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quote:
mixed some FFAs from split byproduct


From basic transestrification not supercritical of course. No soap in supercritical to crack to FFAs.

You are aware that only around 25% of that layer is actually FFAs?


mathematical elegance -- desired result achieved with minimal complication
 
Location: Manchester UK | Registered: June 03, 2003Reply With QuoteReport This Post
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I said "mixed some FFAs from split byproduct "

To which Ant replied:



quote:
From basic transestrification not supercritical of course. No soap in supercritical to crack to FFAs.

You are aware that only around 25% of that layer is actually FFAs?



Yes, on both counts. I've been running a pretty much standard system made from a 100 gallon propane tank. I've had plenty of my own byproduct to split and play with.

Most of the "FFAs" from split byproduct titrate around 20. At least mine do, but that may be a little low from adding in the biodiesel that settles out of the stand tank, and other - tamer - stuff. I let the fuel stand for a day or two, GL eco-processor like, and drain the soapiest fuel off the bottom. I split that and toss it in with the byproduct. I try not to waste much.

As a source of serious FFAs to work with I recently took 10 gallons of WVO, added 5 gallons of water, and ran it through the supercritical processor at about 300C and 2000 PSI. I was testing a heat exchanger and most of it went through several times. I took a sample that would have been part water and part glycerin as well as FFAs, and it titrated at 80. I think pure FFAs should titrate around 100, and this might well have if I washed out the glycerin and settled the water.

--- David
 
Location: Maine, USA | Registered: July 06, 2007Reply With QuoteReport This Post
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Cool. Or rather very hot. Can I have a supercritical processor if I make you tea and sandwiches while you work? Wink


mathematical elegance -- desired result achieved with minimal complication
 
Location: Manchester UK | Registered: June 03, 2003Reply With QuoteReport This Post
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Dave,
I'm really excited about your results on the higher temp. work with the Macroporous resin????

Any data to report?

GCG

This message has been edited. Last edited by: GCG,
 
Location: Michigan | Registered: May 08, 2007Reply With QuoteReport This Post
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Sorry, no new tests to report on. A friend is currently putting together a nice stainless steel heater and a smallish test chamber to pump stuff through.

I can add that I learned something from a Dow support person. He had a few good things to know:

1) Most of the solid acid catalysts will probably work about the same when you first start. The difference between them comes when it's time to regenerate them.

2) At least the Dowex DR2030 catalyst will absorb the water produced by esterification - to a point. At 8-10% of the resin weight esterification will slow or stop, at which point it needs to be dehydrated.

3) They have solid base catalysts too, some they've tried for transesterification. The problem with the base catalyst is that FFAs will attach to the catalyst, poisoning it. They're not easily regnerated - you can't just wash them off with a bit of lye in a methanol bath.

4) Solid acid catalysts don't have the same problems. Apparently, if they get poisoned by some lye you can wash the lye off with an acid methanol bath.

5) He thought a relatively low pressure would help get the FFAs into the pore structure. He was talking about 3-4 at one point, and maybe 30-40 at another. A thousand PSI was quite uncalled forSmile

6) Elevated temperature, mild pressure, and constant circulation should all help. I can't easily do that in my canning jar test, so it'll have to wait another week or so for the rest of the test gear to be ready.

--- David
 
Location: Maine, USA | Registered: July 06, 2007Reply With QuoteReport This Post
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GCG said:

quote:
David,

Great test and it appears you have stumbled on something we recently discovered while performing a methanol flush of our Lead Resin Column filled with the Thermax' Tulsion T-45 BD Macro ion exchange resin: See the video for methanol flush here: Chads454 photobucket.


It would be really great if you could stitch all the pieces together to make an X minute presentation of the whole cleaning process.

quote:

Anyway while we were filming this procedure we decided on the fly to show everyone the methanol purity test using an alcoholmeter and then follow it up with a soap test titration.

Well when we began to do the titration by adding the flushed methanol sample to the isopropanol/bromophenol blue mixture; it went yellow immediately and when testing the methanol for acidity it came up fairly acidic.

We believe this is due to the resins ability to interact with the free fatty acids created when the soap molecule is converted to a fatty acid.

We are not sure exactly what is happening but it seems possible that the resin is retaining or adsorbing some amount of the FFA's and it takes quite a bit of flushing to remove them all since they seem to be present all the way up to the 5th bed volume of methanol flushing...


I spoke to a very knowledgable Dow techie for a while about solid acid catalysts in general. Since the product is - generically speaking - a sulfuric acid molecule with one end anchored to the plastic bead it's going to act a lot like the acid floating free from a chemical perspective, but of course its easy to pack in a bed.

Being a strong acid it's going to split soap into FFAs and sodium or potassium. The metal is going to bind to the catalyst, poisoning it. The rep said the base could be removed by flushing the bed with a mildly acidic methanol wash. IE, add a bit of sulfuric acid to the rinse methanol.

There are obviously some other things going on that I don't pretend to understand. The soap is not all being split - some is being adsorbed as well. I think some impurities are being trapped on a charge basis as well.

quote:


Lastly in your experiment you only heated the sample to 130 deg. F and this equivalent to 55 deg. C and this isn't hot enough for the resin to esterify the FFA's fully. The manufacturer recommends >70 deg. C or ~160 deg. F. and 120-180 minutes of residence time.

I am very interested in your study - once again simply wonderful work your doing.

By-the-way we sent a sample of the flush methanol to Van Gerpen at Idaho University to be analyzed. Hopefully I will hear something on this soon.

GCG


I hope to try under much better pressures and temperatures in the near future.

I've got a couple of questions about your T45 catalyst...

1) How long should it last between flushes?
2) How long should it last before it needs to be replaced, and is there a regeneration process other than flushing that will extend its life?
3) What sort of dehydration procedure do you use with it? I presume it adsorbs or absorbs water as well, which will make it less effective for either esterification or purification.
4) Are you recommending it for use in pre-process esterification or just post-process purification? Using it to pre-treat the feedstock and make so much less soap just seems like such a natural to me, but I don't see it positioned that way.

Thanks,

--- David
 
Location: Maine, USA | Registered: July 06, 2007Reply With QuoteReport This Post



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quote:
Originally posted by David Miller:

It would be really great if you could stitch all the pieces together to make an X minute presentation of the whole cleaning process.

Thanks,

--- David


David
Here's the compiled video.
http://www.youtube.com/watch?v=cwakgSYVdO0

-


Chad
2000 F350 SD 7.3PSD, 1996 F250 SD 7.3 PSD, 2005 Jeep liberty CRD, 2002 TC29D New Holland Tractor, 6K Diesel Generator, Heated Power Washer 'All Burnin Bio'

http://arborbiofuelscompany.com/ Selling Dry Wash Columns.

http://i88.photobucket.com/alb...icationGCresults.jpg
 
Location: S.E Michigan | Registered: May 12, 2007Reply With QuoteReport This Post
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How goes the project David?


mathematical elegance -- desired result achieved with minimal complication
 
Location: Manchester UK | Registered: June 03, 2003Reply With QuoteReport This Post
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It's sort of stalled at the moment as I rebuild the important parts in stainless.

I have the resin testing rig, but it uses a lot of the same parts as the supercritical rig - pressure pump, heater, etc.

I'm hoping to know more in a couple of weeks.

--- David
 
Location: Maine, USA | Registered: July 06, 2007Reply With QuoteReport This Post
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good luck with it. Feel free to email me if you get the time. I only come on line sporadically at the moment. but have found a prefered spot for access while I sort out my move.


mathematical elegance -- desired result achieved with minimal complication
 
Location: Manchester UK | Registered: June 03, 2003Reply With QuoteReport This Post
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Hi Jack writes them, acquired a strongly acidic resin and then the sulfone with H2SO4. Then wash with water and methanol dry resin and procedures to react yellow grease palm with interesting results. Someone has done something similar

Jorge
 
Location: Lima peru | Registered: March 31, 2006Reply With QuoteReport This Post
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look into rohm and haas bd 19 guard resin, and bd20 strong acid catalyst.

bd20 is a resin that you use "wet" which means the resin beads are used with oil that has methanol in it.

So pump your oil/meoh mix through the coulumn packed with this stuff at temp and it will esterify the ffa's.
 
Registered: June 07, 2008Reply With QuoteReport This Post



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quote:
Originally posted by David Miller:
I've been reading some old threads about solid catalysts, but they're all long dead and I don't see any of them having been generally adopted.

I'm most interested in acid catalysts good for esterification of FFAs.

So what has anyone found to work? Is anyone using amberlyst or DOW 2037 or the sugar catalyst?

--- David
Hi Davis, solid catalysts are being tested for AE. I'm trying to Tulsion T-66. Superacid catalyst. I can send photos.

You've tested resin Down? It's easy to get them where you live?

Greetings

Jorge Zegarra
jzegarrah@hotmail.com
 
Location: Lima peru | Registered: March 31, 2006Reply With QuoteReport This Post
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