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quote:
Originally posted by dkenny:
I'm guessing left over the last batch. stuff in the oil( but might make it something else besides K2SO4). I just know something increase the SG of the mix and it sank.

yield for this batch is better around 60 out of 65 gallons or 92%..I happier with this result than the prior 2.

-dkenny


I should have mentioned that the SG for the combined chems that I gave at .929 isn't taking into account that methanol molecules are smaller than water and sulfuric molecules are larger than water limiting the accuracy of the simple math. We would really need to combine the three chems at the molar ratio's used then weigh an actual sample to determine the actual SG. The SG may still be very close to the .929 though.

Creating the potassium sulfate would have reduced the amount of acid available and created additional H2O.
Wiki has it listed as insoluble in alcohol and soluble in water which "could" help pull the water down but methanol to a lesser extent.
It would be nice to know how much greater an affinity for water H2SO4 has versus CH3OH, I'm suspecting that H2SO4 may have the ability to draw and hold significantly more water than methanol does.
Does anyone know how this is measured?
I'm thinking a good test may be to add the methanol, water, and sulfuric, (in the molar ratios you used) and give it a good shake.
Allow to settle over night, then draw out three or four samples from the top, middle, and bottom.
Titrate the three samples and see if there is any difference.
Any thoughts?
We could also perform the same tests on just a mixture of methanol and sulfuric to see if it is indeed completely miscible?
I'm really thinking that the H2SO4 holds onto enough water that it will stratify with methanol, but I may be wrong.
 
Location: central virginia | Registered: March 13, 2008Reply With QuoteReport This Post
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reese123
-Draining should not be a requirement at this T 9.5 noah/13.3koh. If this batch had been allowed to settle overnite, there would have been a heavier black sludge, that I like to drain off before base processing,I'm not sure what it is composed of. The last wvo I had with T 14koh, had an ending T after 14hr using a .1 multiplier, of 1.25
-the batch that I just complted, I concidered the methanol after ae was 1/2 strenght, and added extra methanol in a single base reaction with very good results. It takes a bit more methanol, but most of it can be recovered. I should note, in 5 years this is the first time I've had sucess with single base processing. Tom


" I don't know what I don't know until I know"
1994 GMC 6.5 Tubo 2005 Dodge ram 3500, 3 VW's 2000, 2002, 2005.
 
Location: Manitoba Canada | Registered: March 24, 2009Reply With QuoteReport This Post
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Double D,

I have been think about this more..
I think you're impling the K2SO4 might not be created, of course I could be wrong..wouldn't be the first time..It got me thinking about the amount the K left over. after washing..maybe not that much. fair enough..but what about other contaminates? say salt? NaCL + H2SO4?. of course the worst would be NaOH for oven cleaners...

for your other question about the mix..I don't think you'll get layers. or atleast you'll need and alcohol soluable only dye.

flyinit,
I think Biotom's on the right track..your oil wasn't dry enough to start with. did you test your oil for dryness before the acid stage? as for the stuff..4NaOH is 5.6KOH..still marginal..using NaOH this is much harder to process..I think the hard stuff you have on top is soap..try taking a chunk and washing something with it?
by all mean provide the rest of the processing details..if you have them. My other thought is for 200+ gallons you don't a large enough pump! I a pump 2x that size on batches 1/3 that size.. but pump volume isn't the only factor involved..so please provide setup details if you can..this pump is fine for acid stages but not base stages..

it seems acid stage need just enough to turn the mix. base stage need to mix the crap out of it.

-dkenny


'84 bluebird school bus, DD8.2L turbo( 4/2011, the bus tranny has died..Frown 8.23.11 bus driven to scrap yard Frown )
2006 Jeep Liberty CRD Smile - the wife's
99 dodge 2500 5.9l 24v..-mine Smile
everything run B100 when its warm enough Smile
 
Location: RTP, North Carolina | Registered: December 15, 2004Reply With QuoteReport This Post
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Biotom,

Thank you for the info.

My preliminary test batches are causing a reaction to happen. So far 10ml meth, 2g naoh per liter wvo is getting it to break.

I will continue to perform more tests to determine a precise recipe to finish the reaction.

Next time I will perform AE, let settle overnight, then drain off bottom crap.

Do you then dry the WVO again prior to performing base?
 
Location: Upper South Carolina | Registered: December 11, 2007Reply With QuoteReport This Post
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fltinit
-no drying after the ae process, that would cause you to lose all the methanol. this is another reson we have to ensure the dryness of the wvo before we start. keep in touch, let us know how you makeout. Tom


" I don't know what I don't know until I know"
1994 GMC 6.5 Tubo 2005 Dodge ram 3500, 3 VW's 2000, 2002, 2005.
 
Location: Manitoba Canada | Registered: March 24, 2009Reply With QuoteReport This Post
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quote:
Originally posted by lil'fuelfarmer:
Hello, Just skimmed thru this thread and admittedly haven't had time to read every post but; what about silica gel, stir it in within a porous bag, pull out, sun dry and reuse? It shouldn't absorb oil and is pH neutral.


Not a bad idea, anyone have thoughts on this?

My bentonite tests went well but never could get it to pass HPT, got close but never went all the way. I think ts because some of the clay gets stuck in suspension and the particulates are too smll to be completely removed by my 'cooffee' filtration setup Smile

I was going to set up AE tests using the .05 multiplier on a rainy day earlier this week but the sun decided to come out and let me play with my 'fuge' instead Smile

I still have to set this one up. With the results I have gotten so far I would expect the AE to benefit with the addition of powdered bentonite to soak up the water and allowing the reaction to continue to near completion (at least if it doesnt also soak up the H2SO4 and methonal)
I'll try to setup today if I have time.

Biotom, any bentonite retesting on your end? Anyone got some silica gel to test?
 
Location: Buckeye | Registered: July 07, 2009Reply With QuoteReport This Post



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Oh and one last thing, if the bentonite intereferes with the AE process it would still make for a great material to soak up most of the excess water in our waste WVO while it sits. Near zero energy water removal.

My tests were run with 5% H2O to 95% WVO and it removed a large majority (I'm guessing at least 90% of the H2O) of water with no extra mixing after initial blending. The bentonite sinks to the bottom where it can be collected, dried, and reused in the next batch. Good stuff! Big Grin
 
Location: Buckeye | Registered: July 07, 2009Reply With QuoteReport This Post
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Location: Southern WI, USA | Registered: May 18, 2006Reply With QuoteReport This Post
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quote:
Originally posted by dkenny:
Double D,

I have been think about this more..
I think you're impling the K2SO4 might not be created, of course I could be wrong..wouldn't be the first time..It got me thinking about the amount the K left over. after washing..maybe not that much. fair enough..but what about other contaminates? say salt? NaCL + H2SO4?. of course the worst would be NaOH for oven cleaners...

for your other question about the mix..I don't think you'll get layers. or atleast you'll need and alcohol soluable only dye.


-dkenny


I think the K2SO4 would definately be created if there is soap/ residual base left in the processor after your base stage. How much would depend on the amount left in the processor?
Caustic cleaners? Could be.
Is this your 80G water heater?

Last night I mixed
100.5ml CH3OH
3.15 ml H2SO4
12.5ml H2O

Since their all clear, I was thinking I may be able to shine a light through the mix and see if it refracts at any seperated layers. I can't see ant refraction (?) with a flash light.
I'm planning to titrate the sample at different depths later tonight to see if the mix is more acidic toward the bottom.
I'll also check the SG.
 
Location: central virginia | Registered: March 13, 2008Reply With QuoteReport This Post
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I titrated and weighed the sample.
The titration at the top was 57ml KOH(93%)
The titration at the bottom was 55ml.
I take it the difference was in my measurements.

I weighed two samples at 10 ml each.
The first was 9.45g
The second was 9.43g

For a SG of .944g/ml average.
Funny thing about that.

Funny thing is if you add the combined weights it's = 97.892g
The combined volume = 115.25ml
97.892/115.25 = .849 SG.

So the combined ingredients are only occupying a volume of 103.7ml
I can only guess this is due to the size difference in the molecules with the smaller molecules (CH3OH) occupying some of the space amongst the larger ones.
Anyone know how to calculate this one? Confused

This message has been edited. Last edited by: Double D,
 
Location: central virginia | Registered: March 13, 2008Reply With QuoteReport This Post
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Latest results

38gls oil

oil was t20 ae .13 w/22% total meth.
allowed to dry overnight Sunday with pump and heater in reactor.
started ae at 10am Mon. morning. at 4pm t was 6 @ 6pm t4.5 @ 8pm t4. drained and didnt remix this time(it has never lowered my t) Started 80/20 at 8pm. drained glyc tues morn. and added the 20%. passed 3/27 with instant clairity tues afternoon about 5pm. Final was 35gls bio. Hoping for 36 or 37gls bio but very pleased with 35gls

This is the fastest I have ever turned a tank from start to finish. I might have dropped my t by .5 to 1 point lower if let settle overnight, but I wanted to see if a short turn around affected the final results. I dont think this had any effect on the final.(passed 3/27 with a high return 35gls out of 38gls oil)
any thoughts on the lower t's. I have high t oil and never gotten below a 3. Only got t3 once after letting it set for a week.



Still trying to achieve a 1 or 2 final t. Should I add more acid after the ae stops to push the t lower? If so how much meth should I add along with the extra acid?


jrunlimited
 
Location: Texas | Registered: June 15, 2008Reply With QuoteReport This Post
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Just off topic for one second;
This is why we all need to use a centrifuge:

This is 200 gallons ran through a VERY coarse filter and then into my rotor centrifuge.
This is just 1 pass! Big Grin
I feel like a proud parent (again) Big Grin

And it does eliminate all variables to help assess the AE process.
 
Location: Buckeye | Registered: July 07, 2009Reply With QuoteReport This Post



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Double D,

this was not in my water heater but in one of my cone bottom tanks. I know about 1qt of finished BD remain in the plumbing. Finished in washed and dried. So since you asked where the KOH comes from I'm moe skeptical about my initial answer. contaniments in the oil is still unknown.

with my next batch I'm going to pull some out first and try a few things. first is mixing water and acid into the oil to see what happens. next just a water rinse to check the tiration of the water before and after

jrunlimited,
cannot complain with getting 35 of out 38 gallons. 4 is lower the calculated minimum for the amount of acid you used. did you check the ph of the stuff you drained? what about a check from some near the top?

-dkenny


'84 bluebird school bus, DD8.2L turbo( 4/2011, the bus tranny has died..Frown 8.23.11 bus driven to scrap yard Frown )
2006 Jeep Liberty CRD Smile - the wife's
99 dodge 2500 5.9l 24v..-mine Smile
everything run B100 when its warm enough Smile
 
Location: RTP, North Carolina | Registered: December 15, 2004Reply With QuoteReport This Post
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Dkenny, I am beginning to notice a trend of finish T's coming in lower than the calculated minimum. What are the chances the equation is off a bit?
 
Location: Buckeye | Registered: July 07, 2009Reply With QuoteReport This Post
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buckeyebiodiesel,
I've been seeing the same thing, but there's no pattern.
one person used 5 times too much acid but the final result was way less than calculated?
others just get close to calculated?

maybe we should try the experiment again but using a large test sample. I might try this again this weekend. it supposed to rain. we'll have a hurricane about 400 miles off shore.

-dkenny


'84 bluebird school bus, DD8.2L turbo( 4/2011, the bus tranny has died..Frown 8.23.11 bus driven to scrap yard Frown )
2006 Jeep Liberty CRD Smile - the wife's
99 dodge 2500 5.9l 24v..-mine Smile
everything run B100 when its warm enough Smile
 
Location: RTP, North Carolina | Registered: December 15, 2004Reply With QuoteReport This Post
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quote:
Originally posted by buckeyebiodiesel:
Dkenny, I am beginning to notice a trend of finish T's coming in lower than the calculated minimum. What are the chances the equation is off a bit?


The 2.25 That Dkenny came up with is from an actual titration using his solution and his Acid. There is going to be some difference in the "1ml Acid = T 2.25"
It should be close though.
For example my KOH say 93% on the bag, and my H2SO4 says 96%

My 1% w/v titrating solution contains 1/56.1(MW of KOH) = .0178 moles KOH x .93 = .01655 moles / 1000ml = .0000165 moles KOH in 1ml titrant.

My H2SO4 weighs 1.84g/ml
Molecular weight = 98.08g per mole.
1.84/98.08 = .0187 moles per ml. H2SO4/ 1000ml = .0000187 moles x .96 = .0000179 moles H2SO4 diluted in one L oil.
So when I pull 1ml of oil out to titrate, it contains .0000179 moles H2SO4.

It takes two moles of KOH to neutralize one mole of H2SO4.
So I would take the .0000179 x 2 =.0000358m / .0000165m KOH = 2.16ml of my titrant are required to neutralize 1ml of my H2SO4 diluted into 1 L of oil.

This would be the absolute lowest I can go unless some of my H2SO4 is consumed by something in the oil.
Even this is dependant upon the strength of my chemicals being what is listed on the labels.

HTH.

By the way that's sure some good looking fuged oil. Do you have plans for how to build one of those?

This message has been edited. Last edited by: Double D,
 
Location: central virginia | Registered: March 13, 2008Reply With QuoteReport This Post
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Double D, makes sense except isn't the one part of your equation supposed to be 1.84/98.08=.0187 moles per ml instead of:
98.08/1.84 = .0187 moles per ml

Even so, I get what you are saying.

I am trying to start a new thread for the cetrifuge. I didn't take many pictures of this one, but will for the next unit. This lil' guy is just a prototype leading to our 'Big Bertha' centrifuge Big Grin

The big girl will spin much faster with a much larger diameter rotor to kick the centripital force well above 5000G's. The lil' guy is about 2000G's which does an amazing job, but I want more GPM with even better cleaning.

The last batch shown in the pic was at a little over 3GPM.
 
Location: Buckeye | Registered: July 07, 2009Reply With QuoteReport This Post
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quote:
Originally posted by buckeyebiodiesel:
Double D, makes sense except isn't the one part of your equation supposed to be 1.84/98.08=.0187 moles per ml instead of:
98.08/1.84 = .0187 moles per ml

Even so, I get what you are saying.

I am trying to start a new thread for the cetrifuge. I didn't take many pictures of this one, but will for the next unit. This lil' guy is just a prototype leading to our 'Big Bertha' centrifuge Big Grin

The big girl will spin much faster with a much larger diameter rotor to kick the centripital force well above 5000G's. The lil' guy is about 2000G's which does an amazing job, but I want more GPM with even better cleaning.

The last batch shown in the pic was at a little over 3GPM.


Thanks for checking the math Buckeye. I changed the post above.
 
Location: central virginia | Registered: March 13, 2008Reply With QuoteReport This Post



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No prblem Double D.
And for anyone interested I started the "How to build a centrifuge" thread (that means you especially Dkenny Wink)

It located here:
How to build a centrifuge

I would venture to say anyone that knows how to weld can build a rotor style centrifuge for under $300 easily.

Ok, I won't hyjack this thread any longer with my new 'Fuge' Smile
 
Location: Buckeye | Registered: July 07, 2009Reply With QuoteReport This Post
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It seems to me it would be more beneficial to use molar ratios of Methanol:FFA and FFA:Sulfuric.
Dkenny used a molar ratio of 6:1 methanol:FFA for his last batch and 13.2:1 FFA to sulfuric.
This produced a layer of excess Sulfuric, H20, and methanol that had a SG of of approximately .944.
Being the SG of the combined excess is higher than oil estimated at .92 it allowed the mixture to fall to the bottom where it could be drained. I personally feel that .944 SG is suficiently heavier than .92 to allow for a little error possibly.
The T-3 x .2 formula we've been using creates a difference in molar ratios with the titration. My thought is that keeping the molar ratios of FFA:Methanol, and FFA:Sulfuric consistent at any titration may allow for more consistent results over a wider range of titrations.
Any thoughts?

You can use the following to determine molar ratio.
As the ratio's get closer together the SG of the resulting mix would be raised ensuring that the aqeous layer is under the oil layer. The formula used to determine the following is not without error due to uncontrollable variables but should be close.

Methanol to add:
methanol to FFA ratio, KOH Titration x multiplier = ml methanol to add per liter of oil.

6:1, T x 4.32 =
5:1, T x 3.60 =
4:1, T x 2.88 =
3:1, T x 2.16 =

Sulfuric to add:
FFA:Sulfuric ratio, KOH Titration x multiplier = ml Sulfuric to add per liter of oil.
18:1, T x .053 =
17:1, T x .056 =
16:1, T x .059 =
15:1, T x .063 =
14:1, T x .068 =
13:1, T X .072 =
12:1, T x .079 =
11:1, T x .086 =
10:1, T x .095 =
9:1, T x .105 =
8:1, T x .119 =
7:1, T x .136 =
6:1, T x .158 =

Who wants to try it?

Edited to add 18:1 - 13:1 ratio's

OK guys and gals.
Here is a long formula that will take into account icreasing the acid amount while decreasing the Methanol amount at the same time. Or increasing the methanol amount and subsequently reducing the Acid amount at the same time.
This is calibrated to roughly a 7:1 ratio of methanol to water causing the stopping of the reaction (with a molar ratio of 18:1 Sulfuric to FFA used in the beginning).
It is also calibrated to roughly a 5:1 ratio of methanol to water causing the stopping of the reaction (with a molar ratio of 13:1 Sulfuric to FFA used in the beginning).

A = FFA (in the ratio of FFA to sulfuric FFA:Sulfuric)
B = T x.0175
T = Titration KOH

This formula will give you the amount of methanol to use based on a selected molar ratio of FFA:Sulfuric.

The formula is:
(((A x.4xB)+B)x32.05)/.792 = ml Methanol per liter of oil.

For example: Say you want to use a ratio of 20:1 FFA to Sulfuric in order to see a low titration number after the reaction and we have a starting T of 18.

20 x .4 x .315= 2.5 x 32.05= 80/.792= 101ml Methanol

To figure out your acid amount in ml:
(B/A) x54

So
.315/20 =.015x54 = .81ml Sulfuric
To find the estimated ending T,
multiply ml sulfuric x 2.1 or as dkenny has found with his x 2.25 Smile

If you want to see a lower titration just increase the FFA:Sulfuric ratio.
This will reduce the amount of acid used and increase the amount of methanol to compensate.
There is still a limit as to how low an amount of acid can be used, and I havent worked out the upper limit of acid either but I'll try to do that as soon as I can.
The ending titration can be very misleading though in that you may have esterified all the FFA possible in a batch but just be reading the Sulfuric in the titration. Draining above a titration of 15 is still necessary to reduce the amount of water going into the base stage.


That leads me to another point.
The amount of caustic added in the base stage following esterification should be based on the total volume of methanol and oil that is in the mix at the time you titrate. As opposed to just the volume of oil. Since your titration is reading the concentration of acid material in that given 1ml volume and that 1ml is representing the entire mix. The qty of base should be based on the entire qty.

I'm quite excited about this formulas accuracy but need some participants. Smile
Is anyone willing?

This message has been edited. Last edited by: Double D,
 
Location: central virginia | Registered: March 13, 2008Reply With QuoteReport This Post
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