Dear Friends;

Finally I produced Biodiesel from “acid oil” of sunflower. Acid oil is the ceaphest source of FFA which comprise of 100 % of bulk FFA. Naturally, first reaction is an esterification of FFA with glycerol and second reaction is a base-transesterification. In the first step, titration of new oil was decreased from 158 ml to 1,71 ml (Tickel). New oil is manly composed of monoglyceride (% 50 percent, 25 % is di-glyceride and the rest is tri-glyceride. Here are the recipes of base-transesterification.
1- run
New oil -150 ml.
Methanol - 30 ml.
NaOH - 0,85 gram (titration value +3,5 gram NaOH)

2- run
New oil -150 ml.
Methanol - 30 ml.
NaOH - 1 gram (titration value + 5 gram NaOH)

Both of runs, I have got good separation of glycerol and methly ester. You will find attached photo. But in the washing test, I got too much soap and much oily substances. In this forum, completness test is conducted 3/27 protocol. But in our country, we make burnig test. Principally, it shows whether reaction complete or not. Biodiesel is burnt in the teaspoon until no substances remains. I am sceptical that too much soap is stemming from diglyceride. Altouug titration value is between acceptible limit, why don’tI burn methly ester completely in burning test. Any help would be appreciated.

Best regards

Photo is not loaded due to capacity proglem of forum. If you would like to send it you, I will.

quote:

Acid oil is the ceaphest source of FFA which comprise of 100 % of bulk FFA. Naturally, first reaction is an esterification of FFA with glycerol and second reaction is a base-transesterification. In the first step, titration of new oil was decreased from 158 ml to 1,71 ml (Tickel). New oil is manly composed of monoglyceride (% 50 percent, 25 % is di-glyceride and the rest is tri-glyceride.

What did you start with? What new oil is 50% MG, 25% DG and 25% TG?

What did you start with?
"Acid oil" is produced from soapstock of edible oil and is used mainly in animal feed. After oily seed is crushed and pressed, oil is separated from husk. Then Raw oil is subjected to caustic refining to neutralize free fatty acid, which is called "soapstock." Soapstock is then processed with mineral acid to spring free fatty acid. "acid oil" can be a starting material for biodiesel.

New oil
I gave its name as new oil. Because It doesn't has a characteristics of virgin oil and waste vegetable oil. At glycerolysis of free fatty acid with glycerol is mainly produced monoglyceride, di and little bit tri-glyceride. And we can transestrify them to produce biodiesel.
Let me give you some physical properties of new oil.
Specific gravity : 0,963 gr/ml
Not liquid at room temparature
Color : Dark brown
Ph : 6-7

thanks

if you notify a different e-mail, I will send a photo of biodiesel genarated fornew oil.

quote:

New oil

So, do I understand right that this is the product of your glycerol esterification? If so, then those #'s make sense.

Dear Andrew Morris;

yes.correct. New oil is product of glycerolysis. Due to my poor english, I did not understand "#'s"

thanks

Dear erdem-ozcan
You said you esterified with glycerol and reduced titration from 158 to 1.7. What conditions (temp, mixing etc) and how long did it take to esterify?
Thanks

Dear Funnyfidel;

Temparature; 180-190 C
Time : 6-8 hours with harsh agitation.
Vacumm is needed to push reaction MG side and to get reaction water.
Material : acid oil % 75
Glycerol % 25 (crude glycerol of biodiesel)
ZnCl % 0,1
Starting PH : 3-5

Thanks Erdem-Ozcan
The glycerol you use: is that treated in any way to remove either catalyst (Na/K) and/or methanol. The methanol would also come off under vacuum: hazardous? When you mention starting pH; the pH of what? glycerol?

the glycerol I use is a definetly by-product of biodiesel. I did not crack the glycerol coctail to remove excess catalyst with any acid. Esterification reaction needs less PH. But Crude glycerol ph is between 9-10. Mixture PH of acid oil and gylcerol would be between 6-7. So I have to reduce the PH from 6-7 to 2,5 by adding mineral acid. And also Mixture at higher PH cause to excessive foaming at around 60 C and hindering vacauum application While the heat incerase.

No problem for Methanol. Beacuse nitrogen blanket is a compulsory for preventing oxidation and It enhace evaporation of reaction water. Don't forget not to produce alkyd resin from this mixture instead of monoglycerdide (acid oil+glycerol), Acid oil has not got WATER and Nitrogen blanket must be employed for oxigen.

erdem ozcan,
I asked a chemist about this formula and he was asking if there wouldnt be an increase in glycerol content because you are mixing glycerin to the "new oil"?

Dear Brain;

I don't mix glycerol to new oil. To produce a new oil, we mix glycerol to "acid oil" which is FFA's content more than 96%. We genarate a new oil by binding FFA molecule to glycerol molechule.
thanks

erdem ozcan,
Have you tested the end product and how does it compare with biodiesel standards? Have you made costings per liter in making new oil from acid oil and how does it compare to the other methods? Thanks. This is very informative.

Could you please tell me how you make neotralization of acid oil.?cemalokan@prometa.com.tr

Erdem ozcan,
Please help me understand more fully the characteristics of your NEW OIL. What is the approximate analysis of the glycerol byproduct starting material? How much glycerol, methanol, soap and catalyst? You can estimate this from your previous BD reaction. On completion of the "glycerolsis" of the acid oil do you remove the excess glycerol byproduct? How much of the acid oil remains? With all of the catalyst and other components from the previous steps there could still be components such as FFA soaps (NaFFA's) still in your NEW OIL? You follow your reaction to produce NEW OIL using titration but given the presence of the catalyst from the previous transesterification reaction (NaOH?) does that necessarily mean that the FFA content is greatly reduced?
How do you know that the NEW OIl is 50% monoglyceride, 25% diglycerides and 25% triglycerides? Did you perform an actual chemical analysis.

quote:

Originally posted by erdem_ozcan:
Dear Funnyfidel;

Temparature; 180-190 C
Time : 6-8 hours with harsh agitation.
Vacumm is needed to push reaction MG side and to get reaction water.
Material : acid oil % 75
Glycerol % 25 (crude glycerol of biodiesel)
ZnCl % 0,1
Starting PH : 3-5

I will greatly appreciate you time to answer my questions.
Sincerely,
Rick G.

Dear Rick G;

I sent a message into your private message inbox.
I answered to your guestion on May 29th. But I have not still could not get any comments so far. Please check it out for me. I hope you are ok.

take care
erdem

Rick,

Let me try to translate some of this. I tried glycerolsyis before but gave up before I got to this stage.

you asked:

quote:

Erdem ozcan,
Please help me understand more fully the characteristics of your NEW OIL. What is the approximate analysis of the glycerol byproduct starting material?

What Erdem did was take 4 units of raw FFA's and add 1 unit of standard byproduct from normal biodiesel production. This byproduct was probably about half soap and half glycerin, and might have had up to 20% or so methanol. That wouldn't have mattered too much though because it would have boiled off immediately.

Erdem said he heated the batch to 180-190C, ran harsh agitation for 6-8 hours, maintained a vacuum, and ended up with glycerides that titrated at 1.7.

My speculations start here:

Erdem, if you added standard byproduct from a previous biodiesel reaction, you'd have added about 50% soap and 50% glycerin, after the methanol boiled off. In addition, there may have been leftover caustic that would have combined with the FFA feedstock and produced additional soap. I can see where you'd have a lot more soap after base transesterification. The key to avoiding that would be splitting the soap with some acid before glycerolysis. If you titrate it first to see how much you need to split the soap, and maybe add a little more, you'll probably get a somewhat quicker reaction from the acid catalyst. You'd also get a higher yield as the split soap would add its FFA's to the batch. Lastly, you'll get a salt from splitting the soap that might make the first wash go much easier.

The big safety concern with this is to make sure your reactor vessel is up to the job; mild steel and concentrated H2SO4 don't mix well.

Rick:

The basic operation here is to put the gylcerin and FFA's back together with heat and lack of water - that's why it's hot and in a vacuum, to get rid of the water produced by the reaction.

So Erdem is cooking the glycerin and FFA's at high temperature and agitating for 6-8 hours and gets mostly mono-glycerides. These will transesterify very quickly, faster than triglycerides.