, it's much easier to make a nuclear power plant generate hydrogen gas than it is to put nuclear reactors on every single car! The same would be true with solar, wind, and geothermal energy.

I wanted to address vulture's comment that biodiesel would not solve CO2 emission problems. You forget that fossil fuels are accessing carbon from carbon banks where as biodiesel, and in fact any grown fuel, accesses atmospheric carbon. The issue with fossil fuels is that we are effectively increasing atmospheric concentrations of CO2. Biodiesel would not only create a sustainable carbon cycle but could potentially, through sheer cellulose refuse, reduce atmospheric CO2 concentrations.

One issue that I've always wondered about with regards to cultivated fuels is the source of fertilizers. It is my understanding that we currently derive the majority of our fertilizers from fossil fuels. That could put a serious damper on cultivated fuels if we suck the world dry of fossil fuels, not to mention the whole issue with food. As chemists have been saying for decades, it’s a shame that we burn petroleum for such easy to find things as energy.
Intergalactic_Captain
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A couple of articles to add to the conversation - The first one is an overview of miscellaneous pyrolytic routes to fuel from triglycerides, with a good bit on straight-up catalytic cracking. One of the things that caught my eye was the mention of "H ZSM-5" zeolite to produce highly aromatic gasoline-grade fuels...Definitely gonna do more looking into this.

The second article is from the DOE regarding their goals for biofuel production - Haven't gotten a chance to read into it in any detail yet, but it's quite long and looks like it might yeild some interesting info.

[Edited on 11-14-07 by Intergalactic_Captain]

Attachment: triglyceride pyrolysis.pdf (314kB)

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Ozone
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ZSM-5 and the Mobil process are quite cool, aren't they? Please check out also, a nice Fischer-Tropsch application, which I have attached here.

Cheers,

O3

[Edited on 14-11-2007 by Ozone]

Attachment: Lamprecht 2007.pdf (213kB)

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Intergalactic_Captain
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Cool - I did a little research into synthesis gas last year, but put it on the backburner due to the energy input required to produce it. Interesting part on the composition of the JP-8 fuel - at ~55% heptane, it should be a good starting point for gasoline type fuels....Gotta track down their references and see if there's anything useful.

The way I figure it, gasoline-type fuels, ie. shorter chained, more volatile hydrocarbons, are where the money's at in biofuel production. The average american thinks of biofuel as something they put in their car, not necessarily in the grander terms of the national grid and industry. As such, biodiesel doesn't fit the bill - there just aren't enough diesel cars. However, a renewable gasoline alternative that costs less than \$3/gallon would get more people's attention. Even if the difference was only in the cost to the consumer, the desire for cheap gas would generate a high demand for the product. Whoever can set up for large-scale low-cost production first will end up all the richer, able to invest in other areas of research and carve out a place in the renewable fuels industry.

Here's a link to a preparation of a ZSM-5 zeolite...Looks like it might be the right one by some odd coincidence...An excerpt:

 Quote: lWeigh out about 0.510 g of sodium hydroxide pellets and finely grind with a mortar and pestle. Place this mixture in a 250 ml beaker, and add 2.01 g of silicic acid and 1.01 g of tetrapropylammonium bromide. Mix with 5.0 ml distilled water, then add 1.0 ml of n-propylamine and mix the solution again. Place 1.0 ml of a prepared 1 molar solution of aluminum sulfate along with about 0.05 ml of the concentrated sulfuric acid in a separate 50 ml beaker. Then add the first solution to this beaker as well. Add enough distilled water to raise the volume to about 25 ml, and mix the solution (26 ml total volume) on a stir plate for ten minutes. Then transfer the solution to the Parr "Bomb" and seal it. Gently shake it, before placing in the oven. Heat the sample to 160°C and hold there for 44 hours (note how long it takes to reach 160°C). Do not worry if you cannot remove every last trace of the solid out of the beaker. After 2 days heating, turn off the oven and remove the Parr reactor and let it cool to room temperature. Remove a small sample for x-ray analysis. If the x-ray pattern matches the expected one, see figure 2, then filter the rest of the reactant in a Buchner funnel with fine filter paper (541 grade). Wash it three times with copious amounts of water and then dry for 20 minutes on the filter paper. You are now going to calcine the sample to remove the organic cation, so set-up the tube furnace assembly (Figure 2). Place the zeolite inside, on top of the frit in the middle of the tube, and spread out to maximize the surface area. Fit a ground glass elbow at each end, one attached to a nitrogen cylinder and the other immersed in a beaker of water, to regulate the flow of nitrogen gas. Slowly heat the tube to 500°C in increments of 50 to 100°C, when water vapor will be released, then in increments of 100 to 500°C. Heat for two hours after reaching temperature, where the tetrapropylammonium bromide will decompose to tripropylamine, propylene, and water. Cool and weigh the materials (note the weight in g). Remove another sample for x-ray analysis; how does it compare to the previous x-ray?. Any sodium ions remaining in the zeolite will now be ion exchanged for protons to fully convert the zeolite to the acid form. The sodium product from above is placed in a 100 ml beaker, and stirred with 12.60 ml of 1 M aqueous ammonium sulfate for 15 minutes. Collect the zeolite by Buchner filtration (repeat for a total of 3 washings). Wash the product with small amounts of acetone. Then wash several times with distilled water to remove all sulfate ions. Test the washings for this anion by adding drops of an aqueous solution of BaCl2; the formation of a BaSO4 precipitate indicates the presence of the ion. When the solution no longer produces a precipitate, wash the zeolite once more with acetone to dry it, and then dry in the oven at 120°C for 20 minutes. The acid hydrogen form of the compound is prepared by transferring the oven-dried compound to a tube furnace. Heat the ammonium zeolite for 3 hours to ensure the thermal decomposition of the NH4+ ions. Over the course of this process, the zeolite should turn from a white to brown/black to an off-white color. Cool the material and store in a desiccator to preserve the acid hydrogen form.

Seems like it could be done in an amateur lab...Perhaps not as powerful as the industrial version, but proof of concept might be enough to test its viability as a small-scale method.

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Intergalactic_Captain
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ZSM-5 followup

For anyone interested, I've found a great book on the industrial production and usage of zeolites in the petrolum industry.

"Zeolite Technology and Applications; Recent Advances," Chemical Technology Review #170, Copyright 1980 by Noyes Data Corporation, Edited by Jeanette Scotte

Tons of goodies in here...I'll be scanning what I can on the ZSM-5's and posting them (hopefully) tonight. If anyone's interested in any other zeolites, there are articles on:

Zeolites A, B, X
Zeolites L, VK-2, Phi
Zeolite Y
ZSM 4, 5, 11, 21, 23, 34, 35, 38

...Most include both production and experimental usage results. The majority of the syntheses are on the laboratory scale, with easily attainable apparati, temperature ranges, and precursors.

It's really quite an amazing book - too bad it's the library's copy...I'd highly recommend it to anyone interested in zeolite-based fuel production.

EDIT - Attached is a zip file containing several sections on ZSM-5's and a chapter on ZSM's for hydrocarbon conversion and oxidation

[Edited on 11-29-07 by Intergalactic_Captain]

Attachment: zeolites.zip (734kB)

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chemrox
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higher alcohols in trans reax

I'm going to stick my neck out and raise a question that might have been addressed already. I looked but did not find. Would we get a better fuel if we used higher alcohols such as pentanols, octanols, etc. And if these ols could be made cheaply as from fermentation is this a worthwhile endeavor? Again, if this has been discussed please send me a PM and I'll delete this post.
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not_important
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The fist problem is that those currently can't be produced as cheaply as EtOH and fatty acids for biodiesel. Maybe with enough gene tweaking, but that's not been shown to be true.

Next would be a comparison of the entire system efficiencies of standard IC engines, diesel, the several varieties of hybrids, and pure battery operated electric. The standard automotive engine isn't that efficient, partly because it has to operate over a wide range of loading and speeds. A modern electric power plant can 60% or better, some combined cycle designs with advanced turbines or SOFC can hit 80% efficiency. Is it more efficient to do your burning in a large powerplant, where it's fairly easy to capture CO2 and pollutants, ship that power over lines, charge batteries, and drive electric motors from those batteries? Or is it better to spread the combustion out over thousands of independent small engines?
chemoleo
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I think the idea is that the biodiesel is made organically, by energy harvested using the sun.
However I seem to have read, if we were to plant vast areas of land (country-sized) with Rapeseed and similar, we'd still not provide all the fuel necessary to still humanity's energy hunger.
I really don't understand why these genetic engineering companies haven't reported successes yet in generating plants that have minimal carbohydrate production, and maximal fatty acid yields. I mean, rape seed plants are *big*. Very little effective mass that can be used for oils in the end, mostly it's just useless plant matter. Surely this can be improved? Anyone got some data on this?

[Edited on 11-12-2007 by chemoleo]

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not_important
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You can only cut out so much carbohydrate from a plant before it has no stem or leaves. The mass doesn't got into the oil, but into the energy collectors and supporting them. The seeds don't need much oil, but given the 1 to 3 percent typical conversion of sunlight into stored energy it takes a lot of support area. On top of that is the carbon loss when going from carbohydrates (photosyntheses product) to oil - effectively 3 CHOH => 2 CH2 + H2O + CO2

This is one reason some are strongly in favour of oil producing algae, the oil content can be higher. However there is the additional infrastructure needed; the algae must be grown in sealed systems as the oil producers would be overrun by wild strains that put energy into replicating rather than making oil.
chemrox
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I didn't realize the higher ols lagged so far behind EtOH. I thought pentanol production was a big thing for the brits dring WWII and that fermentation was the process. I'm way behind reading on this; if you know some current literature I'd like to read up.

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not_important
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Weizmann developed the acetone-butanol fermentation prior to WW-I. Because of the shortages of food it wasn't much used in England during either WW, but the US did put it into production. This is a bacterial fermentation, not yeast.

http://mmbr.asm.org/cgi/reprint/50/4/484.pdf

There are companies that claim to have breakthroughs in butanol production, http://www.butanol.com/ for example, but they talk about scaling up to 100 gallons a week pilot plant, and there are some other problems with using it as fuel http://en.wikipedia.org/wiki/Butanol_fuel

There are fermentation routes to pentanols, but SFAIK they are not as productive as the butanol one. A problem with these is that the alcohols become toxic to the bacteria at a lower concentration than ethanol with yeast, meaning you're working with a more dilute solution to pull the alcohol out of. I know that pervaporation has been looked at as a means to continuously pull the alcohols out of the mash to prevent toxic levels from building up, and gene tweaking to increase tolerance to the alcohols also has been studied.

I don't know of any fermentation where pentanols are the primary product, and in quantity to be harvested. They're the major alcohols in fusel oil, but that's a byproduct of ethanol fermentation being present at a level of less than one percent of the ethanol.

I think that doing a Web search for "alcohol-name fermentation" or "alcohol-name fuel" is the best way to get more information; what I have is a series of notes with too few references :-( .

And again, small combustion engines with varying speed and loads will be lower efficiency than those working at near constant speed, and less efficient than large scale power plants. If you want to save money or the ecology or whatever, I suspect you need to get away from IC engines as the prime motivators for vehicles.
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The issue of using 2,5-Dimethylfuran as a gasoline alternative should be considered more closely. Recent advances have allowed its production from glucose and fructose using an acid catalyzed method.

Notable qualities:
Immiscible with water
All current internal combustion engines can use it without modification
40% higher energy density compared to ethanol
Will require +/- no modifications to the current petrol infrastructure

The only issue that seems to be blocking its use is that its toxicity has not been completely evaluated--there are some concerns that in its capacity as a metabolite of hexane, it plays a role in the neurotoxicity of said compound.

Note: http://en.wikipedia.org/wiki/Dimethylfuran

A practical lab synth of DMF would also be appreciated; my cursory digging around has not yielded much in the way of a concrete procedure. (Though, I'll likely continue in a bit more depth.)

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YT2095
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Iv also had a go at making some Biodiesel yesterday/last night, using the formula:

100g virgin rapeseed oil
23.8g EtOH
1.43g KOH

I left it on the magnetic stirrer overnight and then a few mins to settle, and this is the result:

all in all Im quite pleased with it

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chemrox
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 Quote: Recent advances have allowed its production from glucose and fructose using an acid catalyzed method.

Is there a technical ref for this?

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Quote:
Originally posted by chemrox
 Quote: Recent advances have allowed its production from glucose and fructose using an acid catalyzed method.

Is there a technical ref for this?

In my thread devoted to the topic of 2,5-Dimethylfuran, which I believe you have already read. *smirk*