[Biodiesel In Utah] Lots of Oil and methods.

[Graydon Blair]

I'll also add to the discussion...I promise, I'll "TRY" to keep it brief...

Solid Catalysts:
Nickel, as it's defined here, really isn't acting like a solid catalyst. It's more like a semi-solid catalyst because it leaches off into the biodiesel (albeit very slowly) over time and then you have to reimpregnate the alumina with Nickel again.

A true solid catalyst won't leach off.

At current, there really isn't one available to homebrewers on the market today. Domestic Energy Partners a.k.a. BetterBiodiesel.com CLAIM to have a solid catalyst, but they're extremely tight-lipped about how they're pulling it off.

If any supposed "solid catalyst" company CLAIMS to have a catalyst & then claims that you need to "regenerate" their "solid catalyst" after a few hundred uses, it's not really a solid catalyst (by the way, they'll charge you oodles of money to "regenerate their [supposed] solid catalyst" too while they're at it.

Also a bit on the different methods for making bio.

1- Acid Esterification
It works. Requires a lot more methanol than 22%, but it does do it's job. The Van Gerpen recipe goes like this.
A- Measure the FFA % (via a titration test)
B- For every gram of FFA in the oil you plan to use (calculate grams by taking total grams of oil & multiplying it by the FFA% you find in step A), add 2.25 grams of methanol. Yep. That's a TON of methanol by volume if your oil has lot's of FFA's in it
C- Add sulfuric acid (0.05grams for every gram of FFA in your oil)
D- Heat to 60-65 deg C & stir for one hour
E- Allow it to settle. You'll see Biodiesel and a Methanol/Acid/Water layer appear.
F- Drain off the Methanol/Acid/Water layer & you'll hopefully have lowered your FFA percentage
G- To calculate how well you've done, retitrate

2- Base Transesterification
(the current KING of how to make Biodiesel)
Making Biodiesel using this method is pretty simple.
A- Titrate oil & add catalyst according to titration
B- Add 20-22% methanol to oil
C- Heat mixture to 60-65 D C & stir for 1 hour
D- Allow mixture to settle & drain off Glycerin/Methanol/Excess Catalyst layer
E- You'll also get some soap precipitate out as well if you still had FFA's in your oil.

Now, combine #1 & #2 (an Acid/Base method) and you've got a great success recipe.

You can also do an Acid/Base/Base method.

Essentially, to the Esterification the exact same way.
On the Transesterification process, only add 80% of the methanol & 90% of the catalyst & react. 
Then drain off the glycerin/methanol/catalyst mixture and add the remaining 20% methano/10% catalyst & react again.

Because you've removed some of the glycerin in the first stage, it'll cause the reaction to want to move to equilibrium (from triglycerides to esters) a little better.

Dr. Jon Van Gerpen (pretty much one of the authorities in brewing Biodiesel) has measured the above method with a lot of great success.

Now, that said, high conversion rates aren't your only measurements of success. The ASTM standard has a HUGE array of components to it, Free & Total Glycerin measurements are just one aspect of it (however, I'd say they hold a lot more weight and can effect the other measurements more so than the other measurements).

The method by which you wash and then also by which you dry can effect your ASTM quality as well.

The scholars in the field of biodiesel production often say that making biodiesel is a deceptively simple reaction. Just add methanol & catalyst & whamo! You've got Biodiesel!......well....kind of.

Biodiesel, at least in the US, isn't really "biodiesel" until it meets the full ASTM D-6751 specification. If it's "out of spec", it's just Methyl Esters (or Ethyl Esters if made from Ethanol).

I highly recommend becoming aquainted with any of the works of Dr. Jon Van Gerpen & his associates for more information on some high quality studies on the art of making biodiesel (and I use that term with full force "the art"). 

While we all can make a small batch, it's much harder to make good, high quality, ASTM Biodiesel repeatedly without some very good equipment and a high level of attention to detail.

You can read up on some of the works of Van Gerpen & Company here:
http://www3.me.iastate.edu/biodiesel/Technical%20Papers/Tech_papers.html

I just returned from their week long Biodiesel Production Workshop held in Ames Iowa (the next one will be held in Moscow Idaho in March) and thoroughly loved it. We cover, in great detail, each of the things you'd mentioned, plus best practices, lab work & more.

You can see some of the pictures I took while I was there last week here:
http://www.utahbiodieselsupply.com/photos/events/iowabiodieselworkshop200610/

-Graydon
...ok, not so "brief" after all, but, c'mon...when was I ever "short-winded" ;-)


eastmanassociates at comcast.net wrote:  Karl -
  
 Let me add a little bit about the nickel catalyst.  My background is catalysis:  I spent nearly 30 years doing petroleum catalysis for one of the major oil companies.  Nickel-plated things will almost certainly NOT do what you want.  The problem is a matter of surface area. Nickel plate has very low surface area, while most nickel catalysts are specifically engineered to have extremely high surface area, on the order of 200 m2/g.  Making such catalysts is about half science and half black magic (take it from somebody who knows!)  Typically, you will take a high-surface-area support like gamma-alumina, then impregnate it with a dilute solution of a soluble nickel salt, e.g., nickel chloride, followed by reduction in hydrogen at elevated temperature to give the final catalyst.  
  
 The problem with such catalysts is that they are fairly sensitive to oxygen, which re-oxidizes the catalyst to nickel oxide - only the elemental form is active.  
  
 I strongly suggest that you not try to use nickel plate in your reactor.
  
 --
Alan D. Eastman, PhD 
Eastman Associates LLC 
801-278-9560
  
 -------------- Original message -------------- 
From: Karl Peterson <admin at kmjmail.com> 

> Hello all. 
> 
> I have a degree in Chemical Engineering and teach High School 
> Chemistry, Physical Sciene and Earth Science. I have been collecting 
> equipment as my budget (teachers salary) allows. I expect to be able 
> to begin producing BioDiesel in quantity in a few months. I want to 
> get the Federal credit, so I am trying to design a process that 
> virtually guarantees ASTM qualification. I am also looking at 
> producing ethanol. 
> 
> I have scrounged two gas fired water heaters. I am leak and pressure 
> testing them now. I want to make them into "Appleseed" type 
> processors. I may have to break down and purchase a couple of 
> electric heaters if I cannot figure out an easy way to heat these  
> ones. I was thinking of using a Waste Motor Oil setup to heat them, 
> but the laws about waste motor oil are enough to give you grey hairs. 
> 
> For construction, I have had stick and gas welders for years, but it 
> has been a few years since I did much welding. I purchased from 
> Harbor Freight both a MIG and a TIG welder so that I can weld the 
> thin metals that barrels are made of and fabricate my own 
> equipment. Gotta practice. I have a source of lots of small pieces 
> of 10 guage steel that I can practice on. I have a bunch of closed 
> top barrels that I plan to make into settling tanks and other vessels. 
> 
> I am located in American Fork. I have really nice, heavy guage, open 
> top barrels, with more on the way. More than I can use. If anybody 
> is interested, I will sell them for $5 dirty to cover my costs, a 
> little more if you want them clean and pretty. I am also ge tting 
> Intermediate Bulk Containers (IBC) or Totes. These are the big 
> square plastic vessels that I have seen advertised for $80. They 
> each hold just over 275 gallons - I am thinking of $30 dirty if you 
> pick them up and $50 dirty if I deliver in Utah or Salt Lake 
> counties. I am thinking add $20 if you want them clean. 
> 
> I currently have storage (IBC's that are cleaned out) for 825 gallons 
> with another 825 gallons coming on line as soon as I clean the 
> totes. If the guy with "lots of oil" is near me, or within driving 
> distance of me, lets talk. 
> 
> The rest of my comments are from research and not from 
> experience. Take what I say with a grain of salt. 
> 
> The reaction we want is: all the Fatty Acid groups present in the 
> feed-stock, both free and attached to the Glycerine molecule, 
> converted into an Ester. This Ester is what we call BioDiesel. < BR>> 
> The formation of the ester requires an alcohol to donate an R 
> group. The alcohols that are commonly used are Ethanol and 
> Methanol. The ester that is produced is the Fatty Acid with the 
> Ethyl group or the Fatty Acid with a Methyl group. This is about as 
> simple as I can make the organic chemistry. 
> 
> Our goal is to make as much ester as possible and have all the 
> glycerine settle out as glycerol or 1,2,3-propanol. 
> 
> The reaction between Alcohol and Vegetable Oil or Free Fatty Acid is 
> a slow equilibrium. To speed things up, we must use a catalyst and 
> It helps to remove one of the products of the reaction as soon as it 
> is formed. This forces the equilibrium towards one side of the 
> equation or the other. Anybody know how to build liquid-liquid centrifuges? 
> 
> A catalyst is a thing that helps the reaction along, but is not 
> consumed in the  reaction. Generally , the more catalyst you put in, 
> the faster things come to an end. 
> 
> In the case of BioDiesel, many catalytic routes have been suggested and used. 
> 
> The most common method uses base catalysis. Sodium Hydroxide or 
> Potassium Hydroxide are most commonly used. The drawback of this 
> process is that any Free Fatty Acids, Fats that are not tied to a 
> glycerine molecule, will react with, and consume, the base forming 
> soap. This is not a good thing. 
> 
> Recently, some have suggested starting with acid catalyst. The idea 
> here is to convert all the Free Fatty Acids into Ester, then 
> neutralize and introduce the base. No soap, but more chemicals. 
> 
> My searching has revealed some published work on solid 
> catalysts. One study found that Nickel is a catalyst for the 
> BioDiesel reaction. The study found that the time for 80% conversion 
&g t; was 24 hours using only nickel as the catalyst. They were testing a 
> catalyst named ETS-10. ETS-10 showed 94% conversion after about 8 
> hours. Sure wish I could get my hands on some of that catalyst. The 
> company that made ETS-10 has been acquired by BASF and ETS-10 is no 
> longer available. You cannot purchase it even if you could afford 
> it... They tested the nickel to make sure that the reaction vessels 
> would not add to or detract from the action of the catalyst. I found 
> a plating shop that will nickel plate things for me. 
> 
> I want to use no acid or base, just nickel. I am building two 
> reactors, so that I can drain off the glycerol and go round and round 
> forcing the reaction as far to the ester as I can. I am hoping that 
> by removing glycerol from each stage, and using an excess of 
> alcohol. I can force the equilibrium to give me nothing but 
> ester. Experimentati on and testing will tell me how many times to 
> drain the glycerol. I have a good amount of nickel plated copper 
> bits and plan to make a couple of columns out of it and plumb it into 
> the circulation loop of my reactors. If it works as good as I hope, 
> then get some metal packing and have them nickel plated. 
> 
> My biggest problem right now is finding the time to build the 
> reactors and then sources of WVO. 
> 
> Karl Peterson 
> 
> 
> _________________________________________________________________ 
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