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The '''Riesling Trail''' is a 27 kilometre walking and riding track located in the [[Clare Valley]], [[South Australia]]. It runs between [[Auburn]] and [[Clare]], passing through several towns and villages along the way, including [[Leasingham]], [[Watervale]], [[Penwortham, South Australia|Penwortham]] and [[Sevenhill]]. Originally part of the railway branch line which ran between [[Riverton]] in the south to [[Spalding]] in the north, it was abandoned after the [[1983]] [[Ash Wednesday]] bushfires which burnt through the valley and damaged a lot of the trackwork. It was decided that the old railway lines would be removed and in the late 1990s, this part of the route was converted into its present use as a walking and cycle trail. Many of the original rails were sent to [[Queensland]], where they were layed down as tracks used for transporting sugar trains in the north of that state.
'''Biodiesel recipe'''
Like a recipe for making a cake, a biodiesel recipe specifies [[quantity]] of every ingredient required, and the steps for combining and processing them to make biodiesel fuel.
The most common recipe uses waste vegetable oil ([[WVO]]), alcohol ([[methanol]] or [[ethanol]]) and [[sodium hydroxide]] (caustic soda), to produce biodiesel and [[glycerol]]. To produce 1 [[tonne]] of biodiesel:
* One needs 1 t of biolipids (animal or vegetable oil) and 0,1 t of methanol.
* One receives 0,1 t of glycerol.
The most common steps are:
#'''Preparation''': cleaning/heating [[biolipid]] (i.e. [[WVO]]). With '''wet''' oil, you will obtain [[soap]] with the biodiesel, the conversion index from vegetable oil to biodiesel will be smaller and you will obtain an excess of [[triglyceride]]s.
#'''[[Titration]]''' of WVO sample. Optimal '''[[pH]]''' for Biodiesel is '''7''' (neutral), the same as [[distilled water]] (and most tap water). Some fat has a high level of [[free fatty acid]]s which require an acid [[esterification]] (to obtain an pH lower than 3) before the [[alkaline]] [[transesterification]].
#'''Mixing''' the [[bioalcohol]] ([[methanol]] or [[ethanol]]) and [[catalyst]] ([[sodium hydroxide]]) in exact amounts, to produce [[methoxide]]
#'''Combining''' at 50ºC methoxide with the biolipids.
#'''Separation''':
##Of biodiesel and [[glycerol]] (by [[decantation]], [[centrifugation]]...).
##Removing of alcohol (by [[distillation]]).
#Biodiesel '''purification''': separation from the biodiesel of the [[waste]]s (catalyst and soap): washing and drying the biodiesel.
#Disposing of the wastes.
There are three basic routes to biodiesel production from [[biolipid]]s (biological oils and fats):
*Base catalyzed transesterification of the biolipid.
*Direct acid catalyzed transesterification of the biolipid.
*Conversion of the biolipid to its [[fatty acid]]s and then to biodiesel.
Almost all biodiesel is produced using '''base catalyzed transesterification''' as it is the most economical process requiring only low temperatures and pressures and producing a 98% conversion [[yield]]. For this reason only this process will be described bellow.
Transestrification is crucial for producing [[biodiesel]] from biolipids. The transesterification process is the reaction of a [[triglyceride]] (fat/oil) with an [[bioalcohol]] to form [[ester]]s and [[glycerol]].
==Oil preparation==
Biodiesel processor machines, need the vegetable oil to have some specific properties:
*[[Suspension|Suspended]] particles lower than 1% (mass/mass) and than 5 [[micrometer]]s. Because of this, the following are necessary:
**[[Filtration]] to 5 micrometers.
**Washing with hot water.
**[[Decantation]].
**Heating of the oil.
**Second decantation.
*[[Anhydrous]] (waterless). Because of this, the final step of preparation, after the second decantation is drying.
*Easy [[solubility]] in the alcohol to use.
===Reaction===
The reaction may be shown
CH<sub>2</sub>'''COOR1'''<BR>
|<BR>
CHCOOR1 + 3 CH<sub>3'''</sub>OH''' → (CH<sub>2</sub>'''OH''')<sub>2</sub>CH-OH + 3 CH<sub>3</sub>'''COO-R1'''<BR>
|<BR>
CH<sub>2</sub>COOR1
Since we are dealing with nature, the alkyl group on the triglycerides are probably different, so it would actually be more like
CH<sub>2</sub>'''OC=OR1'''<BR>
|<BR>
CHOC=OR2 + 3 CH<sub>3'''</sub>OH''' → (CH<sub>2</sub>'''OH''')<sub>2</sub>CH-OH + CH<sub>3</sub>'''COO-R1''' + CH<sub>3</sub>'''COO-R2''' + CH<sub>3</sub>'''OC=O-R1'''<BR>
|<BR>
CH<sub>2</sub>COOR3
:[[Triglyceride]] + [[methanol]] → Glycerol + Esters
R1, R2, R3 : [[Alkyl]] [[group]].
During the esterification process, the triglyceride is reacted with alcohol in the presence of a catalyst, usually a strong [[alkaline]] ([[Sodium hydroxide|NaOH]], [[Potassium hydroxide|KOH]] or [[sodium silicate]]). The main reason for doing a [[titration]] to produce biodiesel, is to find out how much alkaline is needed to insure a complete transesterfication. [[wiktionary:empirical|Empirical]]ly 6.25 [[gram|g]] / [[litre|l]] NaOH produces a very usable fuel. One uses about 6 g NaOH when the [[WVO]] is light in colour and about 7 g NaOH when it is dark in colour.
The alcohol reacts with the fatty acids to form the mono-alkyl ester (or biodiesel) and crude glycerol. The reaction between the biolipid (fat or oil) and the alcohol is a [[reversible reaction]] so the alcohol must be added in excess to drive the reaction towards the right and ensure complete conversion.
===Base catalysed Mechanism ===
You want to mix the base (KOH,NaOH) with the alcohol to make a reactive anion
KOH + ROH → RO<sup>-</sup> + H<sub>2</sub>O
KOH and NaOH are strong bases, so the reaction equilibrium is far to the right.
The ROH needs to be very dry. Any water in the alcohol will reduce the amount of RO<sup>-</sup> that gets formed.
The RO<sup>-</sup> is a reactive guy, so you must be very careful with this stuff. Often in chemistry alcohols are mixed with KOH to make a "base bath" for cleaning glass. It actually dissolves the surface of the glass, so be really careful with this stuff.
Once the RO<sup>-</sup> group is formed, it is added to the triglyceride. The S<sub>n</sub>2 reaction that follows replaces the alkyl group on the tricglyceride in a series of reactions.
The carbon on the ester of the triglyceride has a slight positive charge, and the oxygens have a slight negative charge, most of which is located on the oxygen in the double bond. This charge is what attracts the RO<sup>-</sup> to the reaction site
<pre>
R1
backside attack |
RO- -----------------> C=O
|
O-CH2-CH-CH2-O-C=O
| |
O-C=O R3
|
R2
</pre>
This yields a transition state that has a pair of electrons from the C=O bond now located on the oxygen that was in the C=O bond.
<pre>
R1
|
RO-C-O- (pair of electrons)
|
O-CH2-CH-CH2-O-C=O
| |
O-C=O R3
|
R2
</pre>
These electrons then fall back to the carbon and push off the glycol forming the ester.
<pre>
R1
|
RO-C=O
+
-O-CH2-CH-CH2-O-C=O
| |
O-C=O R3
|
R2
</pre>
Then 2 more RO's react via this mechanism at the other 2 C=O groups. This type of reaction has several limiting factors. RO<sup>-</sup> has to fit in the space where there is a slight positive charge on the C=O. So MeO- works well because it is small. As the R on RO- gets bigger, reaction rates decrease. This effect is called steric hinderance. That is why methanol and ethanol are typically used.
There are several competing reactions, so care must be taken to ensure the desired reaction pathway occurs. Most methods do this by using an excess of RO<sup>-</sup>.
The acid catalysed method is a slight variance, but is also affected by steric hinderance.
===Process===
*Preparation: care must be taken to monitor the amount of water and [[free fatty acid]]s in the incoming biolipid (oil or fat). If the free fatty acid level or water level is too high it may cause problems with soap formation ([[saponification]]) and the separation of the glycerin by-product downstream.
*Catalyst is dissolved in the alcohol using a standard agitator or mixer.
*The alcohol/catalyst mix is then charged into a closed reaction [[vessel]] and the biolipid (vegetable or animal oil or fat) is added. The system from here on is totally closed to the atmosphere to prevent the loss of alcohol.
:The reaction mix is kept just above the [[boiling point]] of the alcohol (around 70°C) to speed up the reaction though some systems recommend the reaction take place at [[room temperature]]. Recommended reaction time varies from 1 to 8 hours. Excess alcohol is normally used to ensure total conversion of the fat or oil to its esters.
*The glycerin phase is much more dense than biodiesel phase and the two can be gravity [[mixture separation|separated]] with glycerin simply drawn off the bottom of the [[settling]] vessel. In some cases, a [[centrifugation|centrifuge]] is used to separate the two materials faster.
*Once the glycerin and biodiesel phases have been separated, the excess alcohol in each phase is removed with a [[flash evaporation]] process or by distillation. In other systems, the alcohol is removed and the mixture neutralized before the glycerin and esters have been separated. In either case, the alcohol is recovered using [[distillation]] equipment and is re-used. Care must be taken to ensure no water accumulates in the recovered alcohol stream.
* The glycerin by-product contains unused catalyst and soaps that are neutralized with an acid and sent to storage as crude glycerin (water and alcohol are removed later, chiefly using [[evaporation]], to produce 80-88% pure glycerin).
*Once separated from the glycerin, the biodiesel is sometimes purified by washing gently with warm water to remove residual catalyst or soaps, dried, and sent to storage.
==See also==
*[[How to make Biodiesel]]
*[[Biodiesel processor]]
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