Sciencemadness Discussion Board - 1000 gallons of glycerine - What would YOU do with it?

1000 gallons of glycerine - What would YOU do with it?

Intergalactic_Captain - 23-4-2007 at 20:35

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.

The_Davster - 23-4-2007 at 21:00

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 - 23-4-2007 at 21:14

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 - 23-4-2007 at 21:18

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]

not_important - 23-4-2007 at 21:20

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 - 23-4-2007 at 21:30

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]

pantone159 - 23-4-2007 at 21:37

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 - 23-4-2007 at 21:58

Actually the bottle is 6 oz. It is sold OTC as a skin protectant. "99.5% anhydrous"

not_important - 23-4-2007 at 23:03

Quote:

Originally posted by pantone159

Quote:

Originally posted by not_important
Different fermentations of glycerol can produce 1,3-propanediol

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 - 24-4-2007 at 06:07

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 - 24-4-2007 at 06:57

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 - 24-4-2007 at 09:20

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.

pantone159 - 24-4-2007 at 10:17

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 - 24-4-2007 at 10:47

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 - 24-4-2007 at 11:09

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.

dedalus - 24-4-2007 at 15:04

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 - 24-4-2007 at 16:12

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 - 25-4-2007 at 04:53

IIRC then glycerine can be transformed to pyruvic acid in a tube furnance with some Zn catalyst. Dont know if thats better though.

Fleaker - 25-4-2007 at 09:49

You could try and crack it catalytically and end up with a ''syn gas'' composed of CO, CO2, H2, CH4.

Intergalactic_Captain - 25-4-2007 at 12:37

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.

dedalus - 26-4-2007 at 10:05

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 - 26-4-2007 at 13:45

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.

evil_lurker - 26-4-2007 at 13:59

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 - 26-4-2007 at 14:34

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 - 26-4-2007 at 15:02

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.

dedalus - 26-4-2007 at 15:16

Quote:

Originally posted by Intergalactic_Captain
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.

I had much the same idea.

I think the kicker is going to be waste disposal. I have to go look up this URL from the State of Ohio later, when I find it, I'll post it for you. They've (the regulators) already got bio-diesel in their sights.

Ozone - 28-4-2007 at 05:55

Here is another thread concerning "what to do with all of that glycerol".

http://www.sciencemadness.org/talk/viewthread.php?tid=7036&a...

Toward this, I have put together this preamble (please *do not* directly quote this without contacting me first):

The eventual exhaustion of petroleum, coupled with uncertain foreign policy is pushing the United States toward the development and use of bio-derived fuels and feedstock chemicals. The current plan, outlined by the President, calls for the production of 35E9 (billion) gallons of renewable fuels, in the US, by 2015.
Considering a nominal ethanol yield of 355-370 L/t from corn1, and a crop yield of ~135 bushels/acre2, we can expect this to demand 97,062,608 acres. Not counting pasture or idle acres3, the land requirement for this effort is around 22% of the total harvested land or ~123% of all corn in the US. In 2006, the US made 4,855 million gallons of ethanol4 or, approximately 17% of all corn grown. This means that we are using ~83% of our corn for food, be it domestic, foreign or reserve. Following this, we will need to plant 177,732,608 acres in order to meet the desired fuel quota and remain flush with food. This is only ~8% of the total projected agri-capable land, but the projected population of 324,509,473 people by 20155 will increase demand. It becomes clear, that like petroleum, the amount of corn that can be grown without conflicting with the food supply is finite. This can be circumvented by producing cellulosic ethanol.
Cellulosic ethanol, or ethanol produced from biomass mitigates many of the limiting factors associated with ethanol production including: competition with the food supply and feed transport costs. The sugar mill is perfectly suited for the production of cellulosic ethanol since fuel costs are rolled into the price of cane. At the current rate of use, 1/3 of the total bagasse, or about 467 t.bagasse/d (14% fiber) is available for production of ethanol. Cellulose can be expected to yield ~56.82 % w/w1 ethanol from bagasse, which can theoretically provide a sugar mill with ~256 t (190,192 L) of ethanol per day. At $0.51/gallon6, this turns into a profit of $25,526/d ($2,297,320/season.mill). Assuming a cooperative venture, significant savings can also be achieved by routing some of the product ethanol to produce biodiesel sufficient to power the heavy equipment associated with planting, harvest and processing of sugarcane.
Unfortunately, the production of biodiesel yields glycerol at a 1:3 molar ratio. Assuming 35 billion gallons of liquid fuel, and the current rate of consumption (40% of the total in diesel), we will be making ~1.2 billion gallons of glycerol per year. Once a desirable value added product, glycerol prices are streaking downward in response to a glut market. This can convert value added into storage and disposal costs. In order to see a profit on glycerol, we must first convert it into some product of value.

Works cited ( sorry cut-paste parsing was strange)

1. Klass, D.L. (1998). “Biomass for Renewable Energy, Fuels, and Chemicals”. Academic Press Ltd.; an Imprint of Elsevier. ISBN# 978-0-12-410950-6: 416, 418,
2. National Agricultural Statistics Service. (2001). “Crop Production”. USDA, Washington, D.C. http://usda.mannlib.cornell.edu/reports/nassr/field/pcp-bb/2...
3. Lubowski, R.N, Vesterby, M., Bucholtz, S., Baez, A. and Roberts, M.J. (2006). “MajorUses of Land in the United States, 2002.” USDA, Economic Research Service, Economic Information Bulletin No. (EIB-14): 54 pp. http://www.ers.usda.gov/publications/EIB14/eib14d.pdf.
4. Renewable Fuels Association. (2006). “Ethanol Industry Statistics.” http://www.ethanolrfa.org/industry/statistics/
5. U.S. Census Bureau. (2007). “U.S. POPClock Projection: Component Settings for April 2007.” http://www.census.gov/population/www/popclockus.html\
6. DiPardo, J. (2002). “Outlook for Biomass Ethanol Production and Demand”. EIA Forecasts. http://www.eia.doe.gov/oiaf/analysispaper/biomass.html.

Bio-diesel link

dedalus - 30-4-2007 at 18:09

The Ohio EPA url is:

http://www.epa.state.oh.us/ocapp/sb/publications/biodieselgu...

It's fairly exhaustive.

dedalus - 3-5-2007 at 16:19

I finally googled this issue. Everybody's thinking about this.

Anaerobically digesting it...been tried. Doesn't work too well. Some people tried to in conjunction with pig manure, but dosing in too much suppressed methane production.

There was some other people trying to convert it to succinic acid, via fermentation. That sounded kind of promising...is there much demand for that?

The sweet solution would be to convert it into some kind of monomer.

not_important - 3-5-2007 at 16:38

Quote:

Originally posted by dedalus
I finally googled this issue. Everybody's thinking about this.

Anaerobically digesting it...been tried. Doesn't work too well. Some people tried to in conjunction with pig manure, but dosing in too much suppressed methane production.

It needs to be run through an acid-former fermentation, with select microorganisms to convert the glycerol to feed for the methogens. Tends to be slow, unfortunately; perhaps the gene shufflers can do something.

Quote:

There was some other people trying to convert it to succinic acid, via fermentation. That sounded kind of promising...is there much demand for that?

The sweet solution would be to convert it into some kind of monomer.

Already mentioned in my earlier post. The CO2 + glycerol fermentation would couple ethanol or methane fermentations with biodiesel production, using wastes from both to make salable products.

The fermentation to 1,3 propylene glycol would give an alternative to ethylene glycol for making a PET like polyesters. Controlled oxidation gives acids and hydroxy acids that can be used in making plastics.

In theory glycerol could be used to make synth gas

C3H8O3 => 4 H2 + 3 CO

C3H8O3 + 3 H2O => 7H2 + 3 CO2

But there's a lot of engineering in that.

The attached PDF estimates the succinic acid market at 270,000 t yr, if price is low enough.

[Edited on 4-5-2007 by not_important]

Attachment: 21020267.pdf (191kB)
This file has been downloaded 9448 times

UnintentionalChaos - 3-5-2007 at 16:49

What about swapping it out for ethylene glycol for the production of PETE (PGTE?)? The result would most likely be an extremely highly crosslinked polymer (and hence hard and rigid) somewhat resembling bakelite, although properties are somewhat hard to predict before any testing. Any polymer using it would most likely be rigid due to heavy crosslinking What if you made polyglycerol as a substitute for PEG? If you could control the amount of crosslinking, it could probably substitute for many of the same uses. The best part is that of it works, you have the fact that it's "green technology" behind you, which seems to be the most recent "hot word"

not_important - 4-5-2007 at 00:54

Highly cross-linked plastics tend to be thermosetting, which limits what they can be used in, and often are brittle. Typically crosslinking is limited to a few percent.

PEG is made in effect by reacting ethylene oxide with ethylene glycol, givng repeating -O-CH2-CH2- units. How would you do that with glycerol, squeeze out water to form the ether linkages without dehydrating the glycerol?

xxxxx - 29-5-2007 at 12:27

i was wondering if a glycerine water mixture could be used as antifreeze/coolant in an automotive radiator system. presumably the vapor pressure of the mixture would be lower than a comparable mixture of ethylene glycol and water allowing the engine to operate at a somewhat higher temperature, presumably increasing fuel efficiency slightly. there would be the environmental advantage over ethylene glycol, assuming that the glycerine water mixture is not too viscuous to function as a coolant.

[Edited on by xxxxx]

not_important - 29-5-2007 at 21:20

Glycerol has been used as antifreeze in the past, and still is for some applications such as preservation of biological specimens. Besides the cost in the past, I believe there can be a problem with the formation of acrolein and from that gums.

Looks like they're working on making 1,2 propylene glycol from glycerol
http://www3.interscience.wiley.com/cgi-bin/abstract/11277118...

Another application is making glycerol acetals for use as oxygenate additives to (bio)diesel and gasoline. Reactive distillation of glycerol and acetaldehyde made from ethanol appears to be an attractive route. In fact, going to reactive distillation to make the fatty acid esters from oils is a much better method to make biodiesel than the current base catalysed method, it needs no alkali input, produces no waste salts, and the glycerol by-product is neutral and rather pure. Besides that the process can handle high levels of free fatty acids, something the base catalysed method can not.

Research on using glycerol:
http://www3.interscience.wiley.com/cgi-bin/abstract/11422961...
http://www.biodieselmagazine.com/article.jsp?article_id=377

The Glycerol Challenge

dedalus - 5-6-2007 at 13:18

It's a dedicated website, at http://theglycerolchallenge.org/