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The glycerine to gasoline thread....
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Hi,
I have been making Methyl Esters for 10 years. I have come up with a lot of ways of disposing glycerine but always have felt it was wasting it, not to make fuel out of it.
What I used to do was distill the methanol out of it. I'd normally just let the bears have at it.
I used an electric water heater to do the distilling. I'd fill it, (which was a collasal PITA), then let the element boil off the MeOH, and eventually the safety valve would kick open and blow all the water out too. The glycerine would come out of the water tank very hot. So hot, it would melt the cubies I used to store it in. I had to pour it into metal buckets and eventually drums.

Lately, I have been on a "why am I going through all this trouble to make BD" kick. I keep wondering about thermal cracking the tryglcerides directly.
Here are some thoughts...


This a triglyceride molecule.



This is methyl ester.



This is glycerine.



This is Acrolein.

The references I have from the origins of crude oil cracking show a rig like this....



They tell of heating glycerine and getting acrolein.
When I look at acrolein I see an Alkene and CO. Not sure how to go from acrolein to CO and Some Alkene. Lets set that aside for the moment...


"I don't work with collectives. I don't consult, I don't co-operate, I don't collaborate."
Howard Roark
 
Location: Calumet, Michigan, Great White North | Registered: January 20, 2002Reply With QuoteReport This Post
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The thing I am thinking of is building a similar cracking still, and simply dropping the cubies of glycerine and methanol directly into the pot. No more struggling to heat the darn glycerine til it pours out of the cubie. Just throw the whole thing in.
The first stage would be to heat the pot enough to distill off the methanol. So I do that, condense it and set that aside. Next pour the coal to it (or in this case, the oak) and drive off the water. Once the water is gone, then the fun begins. Now I should be able to heat the glycerine to a high enough temp to melt the plastic cubies. The glycerine would act as a heat transfer mechanism to liquify the plastic.
At this point, I have a choice. I could go with what I have in the pot already, or I could start adding the rest of the empty plastic cubies that have piled up (milk jugs, walmart bags, tires, wood, my junk laptop, anything that has some carbon in it). Lets say I have filled the pot with HDPE. Now its time for more oak.

http://www.youtube.com/watch?v=f6NbljcpDew

Have a look at these guys. They are making oil from plastic.

It turns out that inorder to crack crude oil in a catylitic cracking plant, one needs aluminum silicate in a matrix, like a zeolite OR....terra cotta. I dropped my twinkie when I read that. You mean to tell me the big catalyst secret to making short chain molecules out of heavy molecules is broken flower pots? Oh yeah! I gotta try this...
The other big news that I got excited about was the off gas potential. I could heat this whole operation with CO and H2 if I can figure out what the recipe or procedure is.

So right now I am wondering if there are hydraulic pumps that already come with viton seals or can they be retro fit?
Originally I thought to flash the heated feed stock against hot steel but now am wondering if it will be needed after all.
Another thing is whether the raw waste oil could simply be cracked this way. There looks to be plenty of Oxygen in the triglyceride molecule, to make CO with, and that could heat the operation.

Coke was a byproduct in the olden times...perhaps again?
Anyhow, I am going to keep looking around for a procedure. Please throw in any clues or thoughts you might have.
DF
(in this case I am so excited, I do want to collaborate...now thats funny!)


"I don't work with collectives. I don't consult, I don't co-operate, I don't collaborate."
Howard Roark
 
Location: Calumet, Michigan, Great White North | Registered: January 20, 2002Reply With QuoteReport This Post
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Assuming the heater does not burn out due to lack of total thermal contact,"during the run",can you imagine what you would be left with to clean out the pot,or are you seeing the "pot" a a disposable item.
It really interests me what some of these guys are doing cracking and distilling volatiles from plastic,but the temps they are using,put me off on safety grounds.Your pot DF is going to be a bigee to take whole cubies of glyc,but I would love to try something like this-gonna what this with great interest.
 
Location: UK | Registered: October 14, 2008Reply With QuoteReport This Post
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Thanks Taralec,
I plan on heating the pot til there is ash and coke. If you look at the walnut labs video...(I'm rolling my eyes, cause these guys are sooo embarrassing, but if you can get past the mouthbreathing cameraman...) he shows very little ash left.
DF


"I don't work with collectives. I don't consult, I don't co-operate, I don't collaborate."
Howard Roark
 
Location: Calumet, Michigan, Great White North | Registered: January 20, 2002Reply With QuoteReport This Post
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It would be great if you feed waste veg direct into the pot,over here in the UK we can get an abundance of solid palm oil (all our chip shops use it now),and yes it does make great summer bio,but there is all the processing hassle of not letting anything set solid,it would be a prime candidate for me,especially as we are supposed to be in spring and winter hasn't ended yet-can't see me processing much palm into bio this year at the moment.
DF presumably you are looking at temps up to 300c,how would you heat it?Insulation gets tricky at high temps.
Steam passed over hot coal/coke used to be the method for making town gas (mix of CO and HO)prior to north sea methane.
 
Location: UK | Registered: October 14, 2008Reply With QuoteReport This Post
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Taralec,
I would use oak to get the pot hot enough to off-gas. Then jet the off gas into the fire box.

Yes sir, this isn't a trivial exercise. It surely won't be something that takes away from the existing biodiesel infrastructure on these boards.

My vision of this is very similar to the link of the early coal fired cracker. A five hundred gallon propane tank set on a brickwork fire box is my first choice.

Yes, yes, I do ken those gas-o-meters you have over there. Or did have. I use gas producers here, but would junk them all in a heart beat if I could make homemade gasoline or diesel. There are too many moving parts, complex steps, and compromises in the way we are making fuel now (either BD or producer gas).

Another thing I am finding here is that he ethanol they put in the gas is destroying my carburetors and fuel tanks.

Also the oil quality is declining to. Too much water to take out, I need a way to heat large quantities of wet oil to seperate the water.
DF


"I don't work with collectives. I don't consult, I don't co-operate, I don't collaborate."
Howard Roark
 
Location: Calumet, Michigan, Great White North | Registered: January 20, 2002Reply With QuoteReport This Post



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I have done some cracking of WVO, Plastic and WMO and learned a bit about it. I have also tried burning Glyc directly and picked up a few things on that as well.

The Difference in the way I crack the materials as to what is in the illustration is rather than go from the boiler to the condenser, I first run the vapor through a super heater. This seems to be a critical step in ensuring you get clean liquid fuels as against waxy muck that will later solidify.
The super heater is simply the Pipe going from the top of the " Boiler" through the flame heating it so it's basically in my case, red hot, and then to the condenser.

In refinery's and commercial operations, it is the temp that the vapour is condensed at that determines it's weight such as being KEro, Diesel or petrol. I have only done single stage cracking so far but can still bias the output to what I want ( ie Diesel or petrol) by controlling the temp of the superheater. Generally I get an output that will light off it's own vapors like petrol but clearly also has a Diesel type component that is not as aromatic but none the less burns in open air without residue.

IF you burn petrol, Diesel or Kero in a spoon over an open flame you get get nothing left. IF you do the same with WVO, WMO and certainly glyc, you are left with deposits, significant ones in the case of Glyc. To me that is the test of how clean burning a fuel will be inside an engine and why you don't hear of Bio coking engines like you do WVO.

I haven't Tried Cracking Glyc but I do know from burning experiments there is a LOT of energy in it. I'm not a scientific or chemically educated guy so I don't know if that energy content comes from the carbon content or what, I just know from burning the stuff when it does burn, there is a lot of power unleashed.

With the glyc you will go through 3 basic phases. The Vaporisation of the meth and water, the vapourisation of the Glyc itself to a tar and then carbon like substance and then finally that will be come ash.

Not sure in this case if there is any energy to come from the last phase, I tend to think not and the hard carbon that forms will burn but I think it just gives off heat and changes phase to ash. THe carbon may also become powdery rather than hard and crusty depending on how it's " Cooked.

I know this much, If you don't cook it well past the tar and into the Carbon stage, it's going to be near impossible to remove from what ever vessel you heat it in.

My experimental have been smaller scale so far, I just use an Stainless steel keg and a very powerful WVO burner to heat it. I Condense the vapor through a heat exchanger first then bubble the output through a Column of water and I get very, very little gassing from the water.
That gas is in fact un-condensed fuel and the water seems to condense it out very effectively. It comes to the top of the water as fuel which can be drawn off and is perfectly good fuel. I don't understand why other designs I have seen don't also condense the gas. Some seem to have loads of it blowing away in the wind and just catch a few drops their inefficient condenser creates. It's not a waste product, it's just one that hasn't been efficiently condensed.

The trick I believe in this is not how hot you make the primary Boiler, rather how hot you heat the gas that comes off it.

I don't use any sort of Catalyst and don't understand the need for one. The reaction far as I can tell is a simple matter of Boiling and condensation. I'm not sure the role of a Catalyst other than perhaps increasing the efficiency of the process in a commercial application.

I can guarantee you it's easy to make good fuel of either a Petrol or Diesel weight just by heating and condensing at least out of the 3 base materials I have played with.
I don't see why Glyc would be any different.
 
Registered: July 30, 2010Reply With QuoteReport This Post
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Please note: Acrolein is very toxic at quite low concentrations. When you pyrolyze glycerin you generate large amounts of acrolein. Take care.
 
Registered: March 23, 2004Reply With QuoteReport This Post
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http://news.mongabay.com/bioen...iesel-byproduct.html

The glycerine by-product from biodiesel is a viable source from which to make ethanol for gassers.



** Biodiesel Glycerine Soap - The Guide
- on 5 continents helping people make & sell soap from the Biodiesel Glycerine.


 
Location: :-) Great White North eh ? | Registered: December 10, 2004Reply With QuoteReport This Post
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Hi,
Thanks for the thoughts about this...
I too have a fear of the toxicity of Acrolein. Yes you are correct, all my references indicate the pyrolisis of glycerine gives large amounts of Acrolein. But that is where it ends. My question, after looking at the molecule, is how it will behave in a reducing atmosphere. My hunch is that after Acrolein passes through an incandescent bed of carbon, I'll be left with Carbon Monoxide, and perhaps an Alkene, or Alkane. Not sure. Currently reducing pyrolized wood only offers hydrogen and CO with trace amounts of an Alkane.
Just thinking aloud here, but the idea would be to find the right procedure to bias the reduction of that C=O bond in Acrolein, and reconfigure the rest to CH3-CH2-CH2-CH2-CH2-CH2-CH2-CH3. I believe this is possible because we constantly struggle with long chain molecular production in gas producers, due to the reduction zone temp falling off, or too much water.

Another thing that occured to me yesterday, was that I should probably stick with glycerine and plastic, in one pot, and the oils in another. I was remembering from my distillation classes in school that those bubble cap columns are really only used to seperate chemicals that are miscible in each other.

My main thrust here would be to make gasoline and diesel fuel. The type of diesel fuel produced from this process wouldn't have the high gell point that soy based biodiesel would have. I am also primarily looking for benzene, or octane as products to be used as gasoline. Here on the island, I have a real problem with any alcohol based fuel. I have to buy the non-alcoholic premium gasoline for all my ancient spark ignition engines. I would happily settle for low octane fuel as long as the fuel systems didn't suffer the corrosion issue that would be the present case, were I to use alcoholic gasolines.

The Acrolein problem keeps pointing me at that plastic for some reason, I think that the Acrolein and the coke from the plastic could be used to create a reduction zone. The heat input would be the interesting dilema. I have a friend who uses plasma to reduce. I would prefer something a little more old school (less moving parts).

This thing is sounding more and more like a bench. Benches where groups of coal producers with seimens heat exchangers, that used an alternating batch process to make water gas. Or the new gas to liquids tech that Isreal Corp. uses to make gasoline from natural gas. The first reactor makes a product for the second reactor, which makes a product for the third reactor, and the off gas from one reactor heats the process of a different reactor.
Anyhow, this project is just what I needed. I was kinda languishing away, as BD production has fell into the mundane after so long.
DF


"I don't work with collectives. I don't consult, I don't co-operate, I don't collaborate."
Howard Roark
 
Location: Calumet, Michigan, Great White North | Registered: January 20, 2002Reply With QuoteReport This Post
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this really peaked my interest. thank you for the idea. I had been giving it some thought and pondered the following. it may not be in accordance with your old school method desires, however, I believe it may be some valuable ideas/considerations for others reading this thread hoping to do the same.

1.it seems from what ive been reading on the blenders forum, my short term experience with blending, and the youtube video that the distilled hydrocarbon liquids could be blended, filtered, and put straight in a diesel vehicle.

2.
quote:
My experimental have been smaller scale so far, I just use an Stainless steel keg and a very powerful WVO burner to heat it. I Condense the vapor through a heat exchanger first then bubble the output through a Column of water and I get very, very little gassing from the water.
That gas is in fact un-condensed fuel and the water seems to condense it out very effectively. It comes to the top of the water as fuel which can be drawn off and is perfectly good fuel. I don't understand why other designs I have seen don't also condense the gas. Some seem to have loads of it blowing away in the wind and just catch a few drops their inefficient condenser creates. It's not a waste product, it's just one that hasn't been efficiently condensed.


this seems like it would be the best way to do it. it would clean and separate the condensate and improve efficiency

3. I believe you said the gasses given off by the reaction (not the vapors) were CO and H2. if you could channel the gasses somehow I believe you could run an electric generator on them much like with a wood fueled gasifier. of course you would need to input normal air to burn the H2 but the CO should just pass right through the engine. if there is any steam or methyl vapors going into the engine I would think it would be just like running a WMI system improving power and efficiency of the engine.

4. coke is a fuel used in blacksmithing and you have stated that it does burn. it seems that you could use it for many things like fueling the fire for your reactor, or heating your home.

my concern with using wood would be that it would most likely take a large volume to achieve the desired heat and that some sort of aerated jet heater would provide more bang for the buck. there are videos on making turbo (like in vehicles) jet engines that really are just good at burning fuel efficiently. or, something like a propane jet shop heater would work well.

5. a home hot water heater may be the best already fabricated water separator

6. you could drain off the water separator unit into an up-flow settling tower. if you find that you always get the same % yield of each by product (being that you will probably be always putting cubies filled with glycerin in it) than you can put a tap at the respective levels of each liquid to only draw off one at a time vice manual separation via small containers, resettling, and top pouring. using isolation valves at each tap and a transfer pump you could easily fill whatever larger collection container you choose with only the desired liquid. some gas would remain in the diesel, some diesel would remain in the oil but at that small of a quantity shouldn't affect whatever you decide to use it in.

7. also, why couldn't you just put straight beans or some other oil producing crop straight in the unit? it seems like you would be skipping all of the trouble to get the glycerin in the first place. beans are an oil containing hydrocarbon.

I hope I broadened your thought process on the subject.
 
Location: south georgia | Registered: January 13, 2015Reply With QuoteReport This Post
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the bubbler condenser of this unit could double as the fuel tank to a GEET engine. a GEET engine burns 100% of the fuel and has no exhaust. im looking into this more. check it out its pretty crazy.

https://www.youtube.com/watch?v=9FblcOKur8w
 
Location: south georgia | Registered: January 13, 2015Reply With QuoteReport This Post



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Hi mszostek,

quote:
Originally posted by mszostek:
the bubbler condenser of this unit could double as the fuel tank to a GEET engine. a GEET engine burns 100% of the fuel and has no exhaust. im looking into this more. check it out its pretty crazy.

https://www.youtube.com/watch?v=9FblcOKur8w
It's pretty phony-baloney
You do not really believe this do you?

There was an obvious exhaust in the video.
My engine burns 100% of it's fuel






 
Location: ลึก ประเทศอินเดีย | Registered: March 03, 2001Reply With QuoteReport This Post
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Hard as it is to believe there are people who believe in this.
And HHO and Free energy and a bunch of other twaddle.

I'm thinking of selling my 90% ownership of the Sydney Harbour Bridge. Maybe some of these people that see the potential in these things would be interested in purchasing this investment as well?
I'm prepared to let it go cheap as long as they pay cash.
 
Registered: July 30, 2010Reply With QuoteReport This Post
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