Re: [Biofuel] Acid - Base questions
Hi Ken On Jan 8, 2006, at 2:15 AM, Jan Warnqvist wrote: I was referring to acid esterification of FFA:s / oil without passing through the soap step. These reactions are often incomplete, and moreover, quite slow. Not only that, but difficult to isolate your biodiesel from the react- ants. After the acid step? No need. My experience with straight esterification is that you always have two phases, but you can't ever tell what's in each phase. It starts out, of course, with alcohol in one and FFA in the other. After the reaction has gone as far it's going to (many hours of agit- ation at high temps), Well, if you like. Or perhaps not many hours at not very high temps. there's a combination of biodiesel, FFA, acid, and a little methanol in the oily phase, and the huge excess of meth- anol plus water and most of the acid in the aqueous phase. Hard to ever get pure biodiesel, or even know how far the reaction has gone, and you can't easily purify or wash the biodiesel without reversing the reaction to some extent. Huh? Easy washing, high-quality product, no reverse reaction. After completing the second-stage base transesterification step that is, I guess that's what you mean. I'm sure it's doable, once you work out all the variables and have a process down with good testing of your product. For me, the base- catalyzed reaction is much more practical. To each his own, of course. For me, single-stage base is primitive by comparison with acid-base, and I'm not at all alone in thinking that. Just had yet another newbie doing the Foolproof method, as-is, this one another school student doing it for his science fair. It works great, thanks! We tell them don't do it, start at the beginning, learn the whole thing so you can do troubleshooting, but a lot of people jump in anyway and most of them don't seem to have any problems. We get a lot of feedback on it, what I said about it the other day has a firm basis: You try the Foolproof method and sometimes people don't have any success with it and maybe come back later and try again, but most likely it works just fine, or you have to fiddle with it a bit and then it works just fine, or maybe you have to fiddle with it quite a lot, and then it works just fine. (I didn't have to fiddle with it, it worked just fine, but I fiddled with it anyway and now it works even finer.) Just as an aside, I know you didn't say that, but IMHO it's not a good approach to view the acid-base process as a normal single-stage base transesterification with an add-on in front. When the acid step is done and you start the base transesterification step you're not starting from the same place as you would be if you were doing a simple single-stage base reaction with lower-FFA oil. There are some very complicated ways to proceed, and some very easy ways too. Titrating it for instance might not tell you much, or might not tell you what you think it's telling you (though it might work anyway). Best approach it as a single integrated process with two steps. Sorry to be so vague, perforce, but it's a good hint. Aleks's Foolproof method is definitely the place to start with acid-base and maybe to stay with, which most people seem to do. Regards Keith -K ___ 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] Acid - Base questions
Hello Todd, yes, to my knowledge it is favourable producing methyl esters by turning the FFA:s into soaps as a first step. There will be amounts of water created with this method as well, but it seems to be of less importance. There is no need for scaring people off , but there is a need for explaining the mechanisms necessary for success. There will also always be a need for us that are trained to disperse our knowledge with the responsibility required. I was referring to acid esterification of FFA:s / oil without passing through the soap step. These reactions are often incomplete, and moreover, quite slow. With best regards Jan Jan Warnqvist AGERATEC AB [EMAIL PROTECTED] + 46 554 201 89 +46 70 499 38 45 - Original Message - From: Appal Energy [EMAIL PROTECTED] To: Biofuel@sustainablelists.org Sent: Sunday, January 08, 2006 4:29 AM Subject: Re: [Biofuel] Acid - Base questions Jan, Since when are esterifications often incomplete? And since when is a good conversion achieved necessarily through base catalysis? It's relatively simple to take 100% FFAs and achieve a 100% yield of esters. Industry does it daily from soap stock. Let people satisfy their own curiosities rather than scaring them off paths that many have already taken..., and succeeded at one might add. Todd Swearingen Jan Warnqvist wrote: Hello Jim, the sensible thing is to spending time and money producing BD from a cheap feedstock, not the other way around. Acid esterifications are often incomplete, and I assume that oils and fats with max 20% FFA are worth while bothering about, unless you are willing to do several acid esterification steps and draining off the produced water after each step.But in order to have a good conversion into BD, you finally have to run the alkaline transesterification step , also for neutralization. Good luck to you ! Jan Warnqvist AGERATEC AB [EMAIL PROTECTED] + 46 554 201 89 +46 70 499 38 45 - Original Message - From: JJJN [EMAIL PROTECTED] To: Biofuel@sustainablelists.org Sent: Saturday, January 07, 2006 3:26 AM Subject: Re: [Biofuel] Acid - Base questions Thanks Jan, If I had developed a method to separate FFA's from base stock without using chemicals or water say in the range of 95% separation in WVO (still a work in progress but hopeful results) so that I could React the Low FFA's in a Base method then would it be feasible to react the High FFA's In a separate Acid reaction? Or what problems would I encounter like the water problem you noted below? Would the FFA's be worth the trouble? Thanks Jim Jan Warnqvist wrote: Hello Jim, when using the acid esterification, you will have methyl esters, unreacted oil, sulphate ions, oxonium ions and - water. Proceeding to the base step you will create more methyl esters, potassium or sodium soaps, maybe a little unreacted oil or partially reacted oil, potassium or sodium sulphates and - even more water. This method works fine if the water content can be kept on a reasonable level. Please note that the higher the initial FFA level, the more water will be produced. With best regards Jan Jan Warnqvist AGERATEC AB [EMAIL PROTECTED] + 46 554 201 89 +46 70 499 38 45 - Original Message - From: JJJN [EMAIL PROTECTED] To: BIO Biofuel@sustainablelists.org Sent: Thursday, January 05, 2006 3:01 AM Subject: [Biofuel] Acid - Base questions I have decided to try the acid/base method in small test batches as I have some High FFA (4ml) oil I would like to process. Since September I have gone to great lengths to get repeatability and accuracy in all my work with Biodiesel. I have read and re-read JtF and I know that I will no doubt read it several more times if I get stumped. I would like to start with fully understanding the process first. Before I start: Can you use KOH with the Acid Base method? It might be obvious, but I did not see it in the recipe as a substitution. When the acid gets done with Estrification properly then the mix that is left is basically an oil (triglycerides) , Methanol, and Sulfur ions ? Or did I miss something? When the Methoxil is added the Sulfur gets combined with the Sodium ions, (right?) how does this affect the reaction? Any good experienced information would be helpful, Jim ___ 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
Re: [Biofuel] Acid - Base questions
On Jan 8, 2006, at 2:15 AM, Jan Warnqvist wrote: I was referring to acid esterification of FFA:s / oil without passing through the soap step. These reactions are often incomplete, and moreover, quite slow. Not only that, but difficult to isolate your biodiesel from the react- ants. My experience with straight esterification is that you always have two phases, but you can't ever tell what's in each phase. It starts out, of course, with alcohol in one and FFA in the other. After the reaction has gone as far it's going to (many hours of agit- ation at high temps), there's a combination of biodiesel, FFA, acid, and a little methanol in the oily phase, and the huge excess of meth- anol plus water and most of the acid in the aqueous phase. Hard to ever get pure biodiesel, or even know how far the reaction has gone, and you can't easily purify or wash the biodiesel without reversing the reaction to some extent. I'm sure it's doable, once you work out all the variables and have a process down with good testing of your product. For me, the base- catalyzed reaction is much more practical. -K ___ 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] Acid - Base questions
Hello Jim, the sensible thing is to spending time and money producing BD from a cheap feedstock, not the other way around. Acid esterifications are often incomplete, and I assume that oils and fats with max 20% FFA are worth while bothering about, unless you are willing to do several acid esterification steps and draining off the produced water after each step.But in order to have a good conversion into BD, you finally have to run the alkaline transesterification step , also for neutralization. Good luck to you ! Jan Warnqvist AGERATEC AB [EMAIL PROTECTED] + 46 554 201 89 +46 70 499 38 45 - Original Message - From: JJJN [EMAIL PROTECTED] To: Biofuel@sustainablelists.org Sent: Saturday, January 07, 2006 3:26 AM Subject: Re: [Biofuel] Acid - Base questions Thanks Jan, If I had developed a method to separate FFA's from base stock without using chemicals or water say in the range of 95% separation in WVO (still a work in progress but hopeful results) so that I could React the Low FFA's in a Base method then would it be feasible to react the High FFA's In a separate Acid reaction? Or what problems would I encounter like the water problem you noted below? Would the FFA's be worth the trouble? Thanks Jim Jan Warnqvist wrote: Hello Jim, when using the acid esterification, you will have methyl esters, unreacted oil, sulphate ions, oxonium ions and - water. Proceeding to the base step you will create more methyl esters, potassium or sodium soaps, maybe a little unreacted oil or partially reacted oil, potassium or sodium sulphates and - even more water. This method works fine if the water content can be kept on a reasonable level. Please note that the higher the initial FFA level, the more water will be produced. With best regards Jan Jan Warnqvist AGERATEC AB [EMAIL PROTECTED] + 46 554 201 89 +46 70 499 38 45 - Original Message - From: JJJN [EMAIL PROTECTED] To: BIO Biofuel@sustainablelists.org Sent: Thursday, January 05, 2006 3:01 AM Subject: [Biofuel] Acid - Base questions I have decided to try the acid/base method in small test batches as I have some High FFA (4ml) oil I would like to process. Since September I have gone to great lengths to get repeatability and accuracy in all my work with Biodiesel. I have read and re-read JtF and I know that I will no doubt read it several more times if I get stumped. I would like to start with fully understanding the process first. Before I start: Can you use KOH with the Acid Base method? It might be obvious, but I did not see it in the recipe as a substitution. When the acid gets done with Estrification properly then the mix that is left is basically an oil (triglycerides) , Methanol, and Sulfur ions ? Or did I miss something? When the Methoxil is added the Sulfur gets combined with the Sodium ions, (right?) how does this affect the reaction? Any good experienced information would be helpful, Jim ___ 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/ ___ 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] Acid - Base questions
Jan, Since when are esterifications often incomplete? And since when is a good conversion achieved necessarily through base catalysis? It's relatively simple to take 100% FFAs and achieve a 100% yield of esters. Industry does it daily from soap stock. Let people satisfy their own curiosities rather than scaring them off paths that many have already taken..., and succeeded at one might add. Todd Swearingen Jan Warnqvist wrote: Hello Jim, the sensible thing is to spending time and money producing BD from a cheap feedstock, not the other way around. Acid esterifications are often incomplete, and I assume that oils and fats with max 20% FFA are worth while bothering about, unless you are willing to do several acid esterification steps and draining off the produced water after each step.But in order to have a good conversion into BD, you finally have to run the alkaline transesterification step , also for neutralization. Good luck to you ! Jan Warnqvist AGERATEC AB [EMAIL PROTECTED] + 46 554 201 89 +46 70 499 38 45 - Original Message - From: JJJN [EMAIL PROTECTED] To: Biofuel@sustainablelists.org Sent: Saturday, January 07, 2006 3:26 AM Subject: Re: [Biofuel] Acid - Base questions Thanks Jan, If I had developed a method to separate FFA's from base stock without using chemicals or water say in the range of 95% separation in WVO (still a work in progress but hopeful results) so that I could React the Low FFA's in a Base method then would it be feasible to react the High FFA's In a separate Acid reaction? Or what problems would I encounter like the water problem you noted below? Would the FFA's be worth the trouble? Thanks Jim Jan Warnqvist wrote: Hello Jim, when using the acid esterification, you will have methyl esters, unreacted oil, sulphate ions, oxonium ions and - water. Proceeding to the base step you will create more methyl esters, potassium or sodium soaps, maybe a little unreacted oil or partially reacted oil, potassium or sodium sulphates and - even more water. This method works fine if the water content can be kept on a reasonable level. Please note that the higher the initial FFA level, the more water will be produced. With best regards Jan Jan Warnqvist AGERATEC AB [EMAIL PROTECTED] + 46 554 201 89 +46 70 499 38 45 - Original Message - From: JJJN [EMAIL PROTECTED] To: BIO Biofuel@sustainablelists.org Sent: Thursday, January 05, 2006 3:01 AM Subject: [Biofuel] Acid - Base questions I have decided to try the acid/base method in small test batches as I have some High FFA (4ml) oil I would like to process. Since September I have gone to great lengths to get repeatability and accuracy in all my work with Biodiesel. I have read and re-read JtF and I know that I will no doubt read it several more times if I get stumped. I would like to start with fully understanding the process first. Before I start: Can you use KOH with the Acid Base method? It might be obvious, but I did not see it in the recipe as a substitution. When the acid gets done with Estrification properly then the mix that is left is basically an oil (triglycerides) , Methanol, and Sulfur ions ? Or did I miss something? When the Methoxil is added the Sulfur gets combined with the Sodium ions, (right?) how does this affect the reaction? Any good experienced information would be helpful, Jim ___ 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/ ___ 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
Re: [Biofuel] Acid - Base questions
Hello Jim, when using the acid esterification, you will have methyl esters, unreacted oil, sulphate ions, oxonium ions and - water. Proceeding to the base step you will create more methyl esters, potassium or sodium soaps, maybe a little unreacted oil or partially reacted oil, potassium or sodium sulphates and - even more water. This method works fine if the water content can be kept on a reasonable level. Please note that the higher the initial FFA level, the more water will be produced. With best regards Jan Jan Warnqvist AGERATEC AB [EMAIL PROTECTED] + 46 554 201 89 +46 70 499 38 45 - Original Message - From: JJJN [EMAIL PROTECTED] To: BIO Biofuel@sustainablelists.org Sent: Thursday, January 05, 2006 3:01 AM Subject: [Biofuel] Acid - Base questions I have decided to try the acid/base method in small test batches as I have some High FFA (4ml) oil I would like to process. Since September I have gone to great lengths to get repeatability and accuracy in all my work with Biodiesel. I have read and re-read JtF and I know that I will no doubt read it several more times if I get stumped. I would like to start with fully understanding the process first. Before I start: Can you use KOH with the Acid Base method? It might be obvious, but I did not see it in the recipe as a substitution. When the acid gets done with Estrification properly then the mix that is left is basically an oil (triglycerides) , Methanol, and Sulfur ions ? Or did I miss something? When the Methoxil is added the Sulfur gets combined with the Sodium ions, (right?) how does this affect the reaction? Any good experienced information would be helpful, Jim ___ 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] Acid - Base questions
Thanks Jan, If I had developed a method to separate FFA's from base stock without using chemicals or water say in the range of 95% separation in WVO (still a work in progress but hopeful results) so that I could React the Low FFA's in a Base method then would it be feasible to react the High FFA's In a separate Acid reaction? Or what problems would I encounter like the water problem you noted below? Would the FFA's be worth the trouble? Thanks Jim Jan Warnqvist wrote: Hello Jim, when using the acid esterification, you will have methyl esters, unreacted oil, sulphate ions, oxonium ions and - water. Proceeding to the base step you will create more methyl esters, potassium or sodium soaps, maybe a little unreacted oil or partially reacted oil, potassium or sodium sulphates and - even more water. This method works fine if the water content can be kept on a reasonable level. Please note that the higher the initial FFA level, the more water will be produced. With best regards Jan Jan Warnqvist AGERATEC AB [EMAIL PROTECTED] + 46 554 201 89 +46 70 499 38 45 - Original Message - From: JJJN [EMAIL PROTECTED] To: BIO Biofuel@sustainablelists.org Sent: Thursday, January 05, 2006 3:01 AM Subject: [Biofuel] Acid - Base questions I have decided to try the acid/base method in small test batches as I have some High FFA (4ml) oil I would like to process. Since September I have gone to great lengths to get repeatability and accuracy in all my work with Biodiesel. I have read and re-read JtF and I know that I will no doubt read it several more times if I get stumped. I would like to start with fully understanding the process first. Before I start: Can you use KOH with the Acid Base method? It might be obvious, but I did not see it in the recipe as a substitution. When the acid gets done with Estrification properly then the mix that is left is basically an oil (triglycerides) , Methanol, and Sulfur ions ? Or did I miss something? When the Methoxil is added the Sulfur gets combined with the Sodium ions, (right?) how does this affect the reaction? Any good experienced information would be helpful, Jim ___ 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/
[Biofuel] Acid - Base questions
I have decided to try the acid/base method in small test batches as I have some High FFA (4ml) oil I would like to process. Since September I have gone to great lengths to get repeatability and accuracy in all my work with Biodiesel. I have read and re-read JtF and I know that I will no doubt read it several more times if I get stumped. I would like to start with fully understanding the process first. Before I start: Can you use KOH with the Acid Base method? It might be obvious, but I did not see it in the recipe as a substitution. When the acid gets done with Estrification properly then the mix that is left is basically an oil (triglycerides) , Methanol, and Sulfur ions ? Or did I miss something? When the Methoxil is added the Sulfur gets combined with the Sodium ions, (right?) how does this affect the reaction? Any good experienced information would be helpful, Jim ___ 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/
