[biofuel] Re: phosphoric acid in Foolproof method
--- In biofuel@yahoogroups.com, simonswb6 [EMAIL PROTECTED] wrote: how does using hot water help with the bubble wash? Hot water dissolves soap better than cold water does (same reason as why sugar dissolves in hot tea better than in cold tea). Heat also breaks/prevents emulsions. Hot water washing seeems to be cvommonly used in oil chemistry processes of all kinds, if I understand correctly. whenever they use water washing for anything they heat it. I'm seeing less smulsification (or none at all) and think I'm getting everything washed with much less water (which is my aim) Many people have reported wash problems that miraculously go away when summertime comes. Temperature is why- quite low temp changes have an effect on emulsion formation in bubblewashing. I got great results washing some pretty iffy biodiesel at 100F, typical summertime ambient temps in much of the US. . I was looking this info up for someone else the other day and found info that also said that monoglycerides and diglyerides in biodiesel are more soluble in hot water than cold water (where they're not all soluble I believe- otherwise you could just wash your way to ASTM biodiesel glycerol content levels, which you can't). I don' t know what the supporting evidence was for this statement, but it could be another reason for why this works. Or the author of the MG/DG statement might have been making the conclusion from what he was seeing (better washes) and it might be all due to the soap dissolving issue, I d Yahoo! Groups Sponsor -~-- Buy Ink Cartridges or Refill Kits for your HP, Epson, Canon or Lexmark Printer at MyInks.com. Free s/h on orders $50 or more to the US Canada. http://www.c1tracking.com/l.asp?cid=5511 http://us.click.yahoo.com/mOAaAA/3exGAA/qnsNAA/FGYolB/TM -~- Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html Biofuels list archives: http://archive.nnytech.net/ Please do NOT send Unsubscribe messages to the list address. To unsubscribe, send an email to: [EMAIL PROTECTED] Your use of Yahoo! Groups is subject to http://docs.yahoo.com/info/terms/
[biofuel] Re: phosphoric acid in Foolproof method
hot water washes very strongly how does using hot water help with the bubble wash? --- In biofuel@yahoogroups.com, skillshare [EMAIL PROTECTED] wrote: Hmm,, I'm not sure how to respond. I assume you're talking about neutralising, as it's rather rare to make biodiesel that doesn't contain some alkaline substances. If you're reading pH 7 in recently-made, unwashed biodiesel you're probably not getting an accurate reading. If you neutralise the soap and catalyst in your fuel using acid, I believe you are then forming some kind of metallic salt. This should probably be washed out with water for various reasons. what way are you reading this pH? I bubblewash, and I now bubblewash with very hot water which gives great results. I also reuse the 2nd/3rd or 4th wash water for other batches- countercurrent wash water reuse. My goal is to reduce the water I need to use. On my last 45-gallon batch of fuel, I used only 10 gallons of new water (last wash) and 20 gallons of water recycled from previous batches. Here are a lot more details about the bubblewashing that I do: http://www.journeytoforever.org/biodiesel_bubblewash2.html I've changed a few details since I wrote that article. I now recommend hot water washes very strongly, I now use 1/4 water to 3/4 biodiesel, and I usually now do only a 1 or 2-hour bubbling on the first wash. I make my own wash stones out of small grindstones or little pieces of sharpening stones because the aquarium ones I've used all disintegrate in biodiesel eventually. Because it's very hot right now here, and I work outside, all the fuel I make is turning out to be good quality and therefore the washes produce no emulsion due to quality and the higher wash temperatures. I;m curious to see how much this changes once it's winter- the colder weather makes a difference in both washing and in processing if temperatures of the processor drop too much (my experience last winter, slightly improved by adding much more insulation!)). good luck! mark --- In biofuel@yahoogroups.com, Pieter Koole [EMAIL PROTECTED] wrote: Hi girl-mark-fire, Is there any sense in washing the BD when the pH is around 7 ? I use the single stage base method. If you recommend washing, what is the best way to do so ? Met vriendelijke groeten, Pieter Koole Netherlands The information contained in this message (including attachments) is confidential, and is intended for the addressee(s) only. If you have received this message in error please delete it and notify the originator immediately. The unauthorized use, disclosure, copying or alteration of this message is strictly forbidden. We will not be liable for direct, special, indirect or consequential damages arising from alteration of the contents of this message by a third party or in case of electronic communications as a result of any virus being passed on. - Original Message - From: girl_mark_fire [EMAIL PROTECTED] To: biofuel@yahoogroups.com Sent: Sunday, September 21, 2003 8:08 AM Subject: [biofuel] Re: phosphoric acid in Foolproof method I think that part of the acid advice comes from Terry UK's old, old message that's up at your site- 'add a gloop' I think it says. It was the best info there was at the time (a lot better than the bound-for-emulsion suggestions in Tickell's book which tell you to basically spray water at the stuff, I've been there done that and boy did it confuse me when it went to emulsion). Terry's article is where I first saw bubblewashing instructions and though Aleks gives a different way of doing it, the 'just add a gloop' of acid bit sticks in one's mind I think. I thought that 'just keep adding acid' advice from Terry also really threw me off when I was first starting out with washing, as it didn't really explain emulsion other than to suggest fixing it with acid (with little accounting for different strengths of acid, etc...) Which is primarily why I wrote that article you've got up there. Perhaps Terry's article could use a link to your notes on acid in case people don' t find it by themselves? by the way when you use acids to break emulsion, how much acid do people use, compared to the amount needed to get the water pH to go neutral? It seems to me that it takes a while to see visible results by the 'just add some till emulsion clears' method, so people probably overdo the acid waiting to see results. Just a hunch. Maybe a more scientific approach to that particular problem is in order as well? (I am a very big fan of hot water washing now and dont ' get emulsion at all no matter how vigerous the wash is, in fact I've been experimenting with all the 'emulsifying' wash methods- what Todd calls Frog in a Blender'. I'ts still quite hot
[biofuel] Re: phosphoric acid in Foolproof method
Hmm,, I'm not sure how to respond. I assume you're talking about neutralising, as it's rather rare to make biodiesel that doesn't contain some alkaline substances. If you're reading pH 7 in recently-made, unwashed biodiesel you're probably not getting an accurate reading. If you neutralise the soap and catalyst in your fuel using acid, I believe you are then forming some kind of metallic salt. This should probably be washed out with water for various reasons. what way are you reading this pH? I bubblewash, and I now bubblewash with very hot water which gives great results. I also reuse the 2nd/3rd or 4th wash water for other batches- countercurrent wash water reuse. My goal is to reduce the water I need to use. On my last 45-gallon batch of fuel, I used only 10 gallons of new water (last wash) and 20 gallons of water recycled from previous batches. Here are a lot more details about the bubblewashing that I do: http://www.journeytoforever.org/biodiesel_bubblewash2.html I've changed a few details since I wrote that article. I now recommend hot water washes very strongly, I now use 1/4 water to 3/4 biodiesel, and I usually now do only a 1 or 2-hour bubbling on the first wash. I make my own wash stones out of small grindstones or little pieces of sharpening stones because the aquarium ones I've used all disintegrate in biodiesel eventually. Because it's very hot right now here, and I work outside, all the fuel I make is turning out to be good quality and therefore the washes produce no emulsion due to quality and the higher wash temperatures. I;m curious to see how much this changes once it's winter- the colder weather makes a difference in both washing and in processing if temperatures of the processor drop too much (my experience last winter, slightly improved by adding much more insulation!)). good luck! mark --- In biofuel@yahoogroups.com, Pieter Koole [EMAIL PROTECTED] wrote: Hi girl-mark-fire, Is there any sense in washing the BD when the pH is around 7 ? I use the single stage base method. If you recommend washing, what is the best way to do so ? Met vriendelijke groeten, Pieter Koole Netherlands The information contained in this message (including attachments) is confidential, and is intended for the addressee(s) only. If you have received this message in error please delete it and notify the originator immediately. The unauthorized use, disclosure, copying or alteration of this message is strictly forbidden. We will not be liable for direct, special, indirect or consequential damages arising from alteration of the contents of this message by a third party or in case of electronic communications as a result of any virus being passed on. - Original Message - From: girl_mark_fire [EMAIL PROTECTED] To: biofuel@yahoogroups.com Sent: Sunday, September 21, 2003 8:08 AM Subject: [biofuel] Re: phosphoric acid in Foolproof method I think that part of the acid advice comes from Terry UK's old, old message that's up at your site- 'add a gloop' I think it says. It was the best info there was at the time (a lot better than the bound-for-emulsion suggestions in Tickell's book which tell you to basically spray water at the stuff, I've been there done that and boy did it confuse me when it went to emulsion). Terry's article is where I first saw bubblewashing instructions and though Aleks gives a different way of doing it, the 'just add a gloop' of acid bit sticks in one's mind I think. I thought that 'just keep adding acid' advice from Terry also really threw me off when I was first starting out with washing, as it didn't really explain emulsion other than to suggest fixing it with acid (with little accounting for different strengths of acid, etc...) Which is primarily why I wrote that article you've got up there. Perhaps Terry's article could use a link to your notes on acid in case people don' t find it by themselves? by the way when you use acids to break emulsion, how much acid do people use, compared to the amount needed to get the water pH to go neutral? It seems to me that it takes a while to see visible results by the 'just add some till emulsion clears' method, so people probably overdo the acid waiting to see results. Just a hunch. Maybe a more scientific approach to that particular problem is in order as well? (I am a very big fan of hot water washing now and dont ' get emulsion at all no matter how vigerous the wash is, in fact I've been experimenting with all the 'emulsifying' wash methods- what Todd calls Frog in a Blender'. I'ts still quite hot outside right now so it doesn't cost me much in energy to heat. In winter it'll be a different story) . So I still don't recommend acidulating as a matter of course, unless you know what you're doing. It can be done right if you do a titration for soap/catalyst first
[biofuel] Re: phosphoric acid in Foolproof method
Hello Mark I think that part of the acid advice comes from Terry UK's old, old message that's up at your site- 'add a gloop' I think it says. Yes, then it says Not too much, and then it says wait and add another gloop if necessary, in other words a little at a time. But indeed it's not exactly precise. He sent me what I thought was an updater a couple of months back, but it was the same as the previous one, so I guess he still does it that way, and I also guess it works well for him, but that in practice he'd have a much more precise idea of what a gloop means. It was the best info there was at the time (a lot better than the bound-for-emulsion suggestions in Tickell's book which tell you to basically spray water at the stuff, I've been there done that and boy did it confuse me when it went to emulsion). Terry's article is where I first saw bubblewashing instructions and though Aleks gives a different way of doing it, the 'just add a gloop' of acid bit sticks in one's mind I think. I thought that 'just keep adding acid' advice from Terry also really threw me off when I was first starting out with washing, as it didn't really explain emulsion other than to suggest fixing it with acid (with little accounting for different strengths of acid, etc...) Which is primarily why I wrote that article you've got up there. Perhaps Terry's article could use a link to your notes on acid in case people don' t find it by themselves? Unless you already have the url I don't think there's any way of navigating direct to Terry's article except via the main Bubblewashing page, and the acid advice is right there directly below the link, and there are Back buttons at the end of Terry's article: Back to: Bubble washing Aleks Kac's wash method: Washing. Mike Pelly's method: Washing and drying. Bubblewashing 101 by Maria Alovert That should be enough. by the way when you use acids to break emulsion, how much acid do people use, compared to the amount needed to get the water pH to go neutral? It seems to me that it takes a while to see visible results by the 'just add some till emulsion clears' method, so people probably overdo the acid waiting to see results. Just a hunch. Maybe a more scientific approach to that particular problem is in order as well? But wouldn't the more scientific approach be not to make MGs in the first place? And to be less impatient in the second place? Better not to make a mess than to get expert at cleaning it up. (I am a very big fan of hot water washing now and dont ' get emulsion at all no matter how vigerous the wash is, in fact I've been experimenting with all the 'emulsifying' wash methods- what Todd calls Frog in a Blender'. I'ts still quite hot outside right now so it doesn't cost me much in energy to heat. In winter it'll be a different story) . So I still don't recommend acidulating as a matter of course, unless you know what you're doing. It can be done right if you do a titration for soap/catalyst first to find out how much acid to use (that HCL/ bromophenol blue indicator titration that Juan described a week or so ago). Why do a titration? Adding it slowly while monitoring the pH should do. I'd like to test this out against that soap test, see if it turns out the same. Someone's already done the research to figure out what the soap test titration tells you in exact numbers, so it's one of those rare things in biodiesel shadetree testing, a quantitative measure. It's what I was looking for a year ago with quest Let us know what you find. Best Keith Yahoo! Groups Sponsor -~-- Special Sale: 50% off ReplayTV Easily record your favorite shows! CNet Ranked #1 over Tivo! http://us.click.yahoo.com/WUMW7B/85qGAA/ySSFAA/FGYolB/TM -~- Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html Biofuels list archives: http://archive.nnytech.net/ Please do NOT send Unsubscribe messages to the list address. To unsubscribe, send an email to: [EMAIL PROTECTED] Your use of Yahoo! Groups is subject to http://docs.yahoo.com/info/terms/
[biofuel] Re: phosphoric acid in Foolproof method
I think that part of the acid advice comes from Terry UK's old, old message that's up at your site- 'add a gloop' I think it says. It was the best info there was at the time (a lot better than the bound-for-emulsion suggestions in Tickell's book which tell you to basically spray water at the stuff, I've been there done that and boy did it confuse me when it went to emulsion). Terry's article is where I first saw bubblewashing instructions and though Aleks gives a different way of doing it, the 'just add a gloop' of acid bit sticks in one's mind I think. I thought that 'just keep adding acid' advice from Terry also really threw me off when I was first starting out with washing, as it didn't really explain emulsion other than to suggest fixing it with acid (with little accounting for different strengths of acid, etc...) Which is primarily why I wrote that article you've got up there. Perhaps Terry's article could use a link to your notes on acid in case people don' t find it by themselves? by the way when you use acids to break emulsion, how much acid do people use, compared to the amount needed to get the water pH to go neutral? It seems to me that it takes a while to see visible results by the 'just add some till emulsion clears' method, so people probably overdo the acid waiting to see results. Just a hunch. Maybe a more scientific approach to that particular problem is in order as well? (I am a very big fan of hot water washing now and dont ' get emulsion at all no matter how vigerous the wash is, in fact I've been experimenting with all the 'emulsifying' wash methods- what Todd calls Frog in a Blender'. I'ts still quite hot outside right now so it doesn't cost me much in energy to heat. In winter it'll be a different story) . So I still don't recommend acidulating as a matter of course, unless you know what you're doing. It can be done right if you do a titration for soap/catalyst first to find out how much acid to use (that HCL/ bromophenol blue indicator titration that Juan described a week or so ago). Why do a titration? Adding it slowly while monitoring the pH should do. I'd like to test this out against that soap test, see if it turns out the same. Someone's already done the research to figure out what the soap test titration tells you in exact numbers, so it's one of those rare things in biodiesel shadetree testing, a quantitative measure. It's what I was looking for a year ago with quest Yahoo! Groups Sponsor -~-- ReplayTV: Control live television Special Sale: 50% off ReplayTV CNet Ranked #1 over Tivo! http://us.click.yahoo.com/aUMW7B/A6qGAA/ySSFAA/FGYolB/TM -~- Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html Biofuels list archives: http://archive.nnytech.net/ Please do NOT send Unsubscribe messages to the list address. To unsubscribe, send an email to: [EMAIL PROTECTED] Your use of Yahoo! Groups is subject to http://docs.yahoo.com/info/terms/
Re: [biofuel] Re: phosphoric acid in Foolproof method
Hi girl-mark-fire, Is there any sense in washing the BD when the pH is around 7 ? I use the single stage base method. If you recommend washing, what is the best way to do so ? Met vriendelijke groeten, Pieter Koole Netherlands The information contained in this message (including attachments) is confidential, and is intended for the addressee(s) only. If you have received this message in error please delete it and notify the originator immediately. The unauthorized use, disclosure, copying or alteration of this message is strictly forbidden. We will not be liable for direct, special, indirect or consequential damages arising from alteration of the contents of this message by a third party or in case of electronic communications as a result of any virus being passed on. - Original Message - From: girl_mark_fire [EMAIL PROTECTED] To: biofuel@yahoogroups.com Sent: Sunday, September 21, 2003 8:08 AM Subject: [biofuel] Re: phosphoric acid in Foolproof method I think that part of the acid advice comes from Terry UK's old, old message that's up at your site- 'add a gloop' I think it says. It was the best info there was at the time (a lot better than the bound-for-emulsion suggestions in Tickell's book which tell you to basically spray water at the stuff, I've been there done that and boy did it confuse me when it went to emulsion). Terry's article is where I first saw bubblewashing instructions and though Aleks gives a different way of doing it, the 'just add a gloop' of acid bit sticks in one's mind I think. I thought that 'just keep adding acid' advice from Terry also really threw me off when I was first starting out with washing, as it didn't really explain emulsion other than to suggest fixing it with acid (with little accounting for different strengths of acid, etc...) Which is primarily why I wrote that article you've got up there. Perhaps Terry's article could use a link to your notes on acid in case people don' t find it by themselves? by the way when you use acids to break emulsion, how much acid do people use, compared to the amount needed to get the water pH to go neutral? It seems to me that it takes a while to see visible results by the 'just add some till emulsion clears' method, so people probably overdo the acid waiting to see results. Just a hunch. Maybe a more scientific approach to that particular problem is in order as well? (I am a very big fan of hot water washing now and dont ' get emulsion at all no matter how vigerous the wash is, in fact I've been experimenting with all the 'emulsifying' wash methods- what Todd calls Frog in a Blender'. I'ts still quite hot outside right now so it doesn't cost me much in energy to heat. In winter it'll be a different story) . So I still don't recommend acidulating as a matter of course, unless you know what you're doing. It can be done right if you do a titration for soap/catalyst first to find out how much acid to use (that HCL/ bromophenol blue indicator titration that Juan described a week or so ago). Why do a titration? Adding it slowly while monitoring the pH should do. I'd like to test this out against that soap test, see if it turns out the same. Someone's already done the research to figure out what the soap test titration tells you in exact numbers, so it's one of those rare things in biodiesel shadetree testing, a quantitative measure. It's what I was looking for a year ago with quest Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html Biofuels list archives: http://archive.nnytech.net/ Please do NOT send Unsubscribe messages to the list address. To unsubscribe, send an email to: [EMAIL PROTECTED] Your use of Yahoo! Groups is subject to http://docs.yahoo.com/info/terms/ Yahoo! Groups Sponsor -~-- ReplayTV: Control live television Special Sale: 50% off ReplayTV CNet Ranked #1 over Tivo! http://us.click.yahoo.com/aUMW7B/A6qGAA/ySSFAA/FGYolB/TM -~- Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html Biofuels list archives: http://archive.nnytech.net/ Please do NOT send Unsubscribe messages to the list address. To unsubscribe, send an email to: [EMAIL PROTECTED] Your use of Yahoo! Groups is subject to http://docs.yahoo.com/info/terms/
[biofuel] Re: phosphoric acid in Foolproof method
Hello Mark I have to say I'm starting to change my mind about acid in the wash, but I think it has to be used a bit more scientifically than just 'adding some' which is how homebrewers seem to use it. Is that how they use it? I thought the usual way is to add acid until the wash water reads near neutral pH, or 7.5, or whatever, not just adding some. Aleks Kac specifies a set amount to use for the acid-base method, which makes sense because you're using a set amount of catalyst in the first place. That's the reason for using acid, after all, to neutralise the catalyst. Maybe the ones who just add some are the same ones who use it to make washing easier - they don't seem to be trying to neutralise the catalyst so much as cracking a galloping emulsion problem, they start bubblewashing and it froths over. I suppose the some that they add would be enough to stop it frothing. Adding acid may cure the symptom, but they need to get the process right (as you've said previously). Prof. Michael Allen said this on the Biofuels-biz list recntly: The purpose of the acid added to the wash-water after the transesterification is to break down any methoxide left in the ester and to neutralise it. Any strong acid would do for this. We use sulphuric acid to bring the wash water in contact with the methyl ester to a pH of not more than 8. If you don't add acid, you may not break down all the methoxide and there is a good chance that this will cause extra wear in an engine. Water will also break down sodium or potassium methoxide but it will not neutralise it. Maybe your teacher is right because your washing process is very efficient at removing excess catalyst. We found that this efficiency can only be achieved if we use much more water. Perhaps you can give us some details of your washing process... As for how much soap will be reconverted to FFA by adding acid to the wash, to dissolve back into your biodiesel, Mark Schofield just gave a rather precise measure of it: But remember the soap will return back to FFA. The pysical volume with respect to the final bio-diesel is very small indeed, maybe 0.001% v/v. I asked him how he'd arrived at that figure, but he hasn't responded. Michael Allen also said this on the Biofuels-biz list: The acid increases its [the wash'water's] capacity to wash out excess soap formed by the break-down of excess methoxide. But while the something acid may be taking out the soap as a sodium something salt, some free fatty acid is formed as well. Maybe not too much if we keep the wash water at a pH of 7 to 8 because these fatty acids are very weak (poorly ionised). Some of this FFA will probably disperse in the soapy wash water anyway and be removed (but some won't!). The particular fatty acids in a particular oil may have some effect on this too: For example, unsaturated fatty acids could perhaps be made water-soluble by the acid-washing process (I'm thinking of some of those sulphonates used in making shampoos here). Too many variables for a precise figure? Anyway, very little, if you do it right - well within the limits, and a worthwhile trade-off for the advantages. We seldom do it, but I don't think there are valid reasons not to use acid in the wash. But yes, please, let's be a bit scientific about it. Ive messed up a batch while experimenting that way not too long ago, overdid it on the HCL and a serious mess happened (it looked like emulsion and it had a high acid number on a titration (1.5) which wouldn't wash out. I eventually washed the hell out of it, and diluted it with a very high percentage of good fuel before using). So I still don't recommend acidulating as a matter of course, unless you know what you're doing. It can be done right if you do a titration for soap/catalyst first to find out how much acid to use (that HCL/ bromophenol blue indicator titration that Juan described a week or so ago). Why do a titration? Adding it slowly while monitoring the pH should do. Industry does it, but they also don't make particularly soapy biodiesel in the first place (because of using new oil or using acid-base ffa pretreatment), so the amount of ffa that is released when they acidulate isn't as large as it could be in a really problematic batch made by one of us... I want to make a comment on acid-base biodiesel, though- the one thing about it is that is different than singlestage biodiesel, is that you absolutely, positively must wash it. Think what you want about washing in general but for this method it's not an option not to wash. Fuel made with acid pretreatment contains water-soluble sodium sulfate formed by the neutralising of the sulfuric acid by some of the catalyst, and until you wash that stuff out, it's sulfur in your tailpipe emissions. For those wondering about how much of a danger it is that some sulfur might be left (I hear this question all the time)- well, the commercial guys who make fuel this way, pass the ASTM
[biofuel] Re: phosphoric acid in Foolproof method
I have to say I'm starting to change my mind about acid in the wash, but I think it has to be used a bit more scientifically than just 'adding some' which is how homebrewers seem to use it. Ive messed up a batch while experimenting that way not too long ago, overdid it on the HCL and a serious mess happened (it looked like emulsion and it had a high acid number on a titration (1.5) which wouldn't wash out. I eventually washed the hell out of it, and diluted it with a very high percentage of good fuel before using). So I still don't recommend acidulating as a matter of course, unless you know what you're doing. It can be done right if you do a titration for soap/catalyst first to find out how much acid to use (that HCL/ bromophenol blue indicator titration that Juan described a week or so ago). Industry does it, but they also don't make particularly soapy biodiesel in the first place (because of using new oil or using acid-base ffa pretreatment), so the amount of ffa that is released when they acidulate isn't as large as it could be in a really problematic batch made by one of us... I want to make a comment on acid-base biodiesel, though- the one thing about it is that is different than singlestage biodiesel, is that you absolutely, positively must wash it. Think what you want about washing in general but for this method it's not an option not to wash. Fuel made with acid pretreatment contains water-soluble sodium sulfate formed by the neutralising of the sulfuric acid by some of the catalyst, and until you wash that stuff out, it's sulfur in your tailpipe emissions. For those wondering about how much of a danger it is that some sulfur might be left (I hear this question all the time)- well, the commercial guys who make fuel this way, pass the ASTM test for sulfur, and for various reasons they don't wash their fuel quite as thoroughly as homebrewers, so I assume it must wash out quite well. Note also that you don't have to wash biodiesel made by the Foolproof method any special way. That's how Aleks does it, and that's fine, but once it's settled and the by-product (glycerine) layer at the bottom removed, biodiesel is biodiesel and washing it is washing it, no matter what process you used. So you can decide for yourself what's best fo Yahoo! Groups Sponsor -~-- Buy Remanufactured Ink Cartridges Refill Kits at MyInks.com for: HP $8-20. Epson $3-9, Canon $5-15, Lexmark $4-17. Free s/h over $50 (US Canada). http://www.c1tracking.com/l.asp?cid=6351 http://us.click.yahoo.com/0zJuRD/6CvGAA/qnsNAA/FGYolB/TM -~- Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html Biofuels list archives: http://archive.nnytech.net/ Please do NOT send Unsubscribe messages to the list address. To unsubscribe, send an email to: [EMAIL PROTECTED] Your use of Yahoo! Groups is subject to http://docs.yahoo.com/info/terms/
RE: [biofuel] Re: Phosphoric
Thanks for posting that.You answered a lot of my questions too. -Original Message- From: Appal Energy [mailto:[EMAIL PROTECTED] Sent: Sunday, April 28, 2002 7:01 AM To: Keith Addison Cc: [EMAIL PROTECTED]; biofuel@yahoogroups.com Subject: [biofuel] Re: Phosphoric Oky Keith, I've backtracked and got all the late email addressed or deleted. Now what was that question? Phosphoric was it? Here is the ugly little secret. Phosphoric has the propensity of breaking down an ester. What is broken ester? Simply put...it's an FFA. What is an FFA? It's a glyceride minus the glycerin...mono-, di- or tri-...it doesn't matter. So you have a glyceride that has been cracked and turned into an ester. The glycerin has dropped. Yet the addition of an acid such as phosphoric can crack an ester, taking it right back to an FFA. Then there's the really double ugly secret First, you might want to refer to The Soapmaker's Companion, a wonderful soapmaker's guide that can be enormously useful...even to a biodieseler. Both FFAs and glycerides saponify - turn into soap in the presence of base. It's not just FFAs that turn into soap, which apparently many people think when they contemplate turning toward 2 stage acid/base reactions and away from straight base processes. So in an acid/base you esterify the FFAs into esters in the acid stage, and perhaps a few glycerides are transesterified as well - not many, but a few. Cool. One problem solved, as there is now a lesser requirement for base catalyst in the base stage, because none of it will be bound up by FFAs. But from my perspective, there remains one considerable problem - it revolves around the general concept of catalysts and the time hardened tradition of biodieselers who have cut their teeth on straight base reactions and the formulations they have used for so long. Most of us who have performed straight base reactions titrate in order to determine how much compensation must be made to override the presence of FFAs. And most of us have relied upon the 3.5 grams NaOH + x formula. The really fanciful part that few people have given much thought to in the backyard biodieseler's environment is that catalyst is never destroyed. It may get bound up, such as with FFAs or particulates, but if both of those variables are compensated for, the remaining free catalyst is there to do its job. So...define the purpose of a catalyst. Essentially adding extra amounts of catalyst accomplishes virtually nothing save for reducing reaction times, as catalyst is not destroyed. Essentially, even in a straight base esterification, it should only take a gram or less of catalyst beyond the titration requirement to effect a completed reaction over time. The biggest problem is that few people want to take the time. One-half gram of catalyst under heavy agitation might take 24 hours or perhaps even longer to convert 1 liter of oil. But the beauty is that if only one-half gram is used, 3.0 grams are omitted in comparison to some of the tried and true methods in the biodieseler's bibles. If you can get rid of this amount of base, you can also get rid of a relative amount of acid neutralizer, whether it be in a water wash or the FFA recovery from the glycerin layer. But the primary benefit of base catalyst reduction to the lowest possible level (lowest possible level to meet specific demands) is the reduction of soap formation. Yes, the base is a catalyst. But yes, it also saponifies triglycerides - it is conducive to making soap, even in the lack of presence of FFAs. The primary trick is to get rid of the FFAs, thereby reducing the volume of excess base catalyst needed for compensation, then create a system where time is not the most important element...where the method of manufacture and the energy comsumed to create ester manufacture is at a minimum and in balance with the least possible amount of catalyst appropriate to the specific application. If this is 15 gallons expected to react completely in two hours, the catalyst requirement will be heavy, and so will the soap manufacture. If this is 500 gallons expected to react completely in only 24 hours under heavy agitation, the catalyst requirement can be minimized to extremely small levels, which will in turn reduce soap manufacture, and in turn, reduce wash problems. Start throwing phosphoric acid into the esters in order to neutralize base catalyst as a result of impatience, and you start to break down esters into FFAs, as well as any soaps present that have been created by excessive catalyst (or even inexcessive catalyst). Do that to too high a degree and you can kiss meeting the ASTM D-6751 standard, the EU standard, or the Ausie standard good bye. Think of it as walking a tight rope. With a balance bar and sound head about you, it's not a problem for nearly anyone of limitted ability to get across the rope. If one is prone to panic, impatience or need for extrely expeditious reactions
[biofuel] Re: Phosphoric
Oky Keith, Thankyou! I'm proofreading a scan of an old book on fats and oils (1928) which is really teaching me a lot, answering a lot of questions I've had. I'll upload it to the Biofuels Library at Journey to Forever when I've finished it and post a link here. I like old books like this because they're clear, and the technology hasn't gotten too involved with a whole bunch of esoteric and heavily jargonised laboratory stuff that no ordinary earthling can comprehend. It's not as if the old stuff is discredited, not at all. And the technology is about at the level that backyarders can deal with - well, much better than that, of course, but you're not left with a whole bunch of principles you can't possibly adapt without a nuclear reactor or something. Anyway, yes, quite right - FFAs, glycerides, acids. Very interesting, this and your response to Ken on acid-base processes and cutting down on the base - or not, the acid-base process as-is. I think we progress. Better understanding, better information, better processes, better quality, less waste. And then? On to enzymes? Not to say anything's obsolete - 2-stage acid-base doesn't mean single-stage base is no use anymore, it just extends the range of options available. I've backtracked and got all the late email addressed or deleted. Now what was that question? Phosphoric was it? Here is the ugly little secret. Phosphoric has the propensity of breaking down an ester. What is broken ester? Simply put...it's an FFA. What is an FFA? It's a glyceride minus the glycerin...mono-, di- or tri-...it doesn't matter. So you have a glyceride that has been cracked and turned into an ester. The glycerin has dropped. Yet the addition of an acid such as phosphoric can crack an ester, taking it right back to an FFA. Then there's the really double ugly secret First, you might want to refer to The Soapmaker's Companion, a wonderful soapmaker's guide that can be enormously useful...even to a biodieseler. Right again - I don't have that one (I'll check it out, thanks), but I've learnt a lot from soapmaking. Left with some questions too - I think I mentioned one of them here before, and now it's come up again in the fats and oils book. Different fats and oils all have different saponification numbers, and if you're making soap you need to know what they are to calculate the right amount of lye. But we just use 3.5g plus whatever titration says (and it seems to say various things), titrating to pH8.5, mix it up, chuck it in and go, no matter what kind of oil it is. I'm interested to see how Paul's tests turn out, finding that higher-than-titration levels of NaOH seem to be giving a better result. That seems to be true for tallow, and there have been other reports indicating similar inconsistencies. (Paul, if you read this, I got waylaid on the work I'd planned with tallow, but I'll get at it soon, I've got quite a lot of fresh pure tallow here now, enough for a whole series of tests.) That 3.5g figure for virgin oil (of whatever ilk) isn't precise, it varies between 3.1 and 3.5, which makes for quite a big potential error, especially with high FFA oils, where it counts more. Could these saponification numbers be used to correct the basic 3.1-3.5g figure? What you're suggesting below with the acid-base process and reducing NaOH could be one good answer, good stuff. It would also be good, though, to tune up the old single-stage if possible. Both FFAs and glycerides saponify - turn into soap in the presence of base. It's not just FFAs that turn into soap, which apparently many people think when they contemplate turning toward 2 stage acid/base reactions and away from straight base processes. So in an acid/base you esterify the FFAs into esters in the acid stage, and perhaps a few glycerides are transesterified as well - not many, but a few. Cool. One problem solved, as there is now a lesser requirement for base catalyst in the base stage, because none of it will be bound up by FFAs. But from my perspective, there remains one considerable problem - it revolves around the general concept of catalysts and the time hardened tradition of biodieselers who have cut their teeth on straight base reactions and the formulations they have used for so long. Most of us who have performed straight base reactions titrate in order to determine how much compensation must be made to override the presence of FFAs. And most of us have relied upon the 3.5 grams NaOH + x formula. The really fanciful part that few people have given much thought to in the backyard biodieseler's environment is that catalyst is never destroyed. It may get bound up, such as with FFAs or particulates, but if both of those variables are compensated for, the remaining free catalyst is there to do its job. So...define the purpose of a catalyst. Essentially adding extra amounts of catalyst accomplishes virtually nothing save for reducing reaction times,
[biofuel] Re: Phosphoric
Oky Keith, I've backtracked and got all the late email addressed or deleted. Now what was that question? Phosphoric was it? Here is the ugly little secret. Phosphoric has the propensity of breaking down an ester. What is broken ester? Simply put...it's an FFA. What is an FFA? It's a glyceride minus the glycerin...mono-, di- or tri-...it doesn't matter. So you have a glyceride that has been cracked and turned into an ester. The glycerin has dropped. Yet the addition of an acid such as phosphoric can crack an ester, taking it right back to an FFA. Then there's the really double ugly secret First, you might want to refer to The Soapmaker's Companion, a wonderful soapmaker's guide that can be enormously useful...even to a biodieseler. Both FFAs and glycerides saponify - turn into soap in the presence of base. It's not just FFAs that turn into soap, which apparently many people think when they contemplate turning toward 2 stage acid/base reactions and away from straight base processes. So in an acid/base you esterify the FFAs into esters in the acid stage, and perhaps a few glycerides are transesterified as well - not many, but a few. Cool. One problem solved, as there is now a lesser requirement for base catalyst in the base stage, because none of it will be bound up by FFAs. But from my perspective, there remains one considerable problem - it revolves around the general concept of catalysts and the time hardened tradition of biodieselers who have cut their teeth on straight base reactions and the formulations they have used for so long. Most of us who have performed straight base reactions titrate in order to determine how much compensation must be made to override the presence of FFAs. And most of us have relied upon the 3.5 grams NaOH + x formula. The really fanciful part that few people have given much thought to in the backyard biodieseler's environment is that catalyst is never destroyed. It may get bound up, such as with FFAs or particulates, but if both of those variables are compensated for, the remaining free catalyst is there to do its job. So...define the purpose of a catalyst. Essentially adding extra amounts of catalyst accomplishes virtually nothing save for reducing reaction times, as catalyst is not destroyed. Essentially, even in a straight base esterification, it should only take a gram or less of catalyst beyond the titration requirement to effect a completed reaction over time. The biggest problem is that few people want to take the time. One-half gram of catalyst under heavy agitation might take 24 hours or perhaps even longer to convert 1 liter of oil. But the beauty is that if only one-half gram is used, 3.0 grams are omitted in comparison to some of the tried and true methods in the biodieseler's bibles. If you can get rid of this amount of base, you can also get rid of a relative amount of acid neutralizer, whether it be in a water wash or the FFA recovery from the glycerin layer. But the primary benefit of base catalyst reduction to the lowest possible level (lowest possible level to meet specific demands) is the reduction of soap formation. Yes, the base is a catalyst. But yes, it also saponifies triglycerides - it is conducive to making soap, even in the lack of presence of FFAs. The primary trick is to get rid of the FFAs, thereby reducing the volume of excess base catalyst needed for compensation, then create a system where time is not the most important element...where the method of manufacture and the energy comsumed to create ester manufacture is at a minimum and in balance with the least possible amount of catalyst appropriate to the specific application. If this is 15 gallons expected to react completely in two hours, the catalyst requirement will be heavy, and so will the soap manufacture. If this is 500 gallons expected to react completely in only 24 hours under heavy agitation, the catalyst requirement can be minimized to extremely small levels, which will in turn reduce soap manufacture, and in turn, reduce wash problems. Start throwing phosphoric acid into the esters in order to neutralize base catalyst as a result of impatience, and you start to break down esters into FFAs, as well as any soaps present that have been created by excessive catalyst (or even inexcessive catalyst). Do that to too high a degree and you can kiss meeting the ASTM D-6751 standard, the EU standard, or the Ausie standard good bye. Think of it as walking a tight rope. With a balance bar and sound head about you, it's not a problem for nearly anyone of limitted ability to get across the rope. If one is prone to panic, impatience or need for extrely expeditious reactions, the balanced approach might not fit all that well. Thankfully, most biodieselers can afford to wait 24 hours for a reaction. In doing so, presuming they are also effectively able to reduce their base catalyst, they will save themselves enormous time and headache in the wash stages.
