Re: [biofuel] acid catalyzed ... cont...
Thanks Todd, Ken, Jim, and - hey, just about everybody! You educate me, and I'm deeply grateful. Regards Keith Keith, From my perspective, recovery of MeOH is best done at two different stages. The first would be from the ester, after the glycerin has settled, while the fuel is still warm to save energy inputs. The second would be from the glycerin, after the catalyst has been precipitated out, as the alcohol makes the glycerin considerably less viscous which aids in quick and condensed precipitation of the salt. At that point, where the catalyst has precipated out in the form of a salt, the glycerin also separates from of the FFAs - three layers - precipitate, glycerin and FFAs. This can easily be done while still warm after settling out of the base transesterification stage. From here, the alcohol can be recovered from each layer independently, so as to not get the glycerin and the FFAs mixed again. Were alcohol to be recovered from both fluids at the same time (a homogenous mixture of glycerin and FFAs) it is doubtfult that the glycerin would settle out quite as readily or that as great a percentage of FFAs would again separate to the surface, due primarily to the greater viscosity of the now alcohol free environment, in comparison to the more fluid environment where alcohol was present. ... As for the benefits of knowing the saponification value of oils...this might shed a little light. Sap values found in print are generally the amount of KOH required to convert an oil entirely into soap, based upon weight of the oil, not volume. (The molecular wait of NaOH to KOH, respectively is 40.0 - 56.1, meaning that more weight of KOH is required to achieve the same effect as with NaOH - 56.1 grams of pure KOH = 40 grams of pure NaOH.) Biodieselers only want to know how much catalyst it will take to compensate for the FFAs, which are only a fraction of the oil's content. Transfering that kind of data into a transesterification correlation, it takes 192.80 grams of KOH (137.47 grams NaOH) to completely saponify 1# of hemp seed oil. That would equate to approximately 1,100 grams of NaOH per gallon of oil. However, in a straight base reaction, it only takes ~32 grams of NaOH to convert one gallon of hemp seed oil to methyl ester - enough catalyst to counter the oil's FFA content with 3.5 grams / liter of oil remaining for the transesterification. Knowing how soap is made is of value to a biodieseler in many respects. But sap values don't have a direct correlation to transesterification values. Todd Swearingen - Original Message - From: Keith Addison [EMAIL PROTECTED] To: biofuel@yahoogroups.com Sent: Monday, April 29, 2002 3:30 PM Subject: Re: [biofuel] acid catalyzed ... cont... Hello Todd, Jim, Ken and all Jim, Phosphoric would be used as a wash neutralizer and a precipitator when recovering the base from the glycerin. I tend to believe that Aleks is correct when he says that phosphoric won't work in the acid stage. My first guess on the matter is that the sulfuric in concentrated form of 95%-98% has less water than the 85% phosphoric which is most common. By introducing less water, there will inevitably be less soap creation, erego higher yields using one over the other. But the thought of precipitating out the caustic prior to composting is of great value, with the water soluble fertilizer being useable in a yard or field environment. Now, if someone would just design a rather cost effective, simple and Underwriters Laboratories safe, shadetree thin film evaporation/distillation unit to recover the methanol, homebrew will have closed the loop in the waste stream. Todd Swearingen Why not recover the methanol at the end of the processing stage, before settling? Still warm, it's all there, so just heat it up a bit more (to 65 deg C) and distill it off through a simple condenser. Isn't that what most people are doing who're recovering their methanol? And, um, sorry to nag, but any feedback on this below, posted earlier in this thread? 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. 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? Thanks! Keith Yahoo! Groups Sponsor -~-- Buy Stock for $4 and no minimums. FREE Money 2002. http://us.click.yahoo.com/k6cvND/n97DAA/ySSFAA/FGYolB/TM
[biofuel] acid catalyzed ... cont...
I was going to mention it, but the idea of using KOH for a base catalyst and phosphoric acid as the acid catalyst means that you have K3PO4 which is fertilizer and since it would be in aqueous form mixed with the glycerol/water layers, you could make compost with grass clippings, etc... who knows? Yahoo! Groups Sponsor -~-- Buy Stock for $4 and no minimums. FREE Money 2002. http://us.click.yahoo.com/orkH0C/n97DAA/ySSFAA/FGYolB/TM -~- Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html 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] acid catalyzed ... cont...
jmwelter writes: I was going to mention it, but the idea of using KOH for a base catalyst and phosphoric acid as the acid catalyst means that you have K3PO4 which is fertilizer and since it would be in aqueous form mixed with the glycerol/water layers, you could make compost with grass clippings, etc... who knows? That was the original motivation for phosphoric acid, and part of the reason for KOH, ever since Tickell mentioned it in the book. I think you have to look where your effluent is going, tho, before picking the best acid. For compost, phosphoric might be OK, or sulfuric (K2SO4 is also commonly put on plants). If you're dumping into the ocean, like here in the Bay Area, phosphates are probably the LEAST desirable. I'm leaning toward hydrochloric for ocean disposal, and even the potassium is probably no better than sodium. -K Yahoo! Groups Sponsor -~-- Buy Stock for $4 and no minimums. FREE Money 2002. http://us.click.yahoo.com/k6cvND/n97DAA/ySSFAA/FGYolB/TM -~- Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html 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] acid catalyzed ... cont...
Jim, Phosphoric would be used as a wash neutralizer and a precipitator when recovering the base from the glycerin. I tend to believe that Aleks is correct when he says that phosphoric won't work in the acid stage. My first guess on the matter is that the sulfuric in concentrated form of 95%-98% has less water than the 85% phosphoric which is most common. By introducing less water, there will inevitably be less soap creation, erego higher yields using one over the other. But the thought of precipitating out the caustic prior to composting is of great value, with the water soluble fertilizer being useable in a yard or field environment. Now, if someone would just design a rather cost effective, simple and Underwriters Laboratories safe, shadetree thin film evaporation/distillation unit to recover the methanol, homebrew will have closed the loop in the waste stream. Todd Swearingen - Original Message - From: jmwelter [EMAIL PROTECTED] To: biofuel@yahoogroups.com Sent: Monday, April 29, 2002 11:39 AM Subject: [biofuel] acid catalyzed ... cont... I was going to mention it, but the idea of using KOH for a base catalyst and phosphoric acid as the acid catalyst means that you have K3PO4 which is fertilizer and since it would be in aqueous form mixed with the glycerol/water layers, you could make compost with grass clippings, etc... who knows? Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html 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 the Yahoo! Terms of Service. Yahoo! Groups Sponsor -~-- Buy Stock for $4 and no minimums. FREE Money 2002. http://us.click.yahoo.com/orkH0C/n97DAA/ySSFAA/FGYolB/TM -~- Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html 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] acid catalyzed ... cont...
What about Nitric Acid ? Greg H. - Original Message - From: Ken Provost [EMAIL PROTECTED] To: biofuel@yahoogroups.com Sent: Monday, April 29, 2002 10:06 Subject: Re: [biofuel] acid catalyzed ... cont... jmwelter writes: I was going to mention it, but the idea of using KOH for a base catalyst and phosphoric acid as the acid catalyst means that you have K3PO4 which is fertilizer and since it would be in aqueous form mixed with the glycerol/water layers, you could make compost with grass clippings, etc... who knows? That was the original motivation for phosphoric acid, and part of the reason for KOH, ever since Tickell mentioned it in the book. I think you have to look where your effluent is going, tho, before picking the best acid. For compost, phosphoric might be OK, or sulfuric (K2SO4 is also commonly put on plants). If you're dumping into the ocean, like here in the Bay Area, phosphates are probably the LEAST desirable. I'm leaning toward hydrochloric for ocean disposal, and even the potassium is probably no better than sodium. -K Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html 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 -~-- Buy Stock for $4 and no minimums. FREE Money 2002. http://us.click.yahoo.com/k6cvND/n97DAA/ySSFAA/FGYolB/TM -~- Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html 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] acid catalyzed ... cont...
What about Nitric Acid ? Greg H. In a wordBOOM !!! Yahoo! Groups Sponsor -~-- Buy Stock for $4 and no minimums. FREE Money 2002. http://us.click.yahoo.com/k6cvND/n97DAA/ySSFAA/FGYolB/TM -~- Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html 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] acid catalyzed ... cont...
Hello Todd, Jim, Ken and all Jim, Phosphoric would be used as a wash neutralizer and a precipitator when recovering the base from the glycerin. I tend to believe that Aleks is correct when he says that phosphoric won't work in the acid stage. My first guess on the matter is that the sulfuric in concentrated form of 95%-98% has less water than the 85% phosphoric which is most common. By introducing less water, there will inevitably be less soap creation, erego higher yields using one over the other. But the thought of precipitating out the caustic prior to composting is of great value, with the water soluble fertilizer being useable in a yard or field environment. Now, if someone would just design a rather cost effective, simple and Underwriters Laboratories safe, shadetree thin film evaporation/distillation unit to recover the methanol, homebrew will have closed the loop in the waste stream. Todd Swearingen Why not recover the methanol at the end of the processing stage, before settling? Still warm, it's all there, so just heat it up a bit more (to 65 deg C) and distill it off through a simple condenser. Isn't that what most people are doing who're recovering their methanol? And, um, sorry to nag, but any feedback on this below, posted earlier in this thread? 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. 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? Thanks! Keith Yahoo! Groups Sponsor -~-- Buy Stock for $4 and no minimums. FREE Money 2002. http://us.click.yahoo.com/k6cvND/n97DAA/ySSFAA/FGYolB/TM -~- Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html 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] acid catalyzed ... cont...
Keith asks: Why not recover the methanol at the end of the processing stage, before settling? Still warm, it's all there, so just heat it up a bit more (to 65 deg C) and distill it off through a simple condenser. Isn't that what most people are doing who're recovering their methanol? Don't know about most people, but I've got 2 reasons not to do it that way. First, there's a lot more methanol in the glyc phase than in the biodiesel phase, and I'd rather hold 2.8 liters of glyc at 90 C (for 2 hours) than 28 liters of mix. Second, I don't want the recovery phase to hold up my production. I'd rather let the glyc accumulate and spend a weekend doing methanol recovery than have to incorporate it into every batch process. And, um, sorry to nag, but any feedback on this below, posted earlier in this thread? 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. 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? The difference is that NaOH is a REACTANT in soapmaking, but a CATALYST in biodiesel making. The amount has to be dead on for soap, or you end up with bad soap, but for biodiesel, it only has to be enough and not too much -- a lot more forgiving. Yahoo! Groups Sponsor -~-- Buy Stock for $4 and no minimums. FREE Money 2002. http://us.click.yahoo.com/k6cvND/n97DAA/ySSFAA/FGYolB/TM -~- Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html 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] acid catalyzed ... cont...
Greg Nitric Acid is a Big, spell that BIG no no. I can't speak to exact specifics, but I can spell NITRO-GLYCERIN Probably a pretty simple process, whether one knows they are accomplishing it or not. Under the wrong circumstances, deadly in an equally as simple manner. Might I suggest we put the various acids to question before a chemist, rather than hypothesizing and perhaps flattening everything within a 100 foot radius? Todd Swearingen - Original Message - From: Greg and April [EMAIL PROTECTED] To: biofuel@yahoogroups.com Sent: Monday, April 29, 2002 1:33 PM Subject: Re: [biofuel] acid catalyzed ... cont... What about Nitric Acid ? Greg H. - Original Message - From: Ken Provost [EMAIL PROTECTED] To: biofuel@yahoogroups.com Sent: Monday, April 29, 2002 10:06 Subject: Re: [biofuel] acid catalyzed ... cont... jmwelter writes: I was going to mention it, but the idea of using KOH for a base catalyst and phosphoric acid as the acid catalyst means that you have K3PO4 which is fertilizer and since it would be in aqueous form mixed with the glycerol/water layers, you could make compost with grass clippings, etc... who knows? That was the original motivation for phosphoric acid, and part of the reason for KOH, ever since Tickell mentioned it in the book. I think you have to look where your effluent is going, tho, before picking the best acid. For compost, phosphoric might be OK, or sulfuric (K2SO4 is also commonly put on plants). If you're dumping into the ocean, like here in the Bay Area, phosphates are probably the LEAST desirable. I'm leaning toward hydrochloric for ocean disposal, and even the potassium is probably no better than sodium. -K Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html 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 ADVERTISEMENT Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html 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 the Yahoo! Terms of Service. Yahoo! Groups Sponsor -~-- Buy Stock for $4 and no minimums. FREE Money 2002. http://us.click.yahoo.com/k6cvND/n97DAA/ySSFAA/FGYolB/TM -~- Biofuel at Journey to Forever: http://journeytoforever.org/biofuel.html 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] acid catalyzed ... cont...
Keith,
