Quik 'n' Free ™ 

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What is Quik 'n' Free™?

The Problem
Do you want FFA free oil? Wasting catalyst producing soaps instead of biodiesel? Is chemical water production retarding your Transesterification reaction?   Are your purifications resins exhausting faster than expected? Does water washing take too long?

Solve these issues in minutes by refining your WVO or crude vegetable oil (NEW OIL) using Quik 'n' Free™ 

The Benefits of Using QnF 
At first glance one may mistakenly view the usage of Quik 'n' Free™ an incremental cost to the process of making biodiesel.  Nothing could be further from the truth, let's for the moment set aside the advantages of the QnF process compared to other methodologies (detailed below) and focus exclusively an the financial aspects.  To streamline the assessment notations were developed to provide a formula to measure the net contribution of the QnF process to making biodiesel. 

TQnF = Incremental cost of using QnF (negative value means QnF contribute more than it costs)

Qgal = Cost of QnF used in 1 gallon of feedstock

Ngal = Cost of NaOH or KOH saved from not having to neutralize the FFA

Pgal = Cost savings from water or resin not used to clean excess soaps

Lgal = Cost savings from less labor used to purify and deal with soaps or emulsions

Pbd = Incremental Revenues from increased biodiesel yield              

                  TQnF = Qgal - Ngal - Pgal - Lgal -  Pbd  

Quik 'n' Free™
Quik 'n' Free™ is an alkaline compound capable of removing FFAs from both WVO and CVO. Quik 'n' Free™ has a uniform structure that selectively binds FFAs under specific conditions (detailed below). The FFA is then removed once you remove QnF either via simple filtration or via centrifuging. 

Reduction of Free Fatty Acids (FFAs)
If your crude or waste vegetable oil has high levels of FFAs (>10%) then you may use Quik 'n' Free™ to refine your oil to reduced FFAs.

First you need to determine the percentage of FFAs that makes up your oil (see ACID VALUE MEASUREMENT below). 

Next add the required amount of water to the oil to get it to the correct mositure level (see below).  Heat your oil to a temperature between 150O F. Next add the recommended amount of Quik 'n' Free™ in a 1:1 Ratio by weight of FFA and mix aggressively for 20 minutes to maximize contact (e.g., if your FFAs is 3% by weight, then add 3% QnF by weight).

Oil Weight Conversion
1Gal = approx. 7.506 lbs  
1Litre= aprrox. 1.985 lbs

Quik 'n' Free™ will start binding with the FFAs in the oil. After 20 minutes of agressive mixing pass the mixture through a 200 micron filter tower to remove the saturated Quik 'n' Free™ particles (alternatively, a liquid/solid separating centrifuge can be used to remove the particles). The filter tower can be built on the same design lines as the tower design for Quik 'n' Dri™.

Your oil should now have a much reduce Acid Number (a 80+% reduction should be expected). We recommend that you pass the refined oil through your Quik 'n' Dri™ tower to remove any remaining moisture before adding your standard methoxide mix and proceeding to Transesterification.

Performance & Optimization
1) Quik 'n' Free™ works most effectively with oil that has some moisture content.  The moisture content should be approximately twice the weight of the FFA in the oil. So for every 1% FFAs per gallon add 68ml of water:
(example you have 10 gallons of Oil with 3% FFA, you will need 10x3x0.068  = 2.04 litres of water. Of course this assumes you are starting from bone dry oil, if not, allowance should be made for moisture already present)   
2) Absorption is optimized when WVO or "NEW OIL" has a temperature between 150O F.
3) DO NOT use in oil with temperature above 170O F. 
4) Agitate agressively.
5) Filter using a tower like filter based on the Quik 'n' Dri™ Tower. Depending on pressure build up, you may need to attach a pump to overcome the pressure buildup.
6) Estimated Oil loss from using QnF (30% by weight).  Therefore if you used 5% QnF, it will remove 1.5% of triglycerides along with the FFAs.

Measurement Rules of Thumb
1) Determine how much FFA you want to remove.
2) Determine the weight of the FFA to be removed.
3) Add the equivalent weight of QnF as the weight of FFA to be removed.
4) Add water in the amount of twice the weight of the QnF to be used

Physical Characteristics
1) Fine, White, Granules
2) Minimum particle size of 200 microns 
3) 1lb of Quik 'n' Free™ has a dry volume of 600ml
4) pH: 14
5) Level 8 Hazardous Material (corrosive), Packing Group III 

Bench Testing QnF
Equipment & Supplies Required:
1) Quik 'n' Free
2) WVO
3) Water
4) Beaker
5) Thermometer
6) Hot Plate Magnetic Stirrer
7) Filter or Mini-centrifuge
8) Scale
9) 3M FFA Test Strips

Add 100g WVO to the BEAKER and place on HOT PLATE STIRRER.  Heat WVO to between 150O F.  Dip a 3M FFA TEST STRIP into the heated WVO to get a FFA reading. Add WATER to the BEAKER in the amount of twice the FFA reading as a percentage of weight (e.g. if FFA is 3% then add 6g of water). Mix WATER and WVO while maintaing temperature between 150O F. Add QUIK 'n' FREE to the mixture in the BEAKER in the amount of 1:1 the FFA reading as a percentage of weight (i.e. using the before mentioned example you would add 3g of QnF). Stir contents of the BEAKER for 20 minutes. Filter/Centrifuge the mixture to remove QnF.  Test the WVO with a 3M FFA TEST STRIP.  End of bench test.

Quik 'n' Free™ vs. Other Methods to Reduce FFAs
QnF vs. Neutralization (Saponification):   Neutralizations is the treatment of the oil containing FFA with a base such as NaOH or KOH.  This treatment converts the FFAs into soaps thereby effecting their neutralization.  There are a number of techniques available for introducing the caustic such as directly adding the required amount as determined by titration (see below) or via a pre-wash with leftover glycerol which has caustic material still embedded. Direct neutralization (including its variations) is the most popular method employed.  The advantage of QnF over this method:

1. Little or no soap is created with QnF, so the downsides associated with in-process soap production is mitigated.
2. Reduction in the amount of NaOH or KOH used since neutralization is eliminated, resulting in real cost savings.
3. Biodiesel purification via dry or water wash is enhance due to the reduction in the amount of soaps in the final product.
4. Reduction or elimination of emulsification
5. Less resources used in purification. QnF eliminates or seriously lowers the amount of soaps created when making biodiesel. Therefore fewer resources such as water will be need to wash the final product. This means there is both and economic benefit as well as environment benefit as a result of a reduce waste water stream.  If dry-washing then the resins will last much longer between regeneration cycles.
6. Yields are greater with QnF treated oil vs. Neutralized Oil.  This is because soaps tend to lock away some of the neutral oil and can result in yield loss. Further soap production during processing slows down the process of biodiesel production leading to reduced yields. It's estimated by some that the yield loss as a ratio of soap production can be 3 to1.

QnF vs. Caustic Stripping: Caustic stripping involves the separation and removal of the soaps after neutralization via mechanical means.  Even the most sophisticated mechanical separation still results in at least 10% of the soaps remaining in the neutral oil (see above for the downside of having soaps). Also upto 9% of neutral oil is lost in the soaps layer that gets separated due to an attraction between both.

QnF vs. Acid Esterification (AE):  If the FFA in the oil is high enough an AE process may be advisable to convert FFA directly to esters.  This is a potentially dangerous process so should not be entered into without proper safety precautions. While the AE process will significantly reduce the level of FFAs, enough FFAs still remains in the oil such that if converted into soaps will have the undesirable effects detailed above. QnF should be used to treat the remaining FFAs after the AE process.

FFA Recovery 
It should be noted that once QnF is removed from the triglycerides via filtering or centrifuge the FFA is stored in its structure as bounded soaps.  To recover the FFA for use is subsequent processes simply dissolve the saturated QnF in water.  This water will be highly alkaline so you will need to add an acid such as vinegar, citric acid, etc., (the choice is a matter of preference) to neutralize the soap/water to split out the FFA. The FFA can then be recovered via centrifuging, membrane separation or settling. 

Acid Value Measurement
1) Prepare two 600 ml beakers by adding 125 ml of solvent. The solvent consists of 50%
    isopropyl alcohol/50% toluene and should be available in the lab.
2) Add about 5 grams of sample (weigh to get exact amount) to one of the beakers.
3) Add 2 ml of phenolphthalein indicator to both beakers.
4) Titrate both beakers with 0.1 N KOH to the first permanent pink color in each.
5) Calculate the acid value from: AV = (A-B) x N x 56.1/W
      where:
                     A = number of ml of KOH to neutralize sample beaker
                     B = number of ml of KOH to neutralize blank beaker 
                     N = normality of KOH solution (0.1 in this case)
                     W = weight of sample in grams  
%FFA is approximately ½ (AV)
Source: Biodiesel Production Technology August 2002–January 2004, NREL

Alternatively, for homebrewers you can also titrate according to this website www.biodieselcommunity.org.