Re: [Biofuel] Glycerine Settling Time
Hello to All, This is an attempt to get things in focus for myself at least. I think this topic started with Re:Biodiesel Quality Test On 8/7/07 Mike W. stated that he allows his batches to settle for a week before washing; No problems with wash. On 8/7/07 I agreed, stated an observation and asked question: I have been wondering about something. When I started making BD it would never pass the methanol quality test. I inevitably got emulsions in the wash. Now, when I make BD for my oil-fired boiler, I use only about 16-17% (vol/vol) of methanol. The BD does not pass the quality test, but I don't have the same emulsion problems. Is it because I let it settle longer (24+ hours vs 6 - 8 hrs)? Does the presence of a small amount of glycerine/soaps make that much of a difference when trying to wash BD from an incomplete reaction? On 8/7/07 Joe Street wrote: Rod believes that glycerin settles slower in a poorly completed reaction. I believe he is right. And yes it only takes a little glycerin to emulsify your wash. Question: If Mono- and Di- Glycerides are such effective emulsifiers, and they don't settle out with the glycerin mix, why don't they emulsify my poor quality (heating system) BD? It seems that something in the glycerine cocktail (that does settle out) is the culpret. Tom ___ Biofuel mailing list Biofuel@sustainablelists.org http://sustainablelists.org/mailman/listinfo/biofuel_sustainablelists.org Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html Search the combined Biofuel and Biofuels-biz list archives (50,000 messages): http://www.mail-archive.com/biofuel@sustainablelists.org/
Re: [Biofuel] Glycerine Settling Time
Joe, he took washed esters that passed the methanol test and added water and (of course) no emulsion when agitate I used veg oil and water. (No emulsion) Added Glycerin (split) . failed to separate (emulsion?) I'll go back and test BD . will actually do measurements and everything. Tom - Original Message - From: Joe Street To: biofuel@sustainablelists.org Sent: Friday, August 10, 2007 9:45 AM Subject: Re: [Biofuel] Glycerine Settling Time Hi Jan; Ok your post agrees with what Andres said. So how do we explain Tom's experiment then? To recap (Tom correct me if I miss something here) he took washed esters that passed the methanol test and added water and (of course) no emulsion when agitated. Whatever mono and diglycerides were in the esters were small but present I assume, but yet no emusion. Then added some small quantity of glycerol ( which had been separated from the soaps, FFA and salts) and agitated again and did get an emulsion. I have had the feeling glycerin has usually been the cause of emulsion problems when I have had them. No doubt a poorly reacted batch is much more likely to have the problem but is that really due to the glycerides or is it glycerin which hasn't settled. Remember we started this discussion that the glycerin settles much slower in a poorly completed run. BTW as an addition to this discussion look what someone just posted on my yahoo group! Using glycerin cocktail to BREAK an emulsion. Now that's radical!!?? http://www.biodieselcommunity.org/breakingemulsions/ Joe Jan Warnqvist wrote: Hi evereybody. I feel obliged to enter this discussion. Pure glycerine is not a good emulsifier due to the fact that there are three OH-groups and that the carbon s in the first and third positions are surronded by two hydrogene atoms. This makes the glycerine hydrophilic in five places alltogether. However, the mono- and diglycerides are excellent emulsifiers. Only small amounts of these are sufficient to create stable emulsions. Would somebody agree with me on that ? Jan Warnqvist - Original Message - From: Keith Addison [EMAIL PROTECTED] To: biofuel@sustainablelists.org Sent: Friday, August 10, 2007 9:53 AM Subject: Re: [Biofuel] Glycerine Settling Time Hi Tom Hi Keith, Then if you do one-litre test batches first, especially with iffy batches of oil, Ops. I took Joe's point to be: If you have to re-process it is possible to use info from the QT to determine how much (how little) methanol you'll need to use. I also took that point, there were others though. It's a useful method, cheaper reprocessing, but I think we all agree that reprocessing itself is to be avoided if at all possible. Or I thought we did anyway. I think that both Joe and myself have standardize(d) the process so that passing the QT is the rule, not the exception. That's not what Joe said: It makes sense. Glycerin is an emulsifier. Have you ever tried dosing the batch again with a little methoxide? After you remove the glycerin it doesn't take much to get the last bit of the reaction to go and settle out the remaining glycerin. Of course this is well known already. Kenji and many others do straight base catalysis as a two stage deal. You can do a methanol test of sorts and the unreacted oil will settle out. Then you can use the measured amount of unreacted oil in the methanol test vial to estimate the percentage unreacted oil in your batch and dose accordingly with the stoichiometric amount of methoxide. Assume neutral oil for this calculation. Rod and I do this regularly if the batch fails the QT and it works like a charm. Will save you settling time in the long run. Rod and I do this regularly if the batch fails the QT and it works like a charm. That if makes it a little ambiguous, but the regularly bit puts a question-mark on what's the rule and what's the exception. Kenji and many others do straight base catalysis as a two stage deal. Less methanol notwithstanding, my question remains - why reprocess, as a standard procedure, instead of avoiding the problem in the first place? Could be wrong, but it sounds like Kenji and others might be doing this rather than doing a titration - you know the old line: There's no need for titration, just use 6.25 g. And then using the methanol test to try to fix the regularly ensuing disaster. A different version of that here in Japan is to put the stuff through a centrifuge, though the product still doesn't pass any quality test or standards test. What you describe is much the same as what I described, doing (whatever) tests during the processing, adjusting accordingly and conducting the whole thing as a single stage. From Joe's replies so far I can't tell if he (and Rod, and Kenji and many others) are doing it that way or not, but it seems not: Your
Re: [Biofuel] Glycerine Settling Time
Jan Warnqvist wrote: Hello Joe. There were probably small amounts of mono- and diglycerides left in the biodiesel, and/or possibly soaps which together are excellent emulsifiers. So then one would expect that the water added and shaken would emulsify due to those mono and di-glycerides, but it didn't happen. What's up with that? A strong acid will divide the glycerides into fatty acids and glycerine ,and the soaps into salts and fatty acids, which then goes into a fat phanse and an aquaeus phase, possibly with the salts in the bottom.' Best regards Jan - Original Message - *From:* Joe Street mailto:[EMAIL PROTECTED] *To:* biofuel@sustainablelists.org mailto:biofuel@sustainablelists.org *Sent:* Friday, August 10, 2007 3:45 PM *Subject:* Re: [Biofuel] Glycerine Settling Time Hi Jan; Ok your post agrees with what Andres said. So how do we explain Tom's experiment then? To recap (Tom correct me if I miss something here) he took washed esters that passed the methanol test and added water and (of course) no emulsion when agitated. Whatever mono and diglycerides were in the esters were small but present I assume, but yet no emusion. Then added some small quantity of glycerol ( which had been separated from the soaps, FFA and salts) and agitated again and did get an emulsion. I have had the feeling glycerin has usually been the cause of emulsion problems when I have had them. No doubt a poorly reacted batch is much more likely to have the problem but is that really due to the glycerides or is it glycerin which hasn't settled. Remember we started this discussion that the glycerin settles much slower in a poorly completed run. BTW as an addition to this discussion look what someone just posted on my yahoo group! Using glycerin cocktail to BREAK an emulsion. Now that's radical!!?? http://www.biodieselcommunity.org/breakingemulsions/ Joe Jan Warnqvist wrote: Hi evereybody. I feel obliged to enter this discussion. Pure glycerine is not a good emulsifier due to the fact that there are three OH-groups and that the carbon s in the first and third positions are surronded by two hydrogene atoms. This makes the glycerine hydrophilic in five places alltogether. However, the mono- and diglycerides are excellent emulsifiers. Only small amounts of these are sufficient to create stable emulsions. Would somebody agree with me on that ? Jan Warnqvist - Original Message - From: Keith Addison [EMAIL PROTECTED] To: biofuel@sustainablelists.org Sent: Friday, August 10, 2007 9:53 AM Subject: Re: [Biofuel] Glycerine Settling Time Hi Tom Hi Keith, Then if you do one-litre test batches first, especially with iffy batches of oil, Ops. I took Joe's point to be: If you have to re-process it is possible to use info from the QT to determine how much (how little) methanol you'll need to use. I also took that point, there were others though. It's a useful method, cheaper reprocessing, but I think we all agree that reprocessing itself is to be avoided if at all possible. Or I thought we did anyway. I think that both Joe and myself have standardize(d) the process so that passing the QT is the rule, not the exception. That's not what Joe said: It makes sense. Glycerin is an emulsifier. Have you ever tried dosing the batch again with a little methoxide? After you remove the glycerin it doesn't take much to get the last bit of the reaction to go and settle out the remaining glycerin. Of course this is well known already. Kenji and many others do straight base catalysis as a two stage deal. You can do a methanol test of sorts and the unreacted oil will settle out. Then you can use the measured amount of unreacted oil in the methanol test vial to estimate the percentage unreacted oil in your batch and dose accordingly with the stoichiometric amount of methoxide. Assume neutral oil for this calculation. Rod and I do this regularly if the batch fails the QT and it works like a charm. Will save you settling time in the long run. Rod and I do this regularly if the batch fails the QT and it works like a charm. That if makes it a little ambiguous, but the regularly bit puts a question-mark on what's the rule and what's the exception. Kenji and many others do straight base catalysis as a two stage deal. Less methanol notwithstanding, my question remains - why reprocess, as a standard procedure, instead of avoiding the problem in the first place? Could be wrong, but it sounds like Kenji and others might be doing this rather than doing a titration - you know the old line: There's no need for titration, just use 6.25 g. And then using the methanol test to try to fix the regularly ensuing disaster. A different version of that here in Japan is to put the stuff through a centrifuge, though the product
Re: [Biofuel] Glycerine Settling Time
Keith, You wrote: I think this is a misunderstanding. I didn't say what you say below, standardized; can't fail, and I didn't mean that standardising the process means there's no need for tests, I apologize for a poor choice of wording suggesting a misunderstanding. You are unquestionably a proponent of quality testing. -Tweak the process to get consistently good BD. -How do you know you have succeeded in tweaking just right? QT -QT each batch Who did I learn this from? Re: Big lunch You and Robert inspired me last summer to grow more edibles. I had moved towards flowers. Now I grow more of what I eat, and I'm eating pretty good. A short while back there was discussion of growing fruits/veggies on lawns, side yards, etc. I mention what I had for lunch or dinner just to keep the thought alive. You can grow good food even on a little patch of land. The experience is priceless. poached Muscovy egg and stir-fried Swiss chard in the offing... M Mm Mm I'm getting hungry Tom - Original Message - From: Keith Addison [EMAIL PROTECTED] To: biofuel@sustainablelists.org Sent: Friday, August 10, 2007 3:53 AM Subject: Re: [Biofuel] Glycerine Settling Time Hi Tom Hi Keith, Then if you do one-litre test batches first, especially with iffy batches of oil, Ops. I took Joe's point to be: If you have to re-process it is possible to use info from the QT to determine how much (how little) methanol you'll need to use. I also took that point, there were others though. It's a useful method, cheaper reprocessing, but I think we all agree that reprocessing itself is to be avoided if at all possible. Or I thought we did anyway. I think that both Joe and myself have standardize(d) the process so that passing the QT is the rule, not the exception. That's not what Joe said: It makes sense. Glycerin is an emulsifier. Have you ever tried dosing the batch again with a little methoxide? After you remove the glycerin it doesn't take much to get the last bit of the reaction to go and settle out the remaining glycerin. Of course this is well known already. Kenji and many others do straight base catalysis as a two stage deal. You can do a methanol test of sorts and the unreacted oil will settle out. Then you can use the measured amount of unreacted oil in the methanol test vial to estimate the percentage unreacted oil in your batch and dose accordingly with the stoichiometric amount of methoxide. Assume neutral oil for this calculation. Rod and I do this regularly if the batch fails the QT and it works like a charm. Will save you settling time in the long run. Rod and I do this regularly if the batch fails the QT and it works like a charm. That if makes it a little ambiguous, but the regularly bit puts a question-mark on what's the rule and what's the exception. Kenji and many others do straight base catalysis as a two stage deal. Less methanol notwithstanding, my question remains - why reprocess, as a standard procedure, instead of avoiding the problem in the first place? Could be wrong, but it sounds like Kenji and others might be doing this rather than doing a titration - you know the old line: There's no need for titration, just use 6.25 g. And then using the methanol test to try to fix the regularly ensuing disaster. A different version of that here in Japan is to put the stuff through a centrifuge, though the product still doesn't pass any quality test or standards test. What you describe is much the same as what I described, doing (whatever) tests during the processing, adjusting accordingly and conducting the whole thing as a single stage. From Joe's replies so far I can't tell if he (and Rod, and Kenji and many others) are doing it that way or not, but it seems not: Your question (and mine): Don't you have to heat up the whole batch again? (Time and energy) Joe's reply: This is all done right after draining the glycerin. I leave the heater on during this period. Do the rough QT right away before wash test. Rough QT? Anyway, how long is it settling before he drains the glyc? I run a QT towards the end of the reaction because I do not want to re-process. Indeed not. It takes me a few minutes and I like the certainty of knowing the BD is good before I pump it into my settling tank. If the test should fail when I'm making a batch for my car, I could use Joe's suggestion to help me better approximate the amount of methanol to add. If the process has been standardized, why bother? I think this is a misunderstanding. I didn't say what you say below, standardized; can't fail, and I didn't mean that standardising the process means there's no need for tests, whether in-process tests or 1-litre test batches or whatever. Anything can
[Biofuel] Glycerin as an Emulsifier (was Glycerine Settling Time)
Andres, Jan, Joe, Keith, and anyone else who has been following the saga, It would seem that glycerine, itself, is not an effective emulsifier. I've spent the morning experimenting in the kitchen. I did Wash Tests on BD that passed the QT and BD that failed the QT. I tested one group with glycerine split from the cocktail (using Phosphoric Acid) and another group with unsplit Glycerin cocktail. Volumes used: Biodiesel 150 ml Water 150 ml Glycerin (split and unsplit) 4 ml Temp: 70F (~22C) I. Glycerin split from the cocktail (used Phosphoric Acid): Controls: Time for clear separation (min) good quality BD + water 1 - 2 poor quality BD + water 3 - 4 Experimental: good quality BD + water + glycerine (split) less than 5 poor quality BD + water + glycerine (split) less than 5 II Glycerin Cocktail: good quality BD + water + glycerine cocktail2 hours* poor quality BD + water + glycerine cocktail2 hours* * At 2 hours there is a thin layer of BD (1 - 2 mm) The rest appears to be an emulsion. Andres and Jan, you are correct. Glycerin, itself, did little to retard separation of BD and water. Something in the cocktail does seem to be an emulsifier. (The soaps??) Some questions remain: 1. The BD that failed the QT (incomplete reaction) was obtained from a tank that feeds my heating system. It contains unreacted glycerides, but does not produce an emulsion when shaken in water, nor did it produce emulsions when it was stir-washed. Why not? 2. At Joe Street's suggestion I took a sample of BD that had settled for about 10 hours. Twelve hours later, more glycerin had settled out. Today, still another 24 hours later, even more has settled out. Could this small amount of unsplit glycerine (with associated soaps) be the cause of the emulsions I got when I started making BD? It would explain why settling for a day or more seems to eliminate the problem. 3. Does the glycerine mix (or soaps) settle out more slowly in BD from incomplete reactions? Tom ___ Biofuel mailing list Biofuel@sustainablelists.org http://sustainablelists.org/mailman/listinfo/biofuel_sustainablelists.org Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html Search the combined Biofuel and Biofuels-biz list archives (50,000 messages): http://www.mail-archive.com/biofuel@sustainablelists.org/
Re: [Biofuel] The Quest for Nutrient-Dense Food--High-Brix Farming and Gardening
Aarghh! - not Arden Anderson again! We went through all this a few weeks ago. http://www.mail-archive.com/biofuel@sustainablelists.org/msg70226.html Re: [Biofuel] Acres USA Don't trust people with brix meters and a box of electrickery who tell you they're going to balance your soil or energise it to rid you of pests and problems. Indeed. To see whole article go to url Don't bother. Arden Andersen, Neal Kinsey, Carey Reams, Dan Skow, Charles Walters and many of the rest of Walters's coterie at Acres USA are not to be taken seriously. They've got brix all upside down, it just doesn't work that way. Do real organics, do it properly, and you'll have high brix readings anyway, and a lot more than that - which you won't get by chasing high brix levels for their own sake. (Nor by reading Acres USA.) http://journeytoforever.org/farm_library.html Small Farms Library - Journey to Forever Best Keith The Quest for Nutrient-Dense Food--High-Brix Farming and Gardening http://www.westonprice.org/farming/nutrient-dense.htmlhttp://www.we stonprice.org/farming/nutrient-dense.html An Interview with Rex Harrill by http://www.westonaprice.org/farming/#authorSuze Fisher Rex Harrill of Keedysville, Maryland has been farming and gardening for the better part of thirty years. Seventeen years ago he moved to a 16-acre farm and started a new garden. In the first few years his crops were tasteless and ridden with spittle bugs, caterpillars and several other garden pests. Yet his previous garden had produced delicious, pest-resistant crops, although he didnâ*t know why at the time. Only later did he realize heâ*d inherited a garden with exceptional soil fertility at his previous farm. But after two years of bitter turnips, radishes and other crops from his new garden, Rex set out to find answers. Thatâ*s when he came across a book called The Anatomy of Life Energy in Agriculture by Dr. Arden Andersen. Heâ*d finally found what heâ*d been seeking--a program that developed fertile soil which in turn produced delicious nutrient-dense crops that were resistant to pests, weeds and disease, year after year. Rex also learned from Dr. Andersen that the brix level of the crop correlated with its nutrient-density--that brix was a valuable measurement in determining the nutritional value of the crop. Ever since then, Rex has followed a high-brix gardening approach, strongly influenced by the works of Dr. Andersen along with those of Dr. William Albrecht, Dr. Carey Reams and Dr. Dan Skow. Suze: Rex, can you explain what Brix is? Most people Iâ*ve spoken to about Brix insist that itâ*s only a measure of a plantâ*s sugar content. Is this true? Rex: Iâ*ve come across many ways to dispel that only sugar notion. A favorite is to sit a Doubting Thomas on my back porch and pour him a glass of ordinary store-bought orange juice. Once he has sipped a little, I add a spoonful of sugar to his glass. Most people quickly understand that sugar is not what makes orange juice taste good--most report that the added sugar just makes the orange juice taste yucky. And it certainly does. The point is that adding the sugar raises the apparent Brix, but it does nothing for the taste. True Brix measures a combination of sugar, amino acids, oils, proteins, flavonoids, minerals and other goodies. Sugar is merely one of the components of Brix. This same scenario holds for any fresh juice you wish to name. Interestingly, the above doesnâ*t hold true for the artificial juices made mostly from chemicals, sugar, and water. Most of them do taste a little better if you add plain sugar. Suze: By fresh juice do you mean the sap of any plant? Rex: Fresh juice means liquid squeezed from a fruit. Be warned that much orange, apple, and other fruit juice is reconstituted from concentrate. Reconstituting can lead to false results. For instance, if you were to use 2 cans of water (instead of the recommended 3) when preparing frozen orange juice, you would get a terrific high Brix reading but not a true Brix reading. Many people are unaware of the fact that the juice they buy in a carton at the grocery store was once in a very concentrated state so that it could be cheaply shipped from another country. If the company reconstituting the juice adds too much water, you get lower Brix. If they donâ*t add enough water, you get higher Brix. Neither is true Brix. To be safe, I guess it is better to use the word sap for Brix test samples. Sap is the juice squeezed out of the leaves, stems, green fruit or roots of a live plant. Suze: How is Brix measured? Rex: The Brix test requires a refractometer. For a consumer to conduct a Brix test, they need a few drops of sap (juice) squeezed from the part of any plant that they wish to eat. In other words, they need to squeeze a small piece of lemon, orange, apple, etc., between their fingers and drop the juice onto their refractometer prism. Harder produce such as
Re: [Biofuel] Glycerine Settling Time
Hi Joe Hi Keith; See my answers below. Keith Addison wrote: Well, settling time is free. Acid-base aside, there's the two-stage base-base process, which quite a lot of people use and like, but otherwise why do more than one stage? Do you mean two separate stages, with a methanol test in between? So you process it twice? Plus extra methanol. No,- more like aiming for a single stage and then using the methanol test right after the settling period (after draining the glycerol of course) it gives you a chance to hit the reactor with another small dose of methoxide if it wasn't quite a complete reaction. The test also tells you how much to use. There is no standardising the process here since the feed is never the same twice. I don't think anybody's feedstock is ever the same twice, unless they're getting it from a food factory with a standardised operation. No restaurant cooks exactly the same food in the same way two days running. Anyway, why should that mean changing anything but the amount of catalyst needed? That's what titration is for, no? Certainly you can standardise the other variables. Rod decided to try a methanol test before washing, just for giggles and it turned out to be a heluva good idea. You know right away if you got a good reaction without having to waste all the time energy and water washing and drying before doing a quality test and then potenially having to reprocess. Before you started using this extra stage, how often did you have to reprocess? In your previous message it sounded like it happened regularly, and it still sounds that way. It turns out this looks just like a two step base -base type deal. but more like 90% of it in one step and then a polishing step. Sometimes if your process was good you don't need to do it, but if it turns out you were not near enough to completion it's nice to know right away. There's still methanol in the esters at that point (before washing) so it's advantageous to push the process further at that point if it is necessary. Joe This seems to raise more questions than provide answers. There were also some other points in my reply to Tom, eg, how long do you let the glycerin settle before draining it and embarking on the second stage/polishing step or whatever? I'll put the rest of my message back, below. Please see my reply to Tom: http://tinyurl.com/3ccqhw [Biofuel] Glycerine Settling Time Best Keith Hi Joe Tom; It makes sense. Glycerin is an emulsifier. Have you ever tried dosing the batch again with a little methoxide? After you remove the glycerin it doesn't take much to get the last bit of the reaction to go and settle out the remaining glycerin. Of course this is well known already. Kenji and many others do straight base catalysis as a two stage deal. You can do a methanol test of sorts and the unreacted oil will settle out. Then you can use the measured amount of unreacted oil in the methanol test vial to estimate the percentage unreacted oil in your batch and dose accordingly with the stoichiometric amount of methoxide. Assume neutral oil for this calculation. Rod and I do this regularly if the batch fails the QT and it works like a charm. Will save you settling time in the long run. Well, settling time is free. Acid-base aside, there's the two-stage base-base process, which quite a lot of people use and like, but otherwise why do more than one stage? Do you mean two separate stages, with a methanol test in between? So you process it twice? Plus extra methanol. Why not do it in a single phase? Todd Swearingen once suggested this here (discussing mixing pump sizes): To judge an appropriate reaction time, pull an exact amount of fluid (200 ml would suffice) out of the reaction stream every half-hour or hour after an arbitrary initial ~1 hour reaction period. Presuming that the contents of the reactor are kept homogenous from the pump flow, the volume of the glycerol cocktail that settles out of each sample will give you a fair gauge as to when your reaction completed. The suggestion would be to continue the reaction for ~1/2 hour beyond the point where your glyc cocktail volume stabilized. That works. Then, surely, you can standardise the process, with the only variable the amount of lye according to the titration level. Then if you do one-litre test batches first, especially with iffy batches of oil, and you have a clear idea of how your test-batch processing relates to your full-scale processing, life should be easier and there shouldn't be any batches failing the QT. What did I miss? ___ Biofuel mailing list Biofuel@sustainablelists.org http://sustainablelists.org/mailman/listinfo/biofuel_sustainablelists.org Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html Search the combined Biofuel and Biofuels-biz list archives (50,000 messages):
[Biofuel] Off Topic- Is Harmon
Seaver out there somewhere? Drop us a line, mate, if you are. Thanks Sorry for the interruption, Back to our regular programming. (btw, sorry I haven't posted in a while, but I just haven't had much to say that I could get in in less than a few thousand words, and who wants to read that?) ___ Biofuel mailing list Biofuel@sustainablelists.org http://sustainablelists.org/mailman/listinfo/biofuel_sustainablelists.org Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html Search the combined Biofuel and Biofuels-biz list archives (50,000 messages): http://www.mail-archive.com/biofuel@sustainablelists.org/
Re: [Biofuel] Glycerine Settling Time
Hi Tom Hi Keith, Then if you do one-litre test batches first, especially with iffy batches of oil, Ops. I took Joe's point to be: If you have to re-process it is possible to use info from the QT to determine how much (how little) methanol you'll need to use. I also took that point, there were others though. It's a useful method, cheaper reprocessing, but I think we all agree that reprocessing itself is to be avoided if at all possible. Or I thought we did anyway. I think that both Joe and myself have standardize(d) the process so that passing the QT is the rule, not the exception. That's not what Joe said: It makes sense. Glycerin is an emulsifier. Have you ever tried dosing the batch again with a little methoxide? After you remove the glycerin it doesn't take much to get the last bit of the reaction to go and settle out the remaining glycerin. Of course this is well known already. Kenji and many others do straight base catalysis as a two stage deal. You can do a methanol test of sorts and the unreacted oil will settle out. Then you can use the measured amount of unreacted oil in the methanol test vial to estimate the percentage unreacted oil in your batch and dose accordingly with the stoichiometric amount of methoxide. Assume neutral oil for this calculation. Rod and I do this regularly if the batch fails the QT and it works like a charm. Will save you settling time in the long run. Rod and I do this regularly if the batch fails the QT and it works like a charm. That if makes it a little ambiguous, but the regularly bit puts a question-mark on what's the rule and what's the exception. Kenji and many others do straight base catalysis as a two stage deal. Less methanol notwithstanding, my question remains - why reprocess, as a standard procedure, instead of avoiding the problem in the first place? Could be wrong, but it sounds like Kenji and others might be doing this rather than doing a titration - you know the old line: There's no need for titration, just use 6.25 g. And then using the methanol test to try to fix the regularly ensuing disaster. A different version of that here in Japan is to put the stuff through a centrifuge, though the product still doesn't pass any quality test or standards test. What you describe is much the same as what I described, doing (whatever) tests during the processing, adjusting accordingly and conducting the whole thing as a single stage. From Joe's replies so far I can't tell if he (and Rod, and Kenji and many others) are doing it that way or not, but it seems not: Your question (and mine): Don't you have to heat up the whole batch again? (Time and energy) Joe's reply: This is all done right after draining the glycerin. I leave the heater on during this period. Do the rough QT right away before wash test. Rough QT? Anyway, how long is it settling before he drains the glyc? I run a QT towards the end of the reaction because I do not want to re-process. Indeed not. It takes me a few minutes and I like the certainty of knowing the BD is good before I pump it into my settling tank. If the test should fail when I'm making a batch for my car, I could use Joe's suggestion to help me better approximate the amount of methanol to add. If the process has been standardized, why bother? I think this is a misunderstanding. I didn't say what you say below, standardized; can't fail, and I didn't mean that standardising the process means there's no need for tests, whether in-process tests or 1-litre test batches or whatever. Anything can fail. I'm all in favour of any tests that are helpful at any stage. So I agree with all you say here. Indeed, whatever rough might mean, using the methanol test to fine-tune the amount of extra methanol needed for reprocessing is a useful technique. But I'm not in favour of using reprocessing as a standard method, which, pending a better explanation, seems to be what's being proposed here. As you say: there shouldn't be any batches failing the QT. I've had a few failed batches in the past year. It seems to happen when I think I have it all figured out; standardized; can't fail. On one occasion the pump was making a bit of a funny noise when I came back to turn it off. Turned out a bit of paper towel or something had gotten into the impeller; inadequate agitation? Had I tested the BD before pumping it into the settling tank I could have avoided re-processing. While condensed water in bottom-of-the-barrel methanol or recovered methanol, contaminated caustic, etc may rear their ugly head in 1L test batches prior to running a batch, I think I would still run a QT prior to settling. Big skies :-) And broad horizons. Big lunch to you, I just had a garden pizza with Brocolli, zucchini, green peppers, sliced tomato, and chopped (v. mild) hot peppers. MMm Mm :-) Great Tom! A big lunch definitely helps when it
Re: [Biofuel] Glycerine Settling Time
Hi Tom Keith, You wrote: I think this is a misunderstanding. I didn't say what you say below, standardized; can't fail, and I didn't mean that standardising the process means there's no need for tests, I apologize for a poor choice of wording suggesting a misunderstanding. Thankyou Tom, but mea culpa, I could have been clearer about it but it was late and I was whacked. You are unquestionably a proponent of quality testing. -Tweak the process to get consistently good BD. -How do you know you have succeeded in tweaking just right? QT -QT each batch Who did I learn this from? :-) Who did I learn it from? Partly from some really bad examples that I think you're aware of, but mostly from the collective wisdom of the Biofuel list. To which you contribute a great deal. I guess we all owe each other eh? Re: Big lunch You and Robert inspired me last summer to grow more edibles. Then Robert and I will go to heaven! (And so will you!) I had moved towards flowers. Now I grow more of what I eat, and I'm eating pretty good. A short while back there was discussion of growing fruits/veggies on lawns, side yards, etc. I mention what I had for lunch or dinner just to keep the thought alive. You can grow good food even on a little patch of land. The experience is priceless. Indeed it is. Thankyou for keeping the thought alive, please don't stop. poached Muscovy egg and stir-fried Swiss chard in the offing... M Mm Mm I'm getting hungry :-) I'm getting sleepy! Later... Best Keith Tom - Original Message - From: Keith Addison [EMAIL PROTECTED] To: biofuel@sustainablelists.org Sent: Friday, August 10, 2007 3:53 AM Subject: Re: [Biofuel] Glycerine Settling Time Hi Tom Hi Keith, Then if you do one-litre test batches first, especially with iffy batches of oil, Ops. I took Joe's point to be: If you have to re-process it is possible to use info from the QT to determine how much (how little) methanol you'll need to use. I also took that point, there were others though. It's a useful method, cheaper reprocessing, but I think we all agree that reprocessing itself is to be avoided if at all possible. Or I thought we did anyway. I think that both Joe and myself have standardize(d) the process so that passing the QT is the rule, not the exception. That's not what Joe said: It makes sense. Glycerin is an emulsifier. Have you ever tried dosing the batch again with a little methoxide? After you remove the glycerin it doesn't take much to get the last bit of the reaction to go and settle out the remaining glycerin. Of course this is well known already. Kenji and many others do straight base catalysis as a two stage deal. You can do a methanol test of sorts and the unreacted oil will settle out. Then you can use the measured amount of unreacted oil in the methanol test vial to estimate the percentage unreacted oil in your batch and dose accordingly with the stoichiometric amount of methoxide. Assume neutral oil for this calculation. Rod and I do this regularly if the batch fails the QT and it works like a charm. Will save you settling time in the long run. Rod and I do this regularly if the batch fails the QT and it works like a charm. That if makes it a little ambiguous, but the regularly bit puts a question-mark on what's the rule and what's the exception. Kenji and many others do straight base catalysis as a two stage deal. Less methanol notwithstanding, my question remains - why reprocess, as a standard procedure, instead of avoiding the problem in the first place? Could be wrong, but it sounds like Kenji and others might be doing this rather than doing a titration - you know the old line: There's no need for titration, just use 6.25 g. And then using the methanol test to try to fix the regularly ensuing disaster. A different version of that here in Japan is to put the stuff through a centrifuge, though the product still doesn't pass any quality test or standards test. What you describe is much the same as what I described, doing (whatever) tests during the processing, adjusting accordingly and conducting the whole thing as a single stage. From Joe's replies so far I can't tell if he (and Rod, and Kenji and many others) are doing it that way or not, but it seems not: Your question (and mine): Don't you have to heat up the whole batch again? (Time and energy) Joe's reply: This is all done right after draining the glycerin. I leave the heater on during this period. Do the rough QT right away before wash test. Rough QT? Anyway, how long is it settling before he drains the glyc? I run a QT towards the end of the reaction because I do not want to re-process.
Re: [Biofuel] Glycerine Settling Time
Hi evereybody. I feel obliged to enter this discussion. Pure glycerine is not a good emulsifier due to the fact that there are three OH-groups and that the carbon s in the first and third positions are surronded by two hydrogene atoms. This makes the glycerine hydrophilic in five places alltogether. However, the mono- and diglycerides are excellent emulsifiers. Only small amounts of these are sufficient to create stable emulsions. Would somebody agree with me on that ? Jan Warnqvist - Original Message - From: Keith Addison [EMAIL PROTECTED] To: biofuel@sustainablelists.org Sent: Friday, August 10, 2007 9:53 AM Subject: Re: [Biofuel] Glycerine Settling Time Hi Tom Hi Keith, Then if you do one-litre test batches first, especially with iffy batches of oil, Ops. I took Joe's point to be: If you have to re-process it is possible to use info from the QT to determine how much (how little) methanol you'll need to use. I also took that point, there were others though. It's a useful method, cheaper reprocessing, but I think we all agree that reprocessing itself is to be avoided if at all possible. Or I thought we did anyway. I think that both Joe and myself have standardize(d) the process so that passing the QT is the rule, not the exception. That's not what Joe said: It makes sense. Glycerin is an emulsifier. Have you ever tried dosing the batch again with a little methoxide? After you remove the glycerin it doesn't take much to get the last bit of the reaction to go and settle out the remaining glycerin. Of course this is well known already. Kenji and many others do straight base catalysis as a two stage deal. You can do a methanol test of sorts and the unreacted oil will settle out. Then you can use the measured amount of unreacted oil in the methanol test vial to estimate the percentage unreacted oil in your batch and dose accordingly with the stoichiometric amount of methoxide. Assume neutral oil for this calculation. Rod and I do this regularly if the batch fails the QT and it works like a charm. Will save you settling time in the long run. Rod and I do this regularly if the batch fails the QT and it works like a charm. That if makes it a little ambiguous, but the regularly bit puts a question-mark on what's the rule and what's the exception. Kenji and many others do straight base catalysis as a two stage deal. Less methanol notwithstanding, my question remains - why reprocess, as a standard procedure, instead of avoiding the problem in the first place? Could be wrong, but it sounds like Kenji and others might be doing this rather than doing a titration - you know the old line: There's no need for titration, just use 6.25 g. And then using the methanol test to try to fix the regularly ensuing disaster. A different version of that here in Japan is to put the stuff through a centrifuge, though the product still doesn't pass any quality test or standards test. What you describe is much the same as what I described, doing (whatever) tests during the processing, adjusting accordingly and conducting the whole thing as a single stage. From Joe's replies so far I can't tell if he (and Rod, and Kenji and many others) are doing it that way or not, but it seems not: Your question (and mine): Don't you have to heat up the whole batch again? (Time and energy) Joe's reply: This is all done right after draining the glycerin. I leave the heater on during this period. Do the rough QT right away before wash test. Rough QT? Anyway, how long is it settling before he drains the glyc? I run a QT towards the end of the reaction because I do not want to re-process. Indeed not. It takes me a few minutes and I like the certainty of knowing the BD is good before I pump it into my settling tank. If the test should fail when I'm making a batch for my car, I could use Joe's suggestion to help me better approximate the amount of methanol to add. If the process has been standardized, why bother? I think this is a misunderstanding. I didn't say what you say below, standardized; can't fail, and I didn't mean that standardising the process means there's no need for tests, whether in-process tests or 1-litre test batches or whatever. Anything can fail. I'm all in favour of any tests that are helpful at any stage. So I agree with all you say here. Indeed, whatever rough might mean, using the methanol test to fine-tune the amount of extra methanol needed for reprocessing is a useful technique. But I'm not in favour of using reprocessing as a standard method, which, pending a better explanation, seems to be what's being proposed here. As you say: there shouldn't be any batches failing the QT. I've had a few failed batches in the past year. It seems to happen when I think I have it all figured out; standardized; can't fail. On one occasion the pump was making a bit of a funny noise when I
Re: [Biofuel] Glycerine Settling Time
Andres, Emulsifiers contains a clear lipofilic and hidrofilic zones in the molecule. In mono- and di- glycerides the glycerin supplies the hydrophilic zone and the fatty acid chain(s) supply the hydrophobic (lipophilic) zones. The -OH groups in the glycerin give it regions of charge making it hydrophilic. In an aquous solution wouldn't these groups rotate towards the water exposing hydrocarbons (hydrophobic) to the BD? I just tried forming an emulsion with veg oil and tap water. The oil rose to the top. I added glycerine that was split from the glycerine cocktail using Phosphoric Acid. It has no soaps, FFA's, methanol or KOH. I shook the bottle and the oil and water did not separate . an emulsion? I then added some vinegar. The emulsion broke. Glycerine seems to be an emulsifier. Am I missing something? Tom Maybe it's worth trying it again and seeing how long it stays emulsified. Best Keith - Original Message - From: mailto:[EMAIL PROTECTED]Andres Secco To: mailto:biofuel@sustainablelists.orgbiofuel@sustainablelists.org Sent: Thursday, August 09, 2007 1:55 PM Subject: Re: [Biofuel] Glycerine Settling Time Joe, For the sake of precise concepts, gliceryn is NOT an emulsifier. Emulsifiers contains a clear lipofilic and hidrofilic zones in the molecule. Which is an emulsifier is the partially reacted mono or di-glicerides, but in a crystal clear liquid there are not emulsions or dispersions. Glycerin is dissolved in the BD and separates from the liquid BD phase with time. - Original Message - From: mailto:[EMAIL PROTECTED]Joe Street To: mailto:biofuel@sustainablelists.orgbiofuel@sustainablelists.org Sent: Thursday, August 09, 2007 11:30 AM Subject: Re: [Biofuel] Glycerine Settling Time Tom; It makes sense. Glycerin is an emulsifier. Have you ever tried dosing the batch again with a little methoxide? After you remove the glycerin it doesn't take much to get the last bit of the reaction to go and settle out the remaining glycerin. Of course this is well known already. Kenji and many others do straight base catalysis as a two stage deal. You can do a methanol test of sorts and the unreacted oil will settle out. Then you can use the measured amount of unreacted oil in the methanol test vial to estimate the percentage unreacted oil in your batch and dose accordingly with the stoichiometric amount of methoxide. Assume neutral oil for this calculation. Rod and I do this regularly if the batch fails the QT and it works like a charm. Will save you settling time in the long run. Big skies Joe Thomas Kelly wrote: Joe, I took a sample from my latest batch of BD destined for my boiler (failed QT; but very little residue dropped out). It had settled for almost 10 hrs. That was yesterday morning. Today there is a small, but noticable, bit of glycerine on the bottom. More settled out after the initial 10 hrs of settling. I don't have any results with good BD to compare it with. If it turns out that glycerine settles out slower from incomplete vs complete reactions, it would answer the question I asked about getting emulsions when I washed low quality BD after letting it settle overnight, but not getting emulsions when it settled for a few days to a week. It would also help with a friendly disagreement I have with a friend. He seems to think that unreacted glycerides will settle out of the BD given time. He has taken to going with about 16% (vol/vol) of methanol in his batches. His logic: Unreacted oil causes emulsions, right? The emulsions I get in the first wash after settling the BD overnight are due to the unreacted oil? When I let it settle for a week or more I don't get emulsions, therefore the unreacted oil must have settled out. More likely: Some unreacted glycerides are still there, but after a week of settling more of the glycerine has settled out. Even a small amount of glycerine compound the emulsifying effects of the unreacted glycerides . Yes? By the way, I always ask him Did you do a quality test? His answer: Oops, I forgot. Thanks Joe and Rod . for bringing this to my attention A push to make a lot of BD for heat is just around the corner. It might be best to include more settling time in the schedule. Tom - Original Message - From: mailto:[EMAIL PROTECTED]Joe Street To: mailto:biofuel@sustainablelists.orgbiofuel@sustainablelists.org Sent: Tuesday, August 07, 2007 3:02 PM Subject: Re: [Biofuel] Biofuel Quality Test Hey Tom; Take a sample from your fuel after settling 6-8 hrs and set it asside in a mason jar for the longer period and see what settles out. Rod believes that glycerin settles slower in a poorly completed reaction. I believe he is right. And yes it only takes a little glycerin to emulsify your wash.
Re: [Biofuel] Glycerine Settling Time
Hi Keith; Most often the process comes to 95% or more complete and that is good enough for me ( personal choice) and doesn't give me wash problems either. Maybe 20% of the time it only gets to somewhere around 90% and this is a problem. It tends to be most likely to happen when the feedstock titrates with a result of higher than 5 (this is titrating with KOH soln rather than NaOH) which is what I consider borderline for going acid-base. Settling time is not less than 12 hours for me. Sorry about snipping the remainder of your post, was trying to save bandwidth. Off for the weekend now will check messages on Monday. Hope you are having a good weekend. And also to those about to start the weekend. Tirah Joe Keith Addison wrote: Hi Joe Hi Keith; See my answers below. Keith Addison wrote: Well, settling time is free. Acid-base aside, there's the two-stage base-base process, which quite a lot of people use and like, but otherwise why do more than one stage? Do you mean two separate stages, with a methanol test in between? So you process it twice? Plus extra methanol. No,- more like aiming for a single stage and then using the methanol test right after the settling period (after draining the glycerol of course) it gives you a chance to hit the reactor with another small dose of methoxide if it wasn't quite a complete reaction. The test also tells you how much to use. There is no standardising the process here since the feed is never the same twice. I don't think anybody's feedstock is ever the same twice, unless they're getting it from a food factory with a standardised operation. No restaurant cooks exactly the same food in the same way two days running. Anyway, why should that mean changing anything but the amount of catalyst needed? That's what titration is for, no? Certainly you can standardise the other variables. Rod decided to try a methanol test before washing, just for giggles and it turned out to be a heluva good idea. You know right away if you got a good reaction without having to waste all the time energy and water washing and drying before doing a quality test and then potenially having to reprocess. Before you started using this extra stage, how often did you have to reprocess? In your previous message it sounded like it happened regularly, and it still sounds that way. It turns out this looks just like a two step base -base type deal. but more like 90% of it in one step and then a polishing step. Sometimes if your process was good you don't need to do it, but if it turns out you were not near enough to completion it's nice to know right away. There's still methanol in the esters at that point (before washing) so it's advantageous to push the process further at that point if it is necessary. Joe This seems to raise more questions than provide answers. There were also some other points in my reply to Tom, eg, how long do you let the glycerin settle before draining it and embarking on the second stage/polishing step or whatever? I'll put the rest of my message back, below. Please see my reply to Tom: http://tinyurl.com/3ccqhw [Biofuel] Glycerine Settling Time Best Keith Hi Joe Tom; It makes sense. Glycerin is an emulsifier. Have you ever tried dosing the batch again with a little methoxide? After you remove the glycerin it doesn't take much to get the last bit of the reaction to go and settle out the remaining glycerin. Of course this is well known already. Kenji and many others do straight base catalysis as a two stage deal. You can do a methanol test of sorts and the unreacted oil will settle out. Then you can use the measured amount of unreacted oil in the methanol test vial to estimate the percentage unreacted oil in your batch and dose accordingly with the stoichiometric amount of methoxide. Assume neutral oil for this calculation. Rod and I do this regularly if the batch fails the QT and it works like a charm. Will save you settling time in the long run. Well, settling time is free. Acid-base aside, there's the two-stage base-base process, which quite a lot of people use and like, but otherwise why do more than one stage? Do you mean two separate stages, with a methanol test in between? So you process it twice? Plus extra methanol. Why not do it in a single phase? Todd Swearingen once suggested this here (discussing mixing pump sizes): To judge an appropriate reaction time, pull an exact amount of fluid (200 ml would suffice) out of the reaction stream every half-hour or hour after an arbitrary initial ~1 hour reaction period. Presuming that the contents of the reactor are kept homogenous from the pump flow, the volume of the glycerol cocktail that settles out of each sample will give you a fair gauge as to when your reaction completed. The suggestion would be to continue the reaction for ~1/2 hour beyond the point where your glyc cocktail
Re: [Biofuel] Glycerine Settling Time
Hi Keith; See my answers below. Keith Addison wrote: Well, settling time is free. Acid-base aside, there's the two-stage base-base process, which quite a lot of people use and like, but otherwise why do more than one stage? Do you mean two separate stages, with a methanol test in between? So you process it twice? Plus extra methanol. No,- more like aiming for a single stage and then using the methanol test right after the settling period (after draining the glycerol of course) it gives you a chance to hit the reactor with another small dose of methoxide if it wasn't quite a complete reaction. The test also tells you how much to use. There is no standardising the process here since the feed is never the same twice. Rod decided to try a methanol test before washing, just for giggles and it turned out to be a heluva good idea. You know right away if you got a good reaction without having to waste all the time energy and water washing and drying before doing a quality test and then potenially having to reprocess. It turns out this looks just like a two step base -base type deal. but more like 90% of it in one step and then a polishing step. Sometimes if your process was good you don't need to do it, but if it turns out you were not near enough to completion it's nice to know right away. There's still methanol in the esters at that point (before washing) so it's advantageous to push the process further at that point if it is necessary. Joe ___ Biofuel mailing list Biofuel@sustainablelists.org http://sustainablelists.org/mailman/listinfo/biofuel_sustainablelists.org Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html Search the combined Biofuel and Biofuels-biz list archives (50,000 messages): http://www.mail-archive.com/biofuel@sustainablelists.org/
Re: [Biofuel] Glycerine Settling Time
Hi all, I just saw the tom experiment results. Think the small quantity of glycerol increased the viscosity and that helps to stabilize the suspension. But I don think this is stable for a long time or if it were an stable emulsion. More likely a suspension wichis like an emulsion but not stable for long time. I did it with water and oil and some happened but nothing to say I have an emulsion here. After a few hours got separated. I agree with Jan that a poorly completed reaction releases mono and di-glicerydes wich have a strong emulsifier capacity and can trap any polar substances in the BD phase, not only glycerine but also proteins and methanol. When I saw the firs time the BD production with a friend in israel he added salt to break any emulsion trace. He left the batch for several days. Now I left for two complete days and all passes the QT test. - Original Message - From: Joe Street To: biofuel@sustainablelists.org Sent: Friday, August 10, 2007 9:45 AM Subject: Re: [Biofuel] Glycerine Settling Time Hi Jan; Ok your post agrees with what Andres said. So how do we explain Tom's experiment then? To recap (Tom correct me if I miss something here) he took washed esters that passed the methanol test and added water and (of course) no emulsion when agitated. Whatever mono and diglycerides were in the esters were small but present I assume, but yet no emusion. Then added some small quantity of glycerol ( which had been separated from the soaps, FFA and salts) and agitated again and did get an emulsion. I have had the feeling glycerin has usually been the cause of emulsion problems when I have had them. No doubt a poorly reacted batch is much more likely to have the problem but is that really due to the glycerides or is it glycerin which hasn't settled. Remember we started this discussion that the glycerin settles much slower in a poorly completed run. BTW as an addition to this discussion look what someone just posted on my yahoo group! Using glycerin cocktail to BREAK an emulsion. Now that's radical!!?? http://www.biodieselcommunity.org/breakingemulsions/ Joe Jan Warnqvist wrote: Hi evereybody. I feel obliged to enter this discussion. Pure glycerine is not a good emulsifier due to the fact that there are three OH-groups and that the carbon s in the first and third positions are surronded by two hydrogene atoms. This makes the glycerine hydrophilic in five places alltogether. However, the mono- and diglycerides are excellent emulsifiers. Only small amounts of these are sufficient to create stable emulsions. Would somebody agree with me on that ? Jan Warnqvist - Original Message - From: Keith Addison [EMAIL PROTECTED] To: biofuel@sustainablelists.org Sent: Friday, August 10, 2007 9:53 AM Subject: Re: [Biofuel] Glycerine Settling Time Hi Tom Hi Keith, Then if you do one-litre test batches first, especially with iffy batches of oil, Ops. I took Joe's point to be: If you have to re-process it is possible to use info from the QT to determine how much (how little) methanol you'll need to use. I also took that point, there were others though. It's a useful method, cheaper reprocessing, but I think we all agree that reprocessing itself is to be avoided if at all possible. Or I thought we did anyway. I think that both Joe and myself have standardize(d) the process so that passing the QT is the rule, not the exception. That's not what Joe said: It makes sense. Glycerin is an emulsifier. Have you ever tried dosing the batch again with a little methoxide? After you remove the glycerin it doesn't take much to get the last bit of the reaction to go and settle out the remaining glycerin. Of course this is well known already. Kenji and many others do straight base catalysis as a two stage deal. You can do a methanol test of sorts and the unreacted oil will settle out. Then you can use the measured amount of unreacted oil in the methanol test vial to estimate the percentage unreacted oil in your batch and dose accordingly with the stoichiometric amount of methoxide. Assume neutral oil for this calculation. Rod and I do this regularly if the batch fails the QT and it works like a charm. Will save you settling time in the long run. Rod and I do this regularly if the batch fails the QT and it works like a charm. That if makes it a little ambiguous, but the regularly bit puts a question-mark on what's the rule and what's the exception. Kenji and many others do straight base catalysis as a two stage deal. Less methanol notwithstanding, my question remains - why reprocess, as a standard procedure, instead of avoiding the problem in the first place? Could be wrong, but it sounds like Kenji and others might be doing this rather than doing a titration - you know the old line: There's no need for titration, just use 6.25 g. And then using the methanol test to try to
Re: [Biofuel] Glycerine Settling Time
Hello Joe. There were probably small amounts of mono- and diglycerides left in the biodiesel, and/or possibly soaps which together are excellent emulsifiers. A strong acid will divide the glycerides into fatty acids and glycerine ,and the soaps into salts and fatty acids, which then goes into a fat phanse and an aquaeus phase, possibly with the salts in the bottom.' Best regards Jan - Original Message - From: Joe Street To: biofuel@sustainablelists.org Sent: Friday, August 10, 2007 3:45 PM Subject: Re: [Biofuel] Glycerine Settling Time Hi Jan; Ok your post agrees with what Andres said. So how do we explain Tom's experiment then? To recap (Tom correct me if I miss something here) he took washed esters that passed the methanol test and added water and (of course) no emulsion when agitated. Whatever mono and diglycerides were in the esters were small but present I assume, but yet no emusion. Then added some small quantity of glycerol ( which had been separated from the soaps, FFA and salts) and agitated again and did get an emulsion. I have had the feeling glycerin has usually been the cause of emulsion problems when I have had them. No doubt a poorly reacted batch is much more likely to have the problem but is that really due to the glycerides or is it glycerin which hasn't settled. Remember we started this discussion that the glycerin settles much slower in a poorly completed run. BTW as an addition to this discussion look what someone just posted on my yahoo group! Using glycerin cocktail to BREAK an emulsion. Now that's radical!!?? http://www.biodieselcommunity.org/breakingemulsions/ Joe Jan Warnqvist wrote: Hi evereybody. I feel obliged to enter this discussion. Pure glycerine is not a good emulsifier due to the fact that there are three OH-groups and that the carbon s in the first and third positions are surronded by two hydrogene atoms. This makes the glycerine hydrophilic in five places alltogether. However, the mono- and diglycerides are excellent emulsifiers. Only small amounts of these are sufficient to create stable emulsions. Would somebody agree with me on that ? Jan Warnqvist - Original Message - From: Keith Addison [EMAIL PROTECTED] To: biofuel@sustainablelists.org Sent: Friday, August 10, 2007 9:53 AM Subject: Re: [Biofuel] Glycerine Settling Time Hi Tom Hi Keith, Then if you do one-litre test batches first, especially with iffy batches of oil, Ops. I took Joe's point to be: If you have to re-process it is possible to use info from the QT to determine how much (how little) methanol you'll need to use. I also took that point, there were others though. It's a useful method, cheaper reprocessing, but I think we all agree that reprocessing itself is to be avoided if at all possible. Or I thought we did anyway. I think that both Joe and myself have standardize(d) the process so that passing the QT is the rule, not the exception. That's not what Joe said: It makes sense. Glycerin is an emulsifier. Have you ever tried dosing the batch again with a little methoxide? After you remove the glycerin it doesn't take much to get the last bit of the reaction to go and settle out the remaining glycerin. Of course this is well known already. Kenji and many others do straight base catalysis as a two stage deal. You can do a methanol test of sorts and the unreacted oil will settle out. Then you can use the measured amount of unreacted oil in the methanol test vial to estimate the percentage unreacted oil in your batch and dose accordingly with the stoichiometric amount of methoxide. Assume neutral oil for this calculation. Rod and I do this regularly if the batch fails the QT and it works like a charm. Will save you settling time in the long run. Rod and I do this regularly if the batch fails the QT and it works like a charm. That if makes it a little ambiguous, but the regularly bit puts a question-mark on what's the rule and what's the exception. Kenji and many others do straight base catalysis as a two stage deal. Less methanol notwithstanding, my question remains - why reprocess, as a standard procedure, instead of avoiding the problem in the first place? Could be wrong, but it sounds like Kenji and others might be doing this rather than doing a titration - you know the old line: There's no need for titration, just use 6.25 g. And then using the methanol test to try to fix the regularly ensuing disaster. A different version of that here in Japan is to put the stuff through a centrifuge, though the product still doesn't pass any quality test or standards test. What you describe is much the same as what I described, doing (whatever) tests during the processing, adjusting accordingly and conducting the whole thing as a single stage. From Joe's replies so far I can't tell if he (and Rod, and Kenji and many others) are doing it that way or not, but
Re: [Biofuel] Glycerine Settling Time
Hi Jan; Ok your post agrees with what Andres said. So how do we explain Tom's experiment then? To recap (Tom correct me if I miss something here) he took washed esters that passed the methanol test and added water and (of course) no emulsion when agitated. Whatever mono and diglycerides were in the esters were small but present I assume, but yet no emusion. Then added some small quantity of glycerol ( which had been separated from the soaps, FFA and salts) and agitated again and did get an emulsion. I have had the feeling glycerin has usually been the cause of emulsion problems when I have had them. No doubt a poorly reacted batch is much more likely to have the problem but is that really due to the glycerides or is it glycerin which hasn't settled. Remember we started this discussion that the glycerin settles much slower in a poorly completed run. BTW as an addition to this discussion look what someone just posted on my yahoo group! Using glycerin cocktail to BREAK an emulsion. Now that's radical!!?? http://www.biodieselcommunity.org/breakingemulsions/ Joe Jan Warnqvist wrote: Hi evereybody. I feel obliged to enter this discussion. Pure glycerine is not a good emulsifier due to the fact that there are three OH-groups and that the carbon s in the first and third positions are surronded by two hydrogene atoms. This makes the glycerine hydrophilic in five places alltogether. However, the mono- and diglycerides are excellent emulsifiers. Only small amounts of these are sufficient to create stable emulsions. Would somebody agree with me on that ? Jan Warnqvist - Original Message - From: Keith Addison [EMAIL PROTECTED] To: biofuel@sustainablelists.org Sent: Friday, August 10, 2007 9:53 AM Subject: Re: [Biofuel] Glycerine Settling Time Hi Tom Hi Keith, Then if you do one-litre test batches first, especially with iffy batches of oil, Ops. I took Joe's point to be: If you have to re-process it is possible to use info from the QT to determine how much (how little) methanol you'll need to use. I also took that point, there were others though. It's a useful method, cheaper reprocessing, but I think we all agree that reprocessing itself is to be avoided if at all possible. Or I thought we did anyway. I think that both Joe and myself have standardize(d) the process so that passing the QT is the rule, not the exception. That's not what Joe said: It makes sense. Glycerin is an emulsifier. Have you ever tried dosing the batch again with a little methoxide? After you remove the glycerin it doesn't take much to get the last bit of the reaction to go and settle out the remaining glycerin. Of course this is well known already. Kenji and many others do straight base catalysis as a two stage deal. You can do a methanol test of sorts and the unreacted oil will settle out. Then you can use the measured amount of unreacted oil in the methanol test vial to estimate the percentage unreacted oil in your batch and dose accordingly with the stoichiometric amount of methoxide. Assume neutral oil for this calculation. Rod and I do this regularly if the batch fails the QT and it works like a charm. Will save you settling time in the long run. Rod and I do this regularly if the batch fails the QT and it works like a charm. That if makes it a little ambiguous, but the regularly bit puts a question-mark on what's the rule and what's the exception. Kenji and many others do straight base catalysis as a two stage deal. Less methanol notwithstanding, my question remains - why reprocess, as a standard procedure, instead of avoiding the problem in the first place? Could be wrong, but it sounds like Kenji and others might be doing this rather than doing a titration - you know the old line: There's no need for titration, just use 6.25 g. And then using the methanol test to try to fix the regularly ensuing disaster. A different version of that here in Japan is to put the stuff through a centrifuge, though the product still doesn't pass any quality test or standards test. What you describe is much the same as what I described, doing (whatever) tests during the processing, adjusting accordingly and conducting the whole thing as a single stage. From Joe's replies so far I can't tell if he (and Rod, and Kenji and many others) are doing it that way or not, but it seems not: Your question (and mine): Don't you have to heat up the whole batch again? (Time and energy) Joe's reply: This is all done right after draining the glycerin. I leave the heater on during this period. Do the rough QT right away before wash test. Rough QT? Anyway, how long is it settling before he drains the glyc? I run a QT towards the end of the reaction because I do not want to re-process. Indeed not. It takes me a few minutes and I like the certainty of knowing the BD is good before I pump it into my
Re: [Biofuel] Off Topic- Is Harmon
Hello Chip Seaver out there somewhere? He was once a list member but that was a few years back. I'll email you offlist. Best Keith Drop us a line, mate, if you are. Thanks Sorry for the interruption, Back to our regular programming. (btw, sorry I haven't posted in a while, but I just haven't had much to say that I could get in in less than a few thousand words, and who wants to read that?) ___ Biofuel mailing list Biofuel@sustainablelists.org http://sustainablelists.org/mailman/listinfo/biofuel_sustainablelists.org Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html Search the combined Biofuel and Biofuels-biz list archives (50,000 messages): http://www.mail-archive.com/biofuel@sustainablelists.org/
[Biofuel] I'm ready to settle this once and for all
Thanks for the write up - has anyone mixed all this discussion up and settled out the most salient points? Joe Street wrote: Thanks a lot Tom for all that work in a short time. You have really shed some light on this discussion. Jumping to your questions at the end, it seems clear then that Jan and Andres were right on and it must be the soap and mono-diglycerides etc rather than the glycerine itself which is the culprit.. It also seems to confirm or at least not in conflict with the theory that glycerin settles more slowly from incomplete reactions. I have never done anything with straight glycerol just the cocktail but it does contain soap al lots of other things. Small amounts of it have a large impact and it appears that incomplete reactions result in a significant amount of it remaining in the fuel after a prolonged period. I normally allow about 12 hours for settling (at least) and when the reaction is good an agressive pump wash is no problem. One of the aims of my project was to reduce cycle time so I really don't want to wait 24 or more hours because sometimes time is not free as Keith had put it. Was going to add more but time's up and the door to my cage is OPEN! Have a good weekend Joe Thomas Kelly wrote: Andres, Jan, Joe, Keith, and anyone else who has been following the saga, It would seem that glycerine, itself, is not an effective emulsifier. I've spent the morning experimenting in the kitchen. I did Wash Tests on BD that passed the QT and BD that failed the QT. I tested one group with glycerine split from the cocktail (using Phosphoric Acid) and another group with unsplit Glycerin cocktail. Volumes used: Biodiesel 150 ml Water 150 ml Glycerin (split and unsplit) 4 ml Temp: 70F (~22C) I. Glycerin split from the cocktail (used Phosphoric Acid): Controls: Time for clear separation (min) good quality BD + water 1 - 2 poor quality BD + water 3 - 4 Experimental: good quality BD + water + glycerine (split) less than 5 poor quality BD + water + glycerine (split) less than 5 II Glycerin Cocktail: good quality BD + water + glycerine cocktail2 hours* poor quality BD + water + glycerine cocktail2 hours* * At 2 hours there is a thin layer of BD (1 - 2 mm) The rest appears to be an emulsion. Andres and Jan, you are correct. Glycerin, itself, did little to retard separation of BD and water. Something in the cocktail does seem to be an emulsifier. (The soaps??) Some questions remain: 1. The BD that failed the QT (incomplete reaction) was obtained from a tank that feeds my heating system. It contains unreacted glycerides, but does not produce an emulsion when shaken in water, nor did it produce emulsions when it was stir-washed. Why not? 2. At Joe Street's suggestion I took a sample of BD that had settled for about 10 hours. Twelve hours later, more glycerin had settled out. Today, still another 24 hours later, even more has settled out. Could this small amount of unsplit glycerine (with associated soaps) be the cause of the emulsions I got when I started making BD? It would explain why settling for a day or more seems to eliminate the problem. 3. Does the glycerine mix (or soaps) settle out more slowly in BD from incomplete reactions? Tom ___ Biofuel mailing list Biofuel@sustainablelists.org http://sustainablelists.org/mailman/listinfo/biofuel_sustainablelists.org Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html Search the combined Biofuel and Biofuels-biz list archives (50,000 messages): http://www.mail-archive.com/biofuel@sustainablelists.org/ ___ Biofuel mailing list Biofuel@sustainablelists.org http://sustainablelists.org/mailman/listinfo/biofuel_sustainablelists.org Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html Search the combined Biofuel and Biofuels-biz list archives (50,000 messages): http://www.mail-archive.com/biofuel@sustainablelists.org/ ___ Biofuel mailing list Biofuel@sustainablelists.org http://sustainablelists.org/mailman/listinfo/biofuel_sustainablelists.org Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html Search the combined Biofuel and Biofuels-biz list archives (50,000 messages): http://www.mail-archive.com/biofuel@sustainablelists.org/
Re: [Biofuel] Glycerin as an Emulsifier (was Glycerine Settling Time)
Thanks a lot Tom for all that work in a short time. You have really shed some light on this discussion. Jumping to your questions at the end, it seems clear then that Jan and Andres were right on and it must be the soap and mono-diglycerides etc rather than the glycerine itself which is the culprit.. It also seems to confirm or at least not in conflict with the theory that glycerin settles more slowly from incomplete reactions. I have never done anything with straight glycerol just the cocktail but it does contain soap al lots of other things. Small amounts of it have a large impact and it appears that incomplete reactions result in a significant amount of it remaining in the fuel after a prolonged period. I normally allow about 12 hours for settling (at least) and when the reaction is good an agressive pump wash is no problem. One of the aims of my project was to reduce cycle time so I really don't want to wait 24 or more hours because sometimes time is not free as Keith had put it. Was going to add more but time's up and the door to my cage is OPEN! Have a good weekend Joe Thomas Kelly wrote: Andres, Jan, Joe, Keith, and anyone else who has been following the saga, It would seem that glycerine, itself, is not an effective emulsifier. I've spent the morning experimenting in the kitchen. I did Wash Tests on BD that passed the QT and BD that failed the QT. I tested one group with glycerine split from the cocktail (using Phosphoric Acid) and another group with unsplit Glycerin cocktail. Volumes used: Biodiesel 150 ml Water 150 ml Glycerin (split and unsplit) 4 ml Temp: 70F (~22C) I. Glycerin split from the cocktail (used Phosphoric Acid): Controls: Time for clear separation (min) good quality BD + water 1 - 2 poor quality BD + water 3 - 4 Experimental: good quality BD + water + glycerine (split) less than 5 poor quality BD + water + glycerine (split) less than 5 II Glycerin Cocktail: good quality BD + water + glycerine cocktail2 hours* poor quality BD + water + glycerine cocktail2 hours* * At 2 hours there is a thin layer of BD (1 - 2 mm) The rest appears to be an emulsion. Andres and Jan, you are correct. Glycerin, itself, did little to retard separation of BD and water. Something in the cocktail does seem to be an emulsifier. (The soaps??) Some questions remain: 1. The BD that failed the QT (incomplete reaction) was obtained from a tank that feeds my heating system. It contains unreacted glycerides, but does not produce an emulsion when shaken in water, nor did it produce emulsions when it was stir-washed. Why not? 2. At Joe Street's suggestion I took a sample of BD that had settled for about 10 hours. Twelve hours later, more glycerin had settled out. Today, still another 24 hours later, even more has settled out. Could this small amount of unsplit glycerine (with associated soaps) be the cause of the emulsions I got when I started making BD? It would explain why settling for a day or more seems to eliminate the problem. 3. Does the glycerine mix (or soaps) settle out more slowly in BD from incomplete reactions? Tom ___ Biofuel mailing list Biofuel@sustainablelists.org http://sustainablelists.org/mailman/listinfo/biofuel_sustainablelists.org Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html Search the combined Biofuel and Biofuels-biz list archives (50,000 messages): http://www.mail-archive.com/biofuel@sustainablelists.org/ ___ Biofuel mailing list Biofuel@sustainablelists.org http://sustainablelists.org/mailman/listinfo/biofuel_sustainablelists.org Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html Search the combined Biofuel and Biofuels-biz list archives (50,000 messages): http://www.mail-archive.com/biofuel@sustainablelists.org/
[Biofuel] International Biodiesel Day
On this day in 1893 Rudolf Diesel’s engine ran for the first time, and it ran on peanut oil. So today we celebrate “International Biodiesel Day” and raise our glasses to the genius of using fuel that grows back! Praise the Lard! http://en.wikipedia.org/wiki/Biodiesel#Historical_background ___ Biofuel mailing list Biofuel@sustainablelists.org http://sustainablelists.org/mailman/listinfo/biofuel_sustainablelists.org Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html Search the combined Biofuel and Biofuels-biz list archives (50,000 messages): http://www.mail-archive.com/biofuel@sustainablelists.org/
Re: [Biofuel] International Biodiesel Day
___ Biofuel mailing list Biofuel@sustainablelists.org http://sustainablelists.org/mailman/listinfo/biofuel_sustainablelists.org Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html Search the combined Biofuel and Biofuels-biz list archives (50,000 messages): http://www.mail-archive.com/biofuel@sustainablelists.org/
Re: [Biofuel] International Biodiesel Day
Hello Mike On this day in 1893 Rudolf Dieselís engine ran for the first time, and it ran on peanut oil. So today we celebrate ìInternational Biodiesel Dayî and raise our glasses to the genius of using fuel that grows back! Praise the Lard! http://en.wikipedia.org/wiki/Biodiesel#Historical_background :-) And tally the tallow - sorry, but it's a myth. Rudolf Diesel patents the diesel engine in 1893. Diesel is awarded the Grand Prix at both Paris World Fairs (1900 and 1910) for inventing and developing his engine. But he didn't run it on peanut oil. The true story: ... excerpts from some of Dr Diesel's work, that he published 1912 and 1913, where he states that it was the Otto Company that ran one of his engines on peanut oil at the request of the French government during the 1900 World Fair. He later conducted some trails where he determined fuel consumption and assessed operability. He also mentions similar successful experiments in St. Petersburg using castor oil and animal oils. - Darren Hill It WASN'T him! I recently borrowed his book The Development of the Diesel Engine -afaik the last one he published until he drowned himself in the Channel. All kinds of fuels that had been tested are described there, from coal dust over weird chemical mixtures that had been sent to Diesel by the industry to all sorts of crude oil and even tar-oil. Vegoil just got about 4 lines- remarking that it was the French Otto-Company (yes the Otto-engine!) that ran Diesel's engine on peanut oil: The engine was built for crude oil and was used without any modification on vegoilit worked so well that only a few insiders took notice of this insignificant circumstance. (Diesel, Rudolf. 1913. Die Entstehung des Dieselmotors 1st reprint by Braun, Hans-Joachim (Ed). 1984. Moers: Steiger. Page 115.). - Stephan Helbig It'll be a long time before wikipedia gets to be much more than knowledge-lite, IMHO. Worldwide production of vegetable oil and animal fat is not yet sufficient to replace liquid fossil fuel use. Yet? LOL! So all we have to do is wait a bit, what a relief. 5,000 gal/acre from algae, sigh... Best Keith ___ Biofuel mailing list Biofuel@sustainablelists.org http://sustainablelists.org/mailman/listinfo/biofuel_sustainablelists.org Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html Search the combined Biofuel and Biofuels-biz list archives (50,000 messages): http://www.mail-archive.com/biofuel@sustainablelists.org/
[Biofuel] The Anti-Empire Report
http://members.aol.com/bblum6/aer48.htm Anti-Empire Report, August 10, 2007 Read this or George W. Bush will be president the rest of your life August 10, 2007 by William Blum www.killinghope.org Separation of oil and state On several occasions I've been presented with the argument that contrary to widespread opinion in the anti-war movement and on the left, oil was not really a factor in the the United States invasion and occupation of Iraq. The argument's key, perhaps sole, point is that the oil companies did not push for the war. Responding to only this particular point: firstly, the executives of multinational corporations are not in the habit of making public statements concerning vital issues of American foreign policy, either for or against. And we don't know what the oil company executives said in private to high Washington officials, although we do know that such executives have a lot more access to such officials than you or I, like at Cheney's secret gatherings. More importantly, we have to distinguish between oil as a fuel and oil as a political weapon. A reading of the policy papers issued by the neo-conservatives since the demise of the Soviet Union makes it clear that these people will not tolerate any other country or group of countries challenging the global hegemony of the world's only superpower. A sample -- In 1992 they wrote: We must maintain the mechanisms for deterring potential competitors from even aspiring to a larger regional or global role.[1] And in 2002, in the White House National Security Strategy paper: Our forces will be strong enough to dissuade potential adversaries from pursuing a military build-up in hopes of surpassing, or equaling, the power of the United States. ... America will act against such emerging threats before they are fully formed. ... We must deter and defend against the threat before it is unleashed. ... We cannot let our enemies strike first. ... To forestall or prevent such hostile acts by our adversaries, the United States will, if necessary, act preemptively. As the world has been learning in great sorrow, the neo-conservative world-dominators are not just (policy) paper tigers. Japan and the European Union easily fall into the categories of potential competitors or potential adversaries, economically speaking. They both are crucially dependent upon oil imports. To one extent or another so is most of the world. The Bush administration doesn't need the approval of the oil companies to pursue its grandiose agenda of world domination, using the vast Iraqi oil reserves as one more of its weapons. For those who would like to believe that there's a limit to the neo-cons' imperial arrogance, that even the likes of Bush, Cheney, Rumsfeld, Bolton, Wolfowitz, Rice, and the rest of the gang would never treat Europe as anything like an enemy, I suggest a look at a recent article by the former US ambassador to the United Nations, John Bolton, which appeared in the Financial Times of London. In it, the Cheney intimate and current senior fellow at the neo-con citadel, American Enterprise Institute, berates British prime minister Gordon Brown for implying that the UK could have a special relationship with both the United States and the European Union (which Bolton refers to as the European porridge). Like a hurt lover, Bolton exclaims that Britain has been brought to a clear decision point. ... What London needs to know is that its answer will have consequences. The article is entitled: Britain Cannot Have Two Best Friends. Bolton goes on to ask: Why does a 'union' with a common foreign and security policy, and with the prospect of a real 'foreign minister' have two permanent seats on the UN Security Council and often as many as three non-permanent seats out of a total of 15 council members? France and Britain may not relish the prospect of giving up their unique status, but what is it that makes them different -- as members of the 'Union' -- from Luxembourg or Malta? One Union, one seat. Mr Brown cannot have it both ways (nor will President Nicolas Sarkozy). The Empire has not yet made Europe an ODE (Officially Designated Enemy) like Iran, but, Bolton declares, If Mr Bush decides that the only way to stop Iran is to use military force, where will Mr Brown come down? Supporting the US or allowing Iran to goose-step towards nuclear weapons?[2] Washington's exquisite imperial mentality, its stated determination to act against such emerging threats before they are fully formed, sees potential adversaries in China and Russia as well of course. The United States -- with hypocrisy breathtaking even for the Bush administration -- regularly castigates China for its expanding military budget; and tries to surround Russia with military bases, missile shields, and countries with ties to
