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Synthesis reactions
Esterification
The esterification (FIG. 1) involves the reaction of free fatty acid with an alcohol (typically a low
molecular weight alcohol, such as MeOH, EtOH, PrOH, BuOH) to produce an alkyl ester (biodiesel)
and water. To increase the reaction rate can be used both acidic and basic catalysts. However, basic
catalysts can be used only at high temperatures (soap formation leads to deactivation). Typically,
acid catalysts such as sulfuric acid, are used to carry out the esterification reaction in mild conditions.
Transesterification
The reaction of transesterification shown in Fig. 2, involving triglycerides (TG) that react with an
alcohol (usually alcohols are used simply linear such as MeOH, EtOH, PrOH and BuOH) to form
glycerol and mono alkyl esters which are biodiesel fuel. In the reaction, the TG molecule reacts with
three molecules of alcohol in a row in the presence of a catalyst (acid or base) to produce a first
diglyceride (DG), and a monoglyceride (MG), and finally glycerol (GL) and three molecules
monoester. All steps are reversible equilibrium reaction net, favoring the formation of reaction
products. The reaction can either use an alkaline catalyst or one acid, alkaline catalysts are preferred
because they give a higher reaction rate moderate reaction conditions.
RAW MATERIALS
-Vegetable oils and animal fatsFats and oils are chemically equivalent; their differences come from variations in fatty acid
composition modules. Fats have a higher content of saturated fatty acids as training units, while
unsaturated oils have more units. The largest amount of Biodiesel is produced in batch reactors.
Currently, most production facilities are located in Europe continue where demand for biodiesel is
higher.
Table 1 The composition of vegetable oils and fats feature common animals.
Fatty acid composition, %gr
Long C (nr.=
links)
Rapeseed oil
Crude olive oil
Myristic
Palmitic
Palmitol
eic
Stearic
Oleic
Linoleic
Linolenic
14:00
16:00
16:01
18:00
18:01
18:02
18:03
0,8
0,9
3,4
64,4
80,4
22,3
4,5
8,2
0,6
3,5
9,2
Sat.
(%)
4,4
12,6
Sunflower oil
6,1
3,3
16,9
73,7
9,4
Soybean oil
0,1
10,6
4,8
22,5
52,3
8,2
15,5
Palm oil
35,0
7,0
44,0
14,0
42,0
Fat white
23,3
3,5
11,0
47,1
11
1,0
37,8
Poultry fat
22,2
8,4
5,1
42,3
19,3
1,0
35,7
Lard
1,7
17,3
1,9
15,6
42,5
9,2
0,4
34,6
Tallow
4,8
28,4
14,8
44,6
2,7
52,0
Yellow fat
2,4
23,2
3,8
13,0
44,3
7,0
0,7
38,6
(Tallow)
Brown Fat
1,7
22,8
3,1
12,5
42,4
12,1
0,8
37,0
Some continuous processes for the production of biodiesel - site have been described in the
literature. The production of biodiesel is expected to skyrocket in the near future due to current
companies that deliver long-term conventional hydrocarbon fuels and increasing demand for
renewable fuels. Significant production of Biodiesel is obtained only by using a continuous flow
processing.
Although continuous flow production facilities can obtain larger amounts of Biodiesel throughput and
are cheaper as investment, batch plants are cheaper to build and can be easily adapted to change.
However, the current trend is for building manufacturing facilities continue, with higher production
capacities and lower operating costs, in line with current demand for biodiesel.
6:1
Temperature
60-65C
Pressure
1,4-4,1 bar
Catalyst
NaOH
Figure 4. a) The reaction of free fatty acids basic catalyst to produce soap and water, undesirable byproducts
b) hydrolysis of the ester from the reactions with water, forming free fatty acid
For these reasons, ideally, the raw material used in the transesterification catalyzed oily base must
not exceed 0.5% weight content of free fatty acid and both alcohol and catalyst must be Anhydrous.
Otherwise, production yields are affected in proportion and major operating problems. In Fig. 5 shows
a simplified block diagram of the technological process for a typical process for producing Biodiesel
using basic catalysts.
The alcohol, the catalyst and the oil were combined in a stirred reactor where it is stirred for one hour
at 600C. Small capacity plants generally use descontinue reactors, but most large capacity plants
(more than 4 million liters / year) using continuous processes - mixing autoclave or tubular reactors.
After reaction, glycerin is separated from the methyl esters. Due to the low solubility of glycerol
esters, separation is generally faster and can be performed with a decanter or a centrifuge. Excess
methanol tends to act as agent miscibilizare and slow separation. However, this excess is not
separated from the reaction product until it separates glycerin methyl ester transesterification due to
reversible reaction.
The crude biodiesel is initially purified by thorough washing phase with water or by neutralizing the
acid with a polyprotic mineral acid to remove basic catalyst residues. Further, in a settling tank are
separate an aqueous phase precipitates of salt and Biodiesel. Finally, Biodiesel - is distilled in high
vacuum at moderate temperatures (approx. 190-270C) to be in accordance with ASTM
specifications (or 99.6% pure).
Experimental installation
In the following was analyzed Biodiesel production plant in HYSYS process simulator.
Description of the experimental setup. For biodiesel production plant consists of:
- Mixed - in which methanol is fed with NaOH catalyst.
- Reactor -where with a pump and a heat exchanger are added three system components (triolein,
methanol and catalyst).
- Rectificare- column in which is the reaction product to remove excess unreacted methanol which is
then recycled.
- Extractie- column in which water is added to the reaction-product extraction gricerina.
- Splitter - which separates the upper and lower catalyst exits the reaction product.
- The rectification column - which separates the main product of triolein in excess biodiesel.
The catalyst with 50% glycerol was added to a mixer where the mixture obtained passes in a reactor
in which energisation H3PO4. This reactor is separate upper and lower methanol 85% crude glycerin.
The working - consisted of the following steps:
- Analysis of simulation facility for obtaining's biodieselu with HYSYS simulator and literature data.
- Economic evaluation process using Aspen HYSYS program economic analysis and economic data
V 8.3 Market raw material and product.
The process of maximizing capacity was achieved by increasing the feed rate continues up to 25% of
the initial flow. After each step of increasing the production capacity of the plant, economic evaluation
was performed using Aspen HYSYS evaluator V 8.3.
From the graphical representation shows that the optimal profit production capacity is 10529 tons /
year. At this value of the production capacity is achieved a profit of $ 1.69 million / year biodiesel
plant for obtaining presented.
References
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