Chapter 4

MATERIAL BALANCE

The production of biodiesel from waste cooking oil is divided into six steps:

esterification of free fatty acid, transesterification of triglyceride, biodiesel purification,

glycerol purification, ferric sulfate recycle, and methanol recycle. The production plant

will process 10, 000 kg of waste cooking oil per day.

Material balances permit keeping track and checking of all the materials that

goes in and out of the plant. These include all the raw materials, the main products, the

by-products and the wastes.

The general equation for the material balance around a certain equipment is:

𝐼𝑛𝑝𝑢𝑡 = 𝑂𝑢𝑡𝑝𝑢𝑡 + 𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛

4.1. Esterification of Free Fatty Acid

Figure 4.1. PFD on Esterification of Free Fatty Acid Step

 The esterification of free fatty acid allows the conversion of free fatty acid in

the waste cooking oil into FAME. The process starts with filtering out of solids

from the raw material and proceeds to the reactor where the esterification takes

place. The mixture of FAME, methanol, triglyceride and ferric sulfate produced is

fed to the distillation column to recover the methanol. The bottoms product is then

fed to the decanter where the catalyst is separated and recovered.

4.1.1. Filter

4.1.1.1. Principle

4.1.1.2. Figure

4.1.1.3. Nomenclature

4.1.1.4. Assumptions

4.1.1.5. Calculations

4.1.1.6. Summary

INPUT OUTPUT
Stream Components (kg) Streams Components (kg)
TG 8150 TG 8150
FFA 1500 WC2 FFA 1500
WC1
Water 50 Water 50
Solids 300 Subtotal WC2 9700
Subtotal WC1 10,000 Solids 300
Subtotal Solid 300
Grand Total 10,000 Grand Total 10,000

4.1.2. Reactor 1

4.1.2.1. Principle

4.1.2.2. Figure

4.1.2.3. Nomenclature

4.1.2.4. Assumptions
 4.1.2.5. Calculations

4.1.2.6. Summary

4.1.3. Distillation Column 1

4.1.3.1. Principle

4.1.3.2. Figure

4.1.3.3. Nomenclature

4.1.3.4. Assumptions

4.1.3.5. Calculations

4.1.3.6. Summary

4.1.4. Decanter 1

4.1.4.1. Principle

4.1.4.2. Figure

4.1.4.3. Nomenclature

4.1.4.4. Assumptions

4.1.4.5. Calculations

4.1.4.6. Summary

4.2. Transesterification of Triglycerides

4.2.1. Reactor 2

4.2.1.1. Principle

4.2.1.2. Figure

4.2.1.3. Nomenclature

4.2.1.4. Assumptions

4.2.1.5. Calculations

4.2.1.6. Summary

4.2.2. Distillation Column 2

 4.2.2.1. Principle

4.2.2.2. Figure

4.2.2.3. Nomenclature

4.2.2.4. Assumptions

4.2.2.5. Calculations

4.2.2.6. Summary

4.2.3. Decanter 2

4.2.3.1. Principle

4.2.3.2. Figure

4.2.3.3. Nomenclature

4.2.3.4. Assumptions

4.2.3.5. Calculations

4.2.3.6. Summary
4.3. Biodiesel Purification

The upper layer was the FAME (crude biodiesel) with lighter color, and the

lower layer was the glycerol. The crude biodiesel was washed by 10 wt% of water

at 80oC to remove the soap, which was produced by reaction of the alkali and FFA.

The wet crude biodiesel was dried under vacuum (5 ± 1 mmHg) at 90oC with a

rotational evaporator for an hour (Wang et al., 2006).

Figure 4.2. PFD of Biodiesel Purification Step

4.3.1. Wash Tank

4.3.1.1. Principle

Washing Biodiesel with water is the oldest and most common

method of cleaning biodiesel. About 3% of raw, unwashed biodiesel is

methanol. Methanol is a solvent, it captures soap and other impurities

and holds them dissolved in the biodiesel. Water soaks up that methanol,

releasing impurities to be washed away with water. Keeping the

methanol liquid and diluted in water makes water washing the safest

way to clean biodiesel. Most dry wash methods require we evaporate or

distill the methanol into a flammable and toxic gas as part of the

purification process (Da Tech, 2019).

 Static or gravity washing is applied for this step wherein it is a

method that is less aggressive and less likely to generate an emulsion. It

is simply placing water and biodiesel in the same tank without any

mixing. Impurities migrate from the biodiesel to the water through the

boundary layer over time. This process takes anywhere from 4 hours to

24 hours to saturate the water with contaminants. It is particularly

effective as the first wash on very soapy biodiesel made from high FFA

oils (Da Tech, 2019).

4.3.1.2. Figure

Wash Tank

N2 WW1

WWT1 T1

Figure 4.3. Mass Balance for Wash Tank

4.3.1.3. Nomenclature

Table 4.1. Nomenclature for Wash Tank Mass Balance

Input Output
N2 = Centrate leaving the decanter WW1 = Wastewater produced
(kg) from Wash Tank 1
TGN2 – triglyceride in N2 KOHWW1 – KOH in WW1
WN2 – water in N2 SWW1 – soap in WW1
FAMEN2 – fatty acid methyl ester
FN2 – Ferric Sulfate (kg) T1 = FAME 3
MN2 – methanol in N2 TGT1 – triglyceride in T1
KN2 – KOH in N2 WT1 – water in T1
SN2– soap in N2 FAMET1 – fatty acid methyl
WWT1= Water for washing (kg) ester in T1 (kg)
FT1 – Ferric Sulfate in T1 (kg)
MT1 – methanol in T1
4.3.1.4. Assumptions

1. Complete removal of the KOH and soaps that are present in

the FAME product after washing.

2. Entering water completely leaves the wash tank along with

the wastewater stream.

3. The crude biodiesel was washed by 10 wt% of water at

80OC to remove the soap, which was produced by reaction

of the alkali and FFA.

4.3.1.5. Calculations

Assuming complete removal of KOH and Soap:

𝑇1 = 𝑁2 − (𝐾𝑁2 + 𝑆𝑁2 )

𝑇1 = 9914.9012 − (89.9983 + 47.3233)

𝑇1 = 9777.5797

Assuming water used for washing is 10%:

𝑊𝑊𝑇1 = 0.10𝑁2

𝑊𝑊𝑇1 = 0.10 ∗ 9914.9012

𝑊𝑊𝑇1 = 991.4901

Overall Material Balance:

𝑁2 + 𝑊𝑊𝑇1 = 𝑊𝑊1 + 𝑇1

9914.9012 + 991.4901 = (𝑊𝑊1 ) + 9777.5797)

𝑊𝑊1 = 1128.8117 𝑘𝑔 𝑊𝑎𝑠𝑡𝑒𝑤𝑎𝑡𝑒𝑟 𝑠𝑡𝑟𝑒𝑎𝑚

 Water leaving the system:

𝑊𝑊1 = 𝑊𝑎𝑡𝑒𝑟 𝐿𝑒𝑎𝑣𝑖𝑛𝑔 + 𝐾𝑂𝐻 + 𝑆𝑜𝑎𝑝

𝑊𝑎𝑡𝑒𝑟 𝐿𝑒𝑎𝑣𝑖𝑛𝑔 = 1128.8117 − 89.9983 − 47.3233

𝑊𝑎𝑡𝑒𝑟 𝐿𝑒𝑎𝑣𝑖𝑛𝑔 = 991.4901

4.3.1.6. Summary

4.3.2. Distillation Column 3

4.3.2.1. Principle

4.3.2.2. Figure

4.3.2.3. Nomenclature

4.3.2.4. Assumptions

4.3.2.5. Calculations

4.3.2.6. Summary

4.4. Glycerol Purification

4.4.1. Neutralization Tank

4.4.1.1. Principle

4.4.1.2. Figure

4.4.1.3. Nomenclature

4.4.1.4. Assumptions

4.4.1.5. Calculations

4.4.1.6. Summary

4.4.2. Decanter 3
 4.4.2.1. Principle

4.4.2.2. Figure

4.4.2.3. Nomenclature

4.4.2.4. Assumptions

4.4.2.5. Calculations

4.4.2.6. Summary

4.4.3. Fractional Distillation Column

4.4.3.1. Principle

4.4.3.2. Figure

4.4.3.3. Nomenclature

4.4.3.4. Assumptions

4.4.3.5. Calculations

4.4.3.6. Summary

4.5. Methanol Recycle

4.5.1. Methanol Recycle Mixer

4.5.1.1. Principle

4.5.1.2. Figure

4.5.1.3. Nomenclature

4.5.1.4. Assumptions

4.5.1.5. Calculations

4.5.1.6. Summary

4.6. Ferric Sulfate Recycle

4.6.1. Centrifugal Separator

4.6.1.1. Principle
 4.6.1.2. Figure

4.6.1.3. Nomenclature

4.6.1.4. Assumptions

4.6.1.5. Calculations

4.6.1.6. Summary

4.7. Overall Mass Balance Summary