| Pages:
1
2 |
Intergalactic_Captain
Hazard to Others
Posts: 228
Registered: 4-9-2004
Location: somewhere where i don\'t know where i am
Member Is Offline
Mood: frabjous
|
|
1000 gallons of glycerine - What would YOU do with it?
The topic of this thread is exactly what the title says. In the next couple of weeks, my dad's small-scale biodiesel production plant is going to be
up and running. He's been planning this for a couple years, and has finally got everything gathered together...Everything is set and ready to go,
save for a bit of welding and finding the time to run a couple test batches.
The thing is, the glycerol byproduct has been seen by us as nothing more than that - A useless byproduct. Straight out of the barrel, it's a dirty
mix of garbage that isn't worth the time to purify it for sale. So, I've got access to it by the barrel at no cost.
Aside from making nitroglycerine, which most certainly will be done, my current plans are to make an assload of allyl alcohol and convert a large
portion of it to the bromide. I am also interested in acrolein, though not until I get the money to fund a proper setup for it. Acrylic acid is also
on the list, as are a few experiments with synthetic sugars.
The question is, what else can I do with it? Glycerine on its own isn't that valuable...What I'd like to do is find something I could make with it
that has a proportionally larger monetary value. It doesn't matter what the chemical is, so long as it's worth more than the reagents to make it.
So, what would YOU do with a barrel of glycerine? Do you have some process that uses glycerine (or a byproduct therof)? Rare and esoteric?
- Not a problem...Provided it's doable without needing ultra-specialized equipment, it's on the list. I need to find a way to make money (directly or
inderictly) from glycerine....What's your idea?
oh...one last stipulation...seeing as how it's going to take a couple more decades for me to get a DEA license, anything I make has to be legal...Not
quasi-legal, but a completely legal chemical that could be sold to industry with minimal beaurocratic bullshit.
If you see me running, try to keep up.
|
|
|
The_Davster
A pnictogen
Posts: 2861
Registered: 18-11-2003
Member Is Offline
Mood: .
|
|
You could get a special furnace to burn it and use it to power the biodiesel plant
http://www.ukfueltech.com/biodiesel-glycerine.htm
I could have sworn there was another thread on this, but I can't seem to find it.
|
|
|
not_important
International Hazard
Posts: 3873
Registered: 21-7-2006
Member Is Offline
Mood: No Mood
|
|
Problem is most of the stuff made from glycerol in just a few steps tends to be high volume low cost materials; your 1000 gallons isn't on the chart,
you'd need a tanker car full to even sit at the table.
Products from glycerol.
Most straightforward is refined glycerol, filtering and low pressure distillation.
Next are the famous mono- and di- glycerides, made from select triglycerides and glycerol by transesterification. As these are often used in food
products, refining and food rated production facilities are needed.
Glycerol carbonate is used as a specialty solvent and various polymer products.
Different fermentations of glycerol can produce 1,3-propanediol, ethanol, succinic, lactic, butyric, acetic, and formic acids. One process of
interest that is being researched is coupling a carbohydrate based ethanol fermentation plant with a biodiesel plant, the CO2 from the fermentation
and the glycerol from the transesterification are feed to a bacterial fermentation that produces succinic acid.
Oxidation to polybasic acids is being investigated with the intent of creating feedstocks for new nylons and polysters. Oxidation to the
monocarboxylic glyceric acid may lead to production of a plastic similar to PLA. Oxidations are done with air catalytically.
|
|
|
Magpie
lab constructor
Posts: 5939
Registered: 1-11-2003
Location: USA
Member Is Offline
Mood: Chemistry: the subtle science.
|
|
Are you sure that it would be uneconomical to clean it up to the point where you could sell it? The reason I ask is that I just happened to have
bought a 6 oz bottle of glycerin today at my local pharmacy. It cost me $4.50.
[Edited on by Magpie]
The single most important condition for a successful synthesis is good mixing - Nicodem
|
|
|
not_important
International Hazard
Posts: 3873
Registered: 21-7-2006
Member Is Offline
Mood: No Mood
|
|
| Quote: | Originally posted by The_Davster
You could get a special furnace to burn it and use it to power the biodiesel plant
http://www.ukfueltech.com/biodiesel-glycerine.htm
I could have sworn there was another thread on this, but I can't seem to find it. |
Note that those furnaces are intended for incineration of glycerol as a method of disposing of it :
| Quote: | You may need to mix approx. 10-12% biodiesel with the glycerine ...
Glycerine on its own (i.e. with methanol removed) has little or no calorific value. These burners are NOT suitable for use with methanol free
glycerine. |
So you need to burn some of one of your raw materials - methanol - and some of your product to get rid of the glycerol, it is not a good energy
source.
There was a similar thread.
|
|
|
UnintentionalChaos
International Hazard
Posts: 1454
Registered: 9-12-2006
Location: Mars
Member Is Offline
Mood: Nucleophilic
|
|
Reagent grade, or for topical use? I have a 4oz bottle of "Swan" USP Glycerin. It probably cost me $2, though I only use it (so far) as an additive to
soap that I make at a rate of 20g per pound of oils. All my recipes are in grams, but to match the size of my bar mold, I need 1lb batches.
Edited for above post
[Edited on 4-24-07 by UnintentionalChaos]
Department of Redundancy Department - Now with paperwork!
'In organic synthesis, we call decomposition products "crap", however this is not a IUPAC approved nomenclature.' -Nicodem
|
|
|
pantone159
National Hazard
Posts: 590
Registered: 27-6-2006
Location: Austin, TX, USA
Member Is Online
Mood: desperate for shade
|
|
| Quote: | Originally posted by not_important
Different fermentations of glycerol can produce 1,3-propanediol
|
Do you have any details on the 1,3-propanediol fermentation? That could be used to make malonic acid which needed for most oscillating reactions but
is hard to get. (And would be problematic to sell...)
|
|
|
Magpie
lab constructor
Posts: 5939
Registered: 1-11-2003
Location: USA
Member Is Offline
Mood: Chemistry: the subtle science.
|
|
Actually the bottle is 6 oz. It is sold OTC as a skin protectant. "99.5% anhydrous"
The single most important condition for a successful synthesis is good mixing - Nicodem
|
|
|
not_important
International Hazard
Posts: 3873
Registered: 21-7-2006
Member Is Offline
Mood: No Mood
|
|
| Quote: | Originally posted by pantone159
| Quote: | Originally posted by not_important
Different fermentations of glycerol can produce 1,3-propanediol
|
Do you have any details on the 1,3-propanediol fermentation? That could be used to make malonic acid which needed for most oscillating reactions but
is hard to get. (And would be problematic to sell...) |
http://www.pubmedcentral.nih.gov/articlerender.fcgi?artid=20...
http://www.biodiesel.org/resources/reportsdatabase/reports/g...
http://docs.lib.purdue.edu/dissertations/AAI3133499/
http://www.andrew.cmu.edu/user/mhosier/FinalReport/fermentat...
http://pubs.acs.org/cgi-bin/abstract.cgi/jceaax/2001/46/i03/...
|
|
|
Pyridinium
Hazard to Others
Posts: 258
Registered: 18-5-2005
Location: USA
Member Is Offline
Mood: cupric
|
|
In that formic acid-glycerol reaction I'd be running off that acrolein into another reaction to make pyridine. Just because, for some odd reason,
pyridine is my favorite compound. Like benzene, only more interesting.
I couldn't imagine 1000 gallons of glycerol would be worthless. Even with the energy required to purify it, there should still be some profit margin
on it.
|
|
|
not_important
International Hazard
Posts: 3873
Registered: 21-7-2006
Member Is Offline
Mood: No Mood
|
|
There's so much glycerol now that prices are depressed, shipping it very far eats any profit.
The allyl alcohol from glycerol routes are fairly expensive, being of historic interest or for people who can't buy tank car lots and don't have their
own chemical plant 8-)
They are not that efficient and can't compete with other methods, oxalic acid or formic acid cost enough to make that so.
Neither method produces much acrolein.
|
|
|
Intergalactic_Captain
Hazard to Others
Posts: 228
Registered: 4-9-2004
Location: somewhere where i don\'t know where i am
Member Is Offline
Mood: frabjous
|
|
Excellent...Not too many ideas, but the ones I see are good. Burning it is off the table, as the EPA regs on doing it would probably be horrendous.
That, and why in the hell would I want to burn it? As a fuel, it'd be 10x more expensive than just burning the biodiesel produced...
The pyridine idea sounds pretty interesting though...Anyone have any references I could check out? If I could produce that at any state of purity, it
would definitely be worth the trouble.
As for allyl alcohol, I'm not that worried about efficiency - It is only for my use, and I'm thinking of a semi-continuous process for it...Glycerine
plus oxalic acid for the first run, then glycerine plus the above formed formic acid for subsequent runs. This'll be done in a 15gallon steel drum,
so one or two runs will give me enough to screw around with for at least a year. Provided I find a way to tweak the efficiency, I might find an
economically viable use for it...How much do you think I could get for a 100mL bottle of it on ebay?
Acrolein - Anyone got a reference with better than 50-60% yeilds? After checking the article in "The War Gasses," I did a bit of searching and found
that the process they mentioned is (or was, at least) the industrial method for producing it. NaHSO4 and KHSO4 are cheap enough to run it for my own
use, and it appears that it could be done in a continuous-feed reactor.
Does anyone have a process to go from acrolein to allyl alcohol? Running it through beilstein gave a few old (think mid 19th century) processes that
primarily overreduced the alcohol to n-propanol. I'd rather not go with any fancy weakened hydrides, those just aren't anywheres near economical
enough. I saw a couple of dissolving metal reactions involving HCl, though they had the same problem with overreduction. Considering making acrolein
is at least double the efficiency of allyl alcohol straight from glycerine, a decent cheap method (if one even exists) would be most appreciated.
If you see me running, try to keep up.
|
|
|
pantone159
National Hazard
Posts: 590
Registered: 27-6-2006
Location: Austin, TX, USA
Member Is Online
Mood: desperate for shade
|
|
Thanks, not_important. Unfortunately, the glycerol to 1,3-propanediol fermentation worked best with Klebsiella pneumoniae which doesn't
sound like such a friendly organism to breed in the home lab...
|
|
|
DeAdFX
Hazard to Others
Posts: 339
Registered: 1-7-2005
Location: Brothel
Member Is Offline
Mood: @%&$ing hardcore baby
|
|
You could make glycidyl(sp) nitrate. A very breif summary of a patent. Glycerin is nitrated to dinitro glycerin. This product is then treated with
sodium hydroxide to form NaNO3 and glycidyl nitrate. The glycidyl nitrate monomer can be polyermized using various lewis acids (BF3, PF5, etc...)
A much better procedure can be found using google patents.
I think glycerol can be used in a steam like reforming process AKA the synthesis of H2 gas using water and a carbon hydrogen (oxygen optional)
compound.
[Edited on 24-4-2007 by DeAdFX]
[Edited on 24-4-2007 by DeAdFX]
|
|
|
Levi
Hazard to Others
Posts: 196
Registered: 24-1-2007
Member Is Offline
Mood: No Mood
|
|
| Quote: | Originally posted by DeAdFX
I think glycerol can be used in a steam like reforming process AKA the synthesis of H2 gas using water and a carbon hydrogen (oxygen optional)
compound.
|
Yeah, but I imagine that the energy needed to sustain the reaction would be huge, but provided you had a proper storage system for the hydrogen it may
be profitable. Someone should crunch some numbers to see how much bio-diesel you'd have to burn to make hydrogen (or methanol) from glycerol and
water. It may make a good wartime fuel source. Methanol production would probably be better for a small scale since you wouldn't have to worry about
the hydrogen storage.
Chemcrime does not entail death. Chemcrime is death.
|
|
|
dedalus
Hazard to Self
Posts: 60
Registered: 13-4-2007
Location: New York
Member Is Offline
Mood: No Mood
|
|
I'd do...what I'm going to do. I'm getting into the same business.
Build an anaerobic digestor and see if I could get the buggies to make methane out of it. Then, use the methane for heating things on site. Or, vent
it. Then, dump the digestor contents into the sewer, after getting a permit, and pay them what they bill you. That will be a lot less than it would be
if you didn't anaerobically treat it, the BOD will be a lot lower.
|
|
|
not_important
International Hazard
Posts: 3873
Registered: 21-7-2006
Member Is Offline
Mood: No Mood
|
|
1, 2 propylene glycol
http://www.renewablealternatives.com/publications.htm
| Quote: |
Acrolein - Anyone got a reference with better than 50-60% yeilds? After checking the article in "The War Gasses," I did a bit of searching and found
that the process they mentioned is (or was, at least) the industrial method for producing it. NaHSO4 and KHSO4 are cheap enough to run it for my own
use, and it appears that it could be done in a continuous-feed reactor. |
Overview, plus references the USP number for more details. 99% vapour phase conversion, 70-75% selectivity.
http://www.eng.auburn.edu/users/edenmar/4470/4470_Project_De...
patent
http://www.patentstorm.us/patents/5387720-description.html
Catalytic dehydration of glycerol in sub- and supercritical water: a new chemical process for acrolein production
http://www.rsc.org/publishing/journals/GC/article.asp?doi=b5...
| Quote: | | Does anyone have a process to go from acrolein to allyl alcohol? |
It's a tough one, that C=C-C=O is pretty reactive and the C=C bond tends to react first.
|
|
|
Organikum
resurrected
Posts: 2337
Registered: 12-10-2002
Location: Europe
Member Is Offline
Mood: frustrated
|
|
IIRC then glycerine can be transformed to pyruvic acid in a tube furnance with some Zn catalyst. Dont know if thats better though.
|
|
|
Fleaker
International Hazard
Posts: 1252
Registered: 19-6-2005
Member Is Offline
Mood: nucleophilic
|
|
You could try and crack it catalytically and end up with a ''syn gas'' composed of CO, CO2, H2, CH4.
Neither flask nor beaker.
"Kid, you don't even know just what you don't know. "
--The Dark Lord Sauron
|
|
|
Intergalactic_Captain
Hazard to Others
Posts: 228
Registered: 4-9-2004
Location: somewhere where i don\'t know where i am
Member Is Offline
Mood: frabjous
|
|
Synthesis gas sounds like the best use of it thus far, but the costs to set up and utilize it...One of these days...
I'm currently scaveging together what I can find on n-propanol...Seems like the most valuable thing I can do thus far after balancing the cost to make
it. Figure about 60% yeild from glycerine to acrolein, then over 90% on catalytic hydrogenation to the alcohol.
I'm also doing a bit of research on acrylic acid, though effectively stabilizing it seems a bit tricky. Well, not so much stabilizing it but having a
chemical that needs to be stabilized sitting around and waiting for sale.
However, acrylic ethers seem to be quite valuable - I don't know quite where it comes from, though...Are they of high industrial value, or just
expensive to produce?
The last thing I found today seems to be the best, though - Artifical cinnamaldehyde by the Pt or Nickel catalyzed reaction of acrolein acetals and
halobenzenes. I had a stack of JACS articles pertaining to this about 20 minutes ago, but somehow managed to lose them on the bus back from
the library...I'll post links when I find them again, if anyones interested.
If you see me running, try to keep up.
|
|
|
dedalus
Hazard to Self
Posts: 60
Registered: 13-4-2007
Location: New York
Member Is Offline
Mood: No Mood
|
|
A lot of folks have great ideas, certainly more interesting than my humble suggestion.
One caveat: a great thing about Bio-diesel is that there's little in the way of haz mat/haz waste issues involved. Introduce an element of
manufacturing other chemicals, it may bring up all kinds of permitting issues.
|
|
|
Intergalactic_Captain
Hazard to Others
Posts: 228
Registered: 4-9-2004
Location: somewhere where i don\'t know where i am
Member Is Offline
Mood: frabjous
|
|
Yeah, I guess that's a valid point... The thing is, though, we're not really all that interested in making the biodiesel itself. The primary aim is
to sell relatively small, self-contained, self-powered reactors capable of supplying farmers with cheap fuel. Fortunately, though, the project thus
far has stockpiled several thousand gallons of WVO for experimentation, with a steady supply possible so long as we want it.
My dad's interested in just straight doing something, while I'm interested in the money...Startup cost is the problem, though. I just find it a
little odd that I could use the primary product from the process to fuel a plant for the "enrichment" of the byproduct...
I did, however, find a nice "book" on cyclic amines on JACS - Don't have a link, but it's titled "Heterocyclic Nitrogen Compounds," by Edward Curtis
Franklin and F.W. Bergstrom, it's in one of the 1944 issues...Good read, if anyone's interested in making nitrogen heterocycles - Lots of info on
pyrroles.
If you see me running, try to keep up.
|
|
|
evil_lurker
National Hazard
Posts: 767
Registered: 12-3-2005
Location: United States of Elbonia
Member Is Offline
Mood: On the wagon again.
|
|
Personally, I'd burn the shiznit. All you need is an old freon tank, some pipe, and quite a bit of welding and cutting...
http://www.cybernet1.com/mcquaid/Waste%20Oil%20Burners.htm
Either that or rig up an 80 gallon water heater to run at pretty decent vacuum and distill it.
Also, you can use waste glycerine to re-esterfy the FFA instead of methanol. This has the advantage that you can heat it up a LOT more without the
need of a pressure reactor.
|
|
|
roamingnome
Hazard to Others
Posts: 363
Registered: 9-9-2006
Member Is Offline
Mood: No Mood
|
|
when evil_lurker mentioned the words 80 gallon water heater....
it would make a great solar water heater system
United States Patent 4482467
....mixture of propylene glycol with water and glycerin, and mixture of glycerin with water......
The heat-absorbing liquid according to this invention contains as a black coloring material powdered activated carbon which has excellent stability to
withstand the sunlight. The powdered activated carbon exhibits no desirable dispersibility in water.
it would cost a grip to set up from nothing....
|
|
|
S.C. Wack
bibliomaster
Posts: 2419
Registered: 7-5-2004
Location: Cornworld, Central USA
Member Is Offline
Mood: Enhanced
|
|
What I would do with it is become great friends with the manager of the local plant/animal source glycerin refinery and beg him to look into analysis
of a sample and if acceptable whether they would take it if delivered to their door. That slim chance sounds to me like the best hope of not getting
sucked into a black hole from whose forces time and money cannot escape.
Maybe a co-op with other biodiesel producers?
The Captain is right that glycerin by itself is an inexpensive product. Not long ago I worked for a company that purchased kosher glycerin from
Indonesia by the pallet of 55 gal. drums and even with the shipping costs, one would have a hard time competing with even synthetic 99.8 industrial
glycerin. But I suspect that using glycerin as a feedstock for other chemicals is just as non-viable if not more so as a small business venture,
unless one can create a new product and a market for it.
|
|
|
| Pages:
1
2 |
![[*]](images/xpblue/default_icon.gif){kind=icon}
