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Thai Chemists report a continuous process for biodiesel production.

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NNadir Donating Member (1000+ posts) Send PM | Profile | Ignore Thu Mar-02-06 07:59 PM
Original message
Thai Chemists report a continuous process for biodiesel production.
One of the major economic drags on biodiesel is represented that most production processes are batch processes, batch processes almost always being more expensive than continuous processes.

Thus this report from Thai scientists of potentially of large commercial significance in the growing biodiesel market:

Biodiesel (fatty acid alkyl esters) is an alternative fuel for diesel engines. It is an alcohol ester product from the transesterification of triglycerides in vegetable oils or animal fats. This can be accomplished by reacting lower alcohols such as methanol or ethanol with triglycerides. The reaction proceeds well in the presence of some homogeneous catalysts such as sodium hydroxide and sulfuric acid, or heterogeneous catalysts such as metal oxides or carbonates or enzymes. Sodium hydroxide is very well accepted and widely used because of its low cost and high product yield, but the solubility of potassium hydroxide in methanol is higher than that of sodium hydroxide. Although the reaction system is simple, one drawback that prevents wider use of biodiesel is its high energy consumption and production cost, partly resulting from the complicated separation and purification of the product. Therefore, to perform the reaction without the presence of a catalyst is one effective way to reduce the biodiesel cost. Various biodiesel production processes employing homogeneous, heterogeneous catalytic, and noncatalytic supercritical methods as reported in the literature are summarized in Table 1.1-5 Recently, there have been some reports on the noncatalytic transesterification reaction employing supercritical methanol conditions.3,6,7


Unfortunately in Asia, where this work was undertaken, much of the biodiesel source material is palm oil, which has been environmentally controversial because of the implications of the destruction of forests. However, I can think of no reason that similar processes could not be successful with oils that are somewhat benign, such as rapeseed oil.

Biological diesel fuel is a promising technology that may represent a small, but significant contribution in the difficult fight against global climate change.

The article abstract, from the ASAP section of Energy and Fuels, can be found here:

http://pubs.acs.org/cgi-bin/abstract.cgi/enfuem/asap/abs/ef050329b.html

The use of supercritical fluids, notably supercritical carbon dioxide and supercritical water, is a burgeoning and exciting area of chemistry, having become within technical viability owing to the grand advances in materials science in the last several decades.

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eppur_se_muova Donating Member (1000+ posts) Send PM | Profile | Ignore Thu Mar-02-06 09:10 PM
Response to Original message
1. Sounds like good science/engineering. Keep chipping away.
However, I'm astonished by this statement: "The reaction proceeds well in the presence of some homogeneous catalysts such as sodium hydroxide.... Sodium hydroxide is very well accepted and widely used because of its low cost and high product yield, but the solubility of potassium hydroxide in methanol is higher than that of sodium hydroxide."

What happened to saponification? Why on earth wouldn't the NaOH (KOH) just cleave the ester and STOP there? (This is from previous work they're citing, not their own work, I gather on first read.)
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NNadir Donating Member (1000+ posts) Send PM | Profile | Ignore Thu Mar-02-06 09:20 PM
Response to Reply #1
2. In the base catalyzed batch process, the reaction is not really
Edited on Thu Mar-02-06 09:23 PM by NNadir
saponification, but rather is transesterification. The reaction is run in methanol.

In an aqueous system the product would be saponified, and this is the industrial basis for soap manufacture.

Biodiesel production can be comprimised because of soap formation (saponification) in the presence of alcohols that have a significant fraction of water.

A good question.
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eppur_se_muova Donating Member (1000+ posts) Send PM | Profile | Ignore Fri Mar-03-06 05:13 PM
Response to Reply #2
3. Interesting, I just didn't think you could get away with that.
I know it only takes a little water to get NaOH/KOH to go into solution in ethanol. The idea that you could do this on a large scale is a bit surprising. I guess that is the difference between academic lab chemistry and industrial -- I do know a little about industrial stuff, but not much. Usually I can understand it in terms of chemistry I already know. They must be able to keep the reactants free of water much more effectively than I thought could be done at reasonable cost.

Of course, they're probably using molecular sieves in there somewhere. They suck up the water, you heat them and reuse them. We tend to think of that as the expensive way to do it in the lab, precisely we do everything in batches, and don't recycle for continuous production.
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NNadir Donating Member (1000+ posts) Send PM | Profile | Ignore Fri Mar-03-06 06:17 PM
Response to Reply #3
4. Surprisingly, there are no sieves.
One industrial process that is used for the removal of water in such cases is azeotropic distillation.

The oils themselves however are very hydrophobic, and in fact the glycerol/water phase comes out quite easily with most oils.

The issue of industrial/lab scale chemistry is one of the most fun issues in the field.

Every time you go to an ACS meeting, you hear all sorts of noble statements on how the two groups are going to start interfacing better in the future. Every company gives a presentation, usually two in fact - one from the process group and one from the research groups - saying how valuable this new cooperation will be. This "new" plan for cooperation is "new" every year, decade after decade.

In the present case, note that this process is in a supercritical fluid. The properties of supercritical fluids can be very surprising. Benzene is miscible with supercritical water.
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eppur_se_muova Donating Member (1000+ posts) Send PM | Profile | Ignore Fri Mar-03-06 07:23 PM
Response to Reply #4
5. I saw the supercritical CO2 part. Thought your snippet was ...
citing previous work not nec. in SC fluids (didn't read the paper itself). Yes, I know lots of "strange" things happen in supercritical fluids, w/CO2 being most people's favorite ("Nature's own effervescence!").

Off topic a bit: Ever hear of SF author Hal Clement? He wrote a novel, "Close to Critical", about humans finding an inhabited planet, larger than Earth so with thicker atmosphere, w/enough H2SO4 (a la Venus), enough H2O, and high enough temps for H2O in the atmosphere to be near the critical point, depending on weather. Not the greatest fiction ever written, but he does include some interesting physical chemistry in some of his novels. Real name: Harry Clement Stubbs. Full-time high-school chemistry teacher. Also wrote "The Nitrogen Fix" and "Still River", two books w/chemistry central to the story.

http://en.wikipedia.org/wiki/Hal_Clement

The Wikipedia entry shows he passed away in 2003, which I hadn't known. Another of the shapers of classic SF lost to us.
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NNadir Donating Member (1000+ posts) Send PM | Profile | Ignore Fri Mar-03-06 07:43 PM
Response to Reply #5
6. Interesting. I don't actually read fiction...
...except what I see here. ;-)

Most science fiction is light on the science and big on the fiction, so it is interesting to see some that actually involves real science.

The supercritical fluid in the system described isn't actually carbon dioxide. It's supercritical methanol; different and exciting I think, although clearly accessible only at elevated temperatures
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eppur_se_muova Donating Member (1000+ posts) Send PM | Profile | Ignore Fri Mar-03-06 10:57 PM
Response to Reply #6
7. Supercritical methanol!?! Look out for leaks!
Edited on Fri Mar-03-06 10:59 PM by eppur_se_muova
And keep a fire extinguisher every 10 feet or so! Not that you're likely to have a chance to use it before the fireball swallows everything.

On the fiction side, I tend to "hard" science fiction myself. Mostly written by physicists, so the science tends to be pretty solid. Tiny errors in the science lead to endless snarking, which none of them want to suffer.

No, I don't read Michael Crichton. :evilgrin:
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NNadir Donating Member (1000+ posts) Send PM | Profile | Ignore Fri Mar-03-06 11:06 PM
Response to Reply #7
8. You're a good guy eppur_se_muova!
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eppur_se_muova Donating Member (1000+ posts) Send PM | Profile | Ignore Fri Mar-03-06 11:13 PM
Response to Reply #8
9. Well, thanks, though I'm not sure what brought that on.
Soon, I should be getting my star, so I can hold my head a little higher...been saying "next paycheck" for the last 20 paychecks or so...
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