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CHAPTER 2

PROCESS SELECTION
2.2. Process Selection
Vegetable oil or in this project we use crude palm oil is having a high
viscosity, low volatility and polyunsaturated character, therefore this oil is
impossible to use directly in a combustion engine. The vegetable oil must be
converted into organic compounds with shorter chain, namely esters (biodiesel).
There are several method for biodiesel production such as pyrorilsis,
microemulsion, hydrocarbon blending, and transesterification. Transesterification
reaction is the most common method that is used for biodiesel production because
this reaction have the highest conversion than the other method (JC, Juan, et. al.,
2011). Beside transesterification process there are several basic process for
biodiesel production, starts with pre-treatment, transesterification, glycerol
separation, and purification.

Figure 2.1 Block Flow Diagram of Basic Biodiesel Production


(source: Sarin, 2012)

In general there are four steps for biodiesel production such as pre-treatment
for the raw material, transesterification for the main process ,purification for
removing impurities and last is drying. For each process there are also several

differences, at this process selection we are going to choose the best option for
each process.
2.2.1.
Pre-Treatment
PERLU DIMASUKIN DEGUMMING KAH? KALO ASUMSI CPO
SUDAH REFINED KAYAKNYA GAPERLU ADA DEGUMMING
Before the main process of production biodiesel begin we have to make
sure that the raw material or in this case is vegetable oil is qualified for
production. There are two main requirement parameter for palm oil, such as
content of free fatty acid (FFA) and water content in oil. FFA is free fatty acid
chain that different from triglyceride because it is not bound by glycerol.
Generally content of FFA in raw material must be under 3 wt % especially for
production that use base catalyst (Ribeiro et al, 2011). FFA can react with the base
catalyst in saponification reaction and produce soap that will harm biodiesel
production (Atadashi et al, 2012).

Figure 2.2 Saponification Reaction


(source: Atadashi et al, 2012)

Pre-treatment process is required for decreasing content of FFA in raw


material. There are two ways, neutralization (caustic refining) and esterification
with acid catalyst (Kombe et al, 2011). Neutralization involves a deliberate
reaction between FFA with alkaline reactant to form the soap with the aim to
facilitate the separation of the raw material prior to entry into the
transesterification reaction. This method is only done for oil with FFA levels
below 5%, because if it is too much, then the oil available for transesterification
will be reduced very significantly (Kombe et al, 2011). Therefore, esterification
with acid catalyst is in common use. This method involves a reaction between
FFA with alcohol to produce methyl ester in the esterification reaction. Thus, the
resulting ester into biodiesel that can be used and not wasted in the form of soap.

Figure 2.3 FFA Esterification Reactions


(source: Marchetti and Errazu, 2008)

2.2.2.

Transesterification

Transesterification

is

the

main

process

of

the

production.

Transesterification is the reaction between triglycerides in the raw material with


alcohol to produce primary products such as alkyl esters (biodiesel) and glycerol
byproducts. Transesterification reaction involves three reversible reactions that
occur sequentially where the first reaction is a chemical reaction of triglycerides
(TG) into diglycerides (DG), then proceed with the conversion reaction
diglycerides (DG) into monoglycerides (MG), and subsequently followed by
conversion reaction of monoglycerides (MG) into glycerol. Each of these
reactions will produce an ester compound so that through the transesterification
reaction of one molecule triglyceride (TG) will be generated three molecules ester
compound. The type of alcohol that can be used in the transesterification reaction
is methanol, ethanol, propanol, butanol, or amyl alcohol. But alcohol compound
that is often used for the production of biodiesel transesterification reaction is
methanol because of its cheap price. Therefore, the transesterification reaction is
alternating, then the rest of the alcohol at the end of the reaction the excess will be
used to shift the reaction equilibrium toward the product.

Figure 2.4 Transesterification Reaction


(source: Sarin, 2012)

2.2.2.1.

Catalyst Selection

The presence of a catalyst in a reaction makes the reaction rate increase


so that the reaction products will also increase. The catalyst used for
transesterification reactions can be classified into three categories, among others:
homogeneous catalysts, heterogeneous catalysts and catalytic enzymes.
Homogeneous catalysts is the catalyst that is commonly used for the
production of biodiesel because its use is easy and requires no long reaction time.

The advantage of using homogeneous catalysts in biodiesel production are the


reaction conditions required not extreme condition. However, in a large scale
biodiesel production, biodiesel production with homogeneous catalysts make
some additional leaching and purification stages so that production of biodiesel
will generate waste water in large quantities. There are 2 types of homogeneous
catalyst, there are homogeneous base catalyst and acid catalyst. The use of base
catalysts for the production of biodiesel has advantages over the use of an acid
catalyst for biodiesel production. Base catalyst made transesterification reactions
run 4000 times faster than the acid catalyst. The use of an acid catalyst for
biodiesel production requires longer reaction time compared with the use of base
catalysts. In addition the use of an acid catalyst also requires high temperatures, ie
above 100 C. However, the use of acid catalysts for biodiesel production more
profitable than the use of an alkaline catalyst. Acid catalyst capable of accelerating
the reaction, a transesterification reaction between triglycerides with alcohol or
esterification reaction between free fatty acid with alcohol. Therefore, the
production of biodiesel by using an acid catalyst is more advantageous if the raw
material used to contain a high free fatty acid.
In addition to using homogeneous catalysts, production of biodiesel can
be performed using a heterogeneous catalyst too. Heterogeneous catalysts has
several advantages that can be separated easily from the biodiesel product that is
formed by filtration and can be regenerated for reuse. Heterogeneous catalysts are
not corrosive.
Besides homogeneous and heterogeneous catalyst there are enzymatic
catalyst. In recent years, some researchers focus on the scientific research on the
production of biodiesel using an enzyme catalyst. One enzyme that is usually used
for the production of biodiesel is lipase. The use of lipase enzymes as catalysts to
make the reaction becomes less sensitive to the high content of free fatty acid
(FFA). the use of an enzyme catalyst also requires low energy because the reaction
takes place in a low temperature and pressure and has no side reaction
(saponification). However, the use of enzymes as catalysts for biodiesel
production has disadvantages include the price of enzymes that are expensive and
slow reaction rate.

To simplify, table below show us the advantages and disadvantages of


each catalyst
Table 2.1 Advantages and Disadvantages of each Catalysts
Type of Catalyst
Homogeneous base
catalyst

Heterogeneous
catalyst

Advantages
- Do not form water
during
transesterification
reaction
- 4000 times faster
reaction rate than
acidcatalyzed
transesterification
- Two-step alkalinecatalyzed
transesterification from
used vegetable oil
is an economic method
for biodiesel
production
- Reaction can occur at
mild reaction
condition and thus less
energy required
- NaOH and KOH are
economically feasible
base - Reusable
- Easy to separate from
product
- Relatively faster
reaction rate than
acidcatalyzed
transesterification
- Reaction can occur at
mild reaction
condition and relatively
lower energy
- Long catalyst life times

Disadvantages
- Sensitive to FFA
content in the oil
- Saponification can
occur if the FFA
content in the oil is more
than 2 wt.%
- Saponification will
decrease the biodiesel
yield and cause problem
during product
purification
- Produce more
wastewater from
purification

-Poisoning of the catalyst


when exposed to
ambient air
- Sensitive to FFA
content in the oil due to
its
basicity property
- Saponification can
occur if the FFA content
in the oil is more than 2
wt.%
- Saponification will
decrease the biodiesel
yield and cause problem
during product
purification

Homogeneous
catalyst

Heterogeneous
catalyst

Enzyme catalyst

- Higher molar ratio of


alcohol to oil
- Produce more
wastewater from
purification
- Diffusion limitation
-Low reaction rate
- Can lead to equipment
corrosion
- Harder separation of

acid -Insensitive to FFA and


water content in the
oil
- Preferred-method if
low-grade oil is used
catalyst from
- Esterification and
transesterification occur
simultaneously
- Saponification can be
avoided
- Produce high yield of
biodiesel
acid -Insensitive to FFA and
water content in the
oil
- Preferred-method if
low-grade oil is used
- Esterification and
transesterification occur
simultaneously
- Easy separation of
catalyst from product
- High possibility to reuse
and regenerate the
catalyst
- Recyclable
-Prevent saponification
- Only simple
purification step is
required
- Environmental friendly
and nonpolluting

-Low reaction rates


- Unfavourable side
reaction
- Higher cost
- High reaction
conditions and longer
reaction times]
- More energy
requirement
- Leaching of catalyst
active sites may result
to product contamination

-Very slow reaction rate


- High cost
- Sensitive to alcohol,
typically methanol that
can deactivate the
enzyme
- Inactivation and
denaturation of enzyme
can lead to decreasing
yield of biodiesel

(source: Overview of Catalysts in Biodiesel Production, 2016)

To choose the catalyst for transesterification process, we use process


scoring. Both of methods will be scored by some criterias. Score of each concept
is evaluated by multiply the value of score with score percentage, where score
percentage is obtained by considering most prioritized criteria. Some criterias that
used in this process scoring are:

Reaction time
Analyze which catalysts are the fastest at reaction
Sensitivity to FFA and water
Analyze the sensitivity to FFA and water because related to saponification
reaction
Operation condition
Analyze which catalysts has the most efficient and simple operation condition

Additional Process
Analyze if there any additional process that must be used if the one of the
catalysts chosen
Economic
Analyze the lower price and most economic

Waste Analysis
Analyze which catalysts have least waste
Next, each of catalysts option will be scored with the scoring value: 1

means worst, 2 means bad, 3 means good, 4 means very good, based on some
literatures and also through a group discussion. The result of process scoring is
shown in the table below:
Table 2.2 Catalysts Selection Scoring
No
.

1
2
3

Criteria

Reaction
Time
Sensitivity to
FFA and
water
Operation

Homogene
ous
Acid
Catalyst
R
S

Homogene
ous
Base
Catalyst
R
S

Heterogene
ous
Acid
Catalyst
R
S

Heterogene
ous
Base
Catalyst
R
S

20%

0.4

0.8

0.4

0.6

0.2

20%
10%

3
2

0.6
0.2

2
3

0.4
0.3

3
2

0.6
0.2

2
3

0.4
0.3

3
3

0.6
0.3

Percenta
ge

Enzyma
tic
Catalyst

4
5
6

condition
Additional
Process
Economic
Waste
Analysis
TOTAL

15%
15%

2
3

0.3
0.45

2
4

0.3
0.6

3
2

0.45
0.3

3
2

0.45
0.3

3
1

0.45
0.15

20%
100%

0.6
2.55

0.4
2.8

0.6
2.55

0.4
2.45

0.8
2.5

From the table above we can see that Homogeneous base catalyst have
the highest score. So for the production of biodiesel that we will design is going to
use homogeneous base catalyst.
2.2.3.
Purification
After the transesterification stage, byproducts such as glycerol need to be
separated from the main product of biodiesel. Separation of biodiesel and
glycerol is generally performed using gravity separation (decantation) or
centrifugation (Atadashi et al, 2012). Glycerol which has been separated can then
be collected and used for other production processes. If there is too high FFA
levels resulting saponification reaction, the resulting soap can interfere with
separation of biodiesel and glycerol. This separation should be made easier
because biodiesel and glycerol not soluble in each other. Biodiesel which is
already separated from the glycerol still needs to be purified to remove the
impurities. These impurities may be residual soap, alcohol, catalyst, and other
impurities. Purification consists of several steps, namely neutralization,
separation of alcohol and washing. Neutralization is a step to separate the
remaining soap produced as a result of the saponification by adding mineral acids
such as K3PO4, H2SO4, HCl, or citric acid into biodiesel. The acid will neutralize
the alkaline soap and reduce the consumption of water needed for washing stage
(Stojkovic et al, 2014). Separation of alcohol is used to take alcohol from the end
product biodiesel that can be collected and reused. Separation of alcohol can be
used by several different methods, but in general, these methods utilize the
boiling point of alcohol to vaporize it. Some examples of this method are vacuum
flash vaporization, falling film vaporization and distillation (Stojkovic et al,
2014). Washing is an important stage in the purification to separate the remains of
various types of impurities such as glycerol, methanol, catalyst, soap, salt, and
many others (Stojkovic et al, 2014) .This step can be done in two ways: through

the wet washing or dry washing. Wet washing is a method of draining mix
deionized water and a mineral acid or organic solvent in the biodiesel to dissolve
residual impurities such as glycerol, methanol, and catalyst, while dry washing is
a method that utilizes adsorption for biodiesel or drain biodiesel on a bed of ion
exchange resins such as magenesol (magnesium silicate), calcium magnesium
silicate, or bioabsorben (Stojkovic et al, 2014). If using this method, impurities in
the solid form can be separated mechanically, for example by using a filtration.
PROSES APALGI YANG HARUS DISELEKSI?

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