Report on

Categorization of Industries Producing Bio- Diesel

from Simple Alkali Catalyst & Lipase Enzyme

Transesterification

December 2019

Environmental Consultant:
Aditya Environmental Services Pvt. Ltd., Mumbai
 Declaration by Experts contributing to the report “Categorization of Industries
Producing Bio-Diesel from Simple Alkali Catalyst & Lipase Enzyme
Transesterification”.
I, hereby, certify that I was a part of the Team in the following capacity that
developed the above report.
Coordinator:
Name: Mr. Rajiv Aundhe

Signature & Date: 24th December 2019

Period of Involvement: since September 2019
Contact information: Mob. 09821513367, E-mail: rajiv@aespl.co.in
Functional Area Experts:
S.N. Functional Areas Name of the Expert/s Involvement Signature
(Period &
Task**)
1 Air pollution Rajiv Aundhe (Assisted since September
by Swapnil Ubale) 2019

2 Water pollution Rajiv Aundhe (Assisted since September

by Swapnil Ubale) 2019

3 Solid waste & Rajiv Aundhe since September

Hazardous waste 2019
management
Declaration by the Head of the Accredited Consultant Organization
I, Rajiv V. Aundhe, hereby, confirm that the above-mentioned experts prepared the report
“Categorization of Industries Producing Bio-Diesel from Simple Alkali Catalyst & Lipase
Enzyme Transesterification”.
I also confirm that Aditya Environmental Service Pvt. Ltd. shall be fully accountable for
any mis-leading information mentioned in this statement.

Name: Rajiv V. Aundhe

Designation: Director
Name of the Consultant Organization: Aditya Environmental Service Pvt. Ltd.
Table of Contents
1 INTRODUCTION ......................................................................................................................................................... 1
1.1 INTRODUCTION .......................................................................................................................................................................... 1
1.1.1 Objective of Study .................................................................................................................................................... 1
1.1.2 Biodiesel Manufacturing in India ...................................................................................................................... 1
1.1.3 Policy for Promotion of Biodiesel Use ............................................................................................................. 5
1.1.3.1 Policy initiatives of Govt of India - Specific to Biodiesel B100 ................................................................................ 5
1.1.4 Specifications for Biodiesel: ................................................................................................................................. 6
1.1.5 Uses of Biodiesel ....................................................................................................................................................... 7
1.2 FEEDSTOCKS USED FOR BIODIESEL MANUFACTURING....................................................................................................... 7
1.2.1 Used cooking Oil application for Biodiesel Manufacturing.................................................................... 7
1.2.2 End Note- UCO use and Pollution Potential .................................................................................................. 8
2 BIODIESEL MANUFACTURING PROCESS USING USED COOKING OIL ...................................................... 9
2.1 METHODOLOGY ADOPTED ....................................................................................................................................................... 9
2.2 PROCESS DETAILS...................................................................................................................................................................... 9
2.2.1 Thermal cracking or Pyrolysis............................................................................................................................ 9
2.2.2 Dilution or Blending ..............................................................................................................................................10
2.2.3 Transesterification ................................................................................................................................................10
2.2.3.1 Alkali catalyst transesterification process: ................................................................................................................... 11
2.2.3.2 Lipase enzyme transesterification process: .................................................................................................................. 14
2.2.3.3 Acid catalyst transesterification process: ...................................................................................................................... 17
3 EVALUATION OF CATEGORIZATION ................................................................................................................21
3.1 EVALUATION OF CATEGORIZATION AS PER CPCB GUIDELINE ....................................................................................... 21
3.1.1 Water requirement & Effluent generation ..................................................................................................21
3.1.2 Fuel requirement & emission ...........................................................................................................................22
3.1.3 Hazardous waste generation .............................................................................................................................22
4 CONCLUSION .............................................................................................................................................................24
4.1 CONCLUSION ........................................................................................................................................................................... 24
List of Tables

Table 1.1 Statewise major Biodiesel manufacturing units ................................................................................................... 2

Table 1.2 Specification of Biodiesel as per IS 15607- 2016 ................................................................................................. 6
Table 2.3 Feedstock analysis- RBD Palm Stearin ................................................................................................................... 12
Table 2.4 Analysis of Bottom Layer generated during Alkali Transesterification .................................................. 13
Table 2.5 Feedstock analysis- Used cooking oil ...................................................................................................................... 16
Table 2.6 Analysis of Bottom Layer generated during Lipase transesterification .................................................. 17
Table 2.1 Feedstock analysis- Palm Fatty Acid Distillate ................................................................................................... 18
Table 2.2 Analysis of water generated during Acid transesterification....................................................................... 19
List of Figures
Figure 2.1 Process flow diagram- Thermal cracking or Pyrolysis .................................................................................. 10
Figure 2.2 Process flow diagram- Alkali catalyst Trans esterification ......................................................................... 12
Figure 2.3 Layer formation during Alkali catalyst Trans esterification ....................................................................... 12
Figure 2.4 Process flow diagram- Lipase enzyme Trans esterification ....................................................................... 15
Figure 2.5 Layer formation during Lipase enzyme Trans esterification ..................................................................... 15
Figure 2.6 Process flow diagram- Acid catalyst Trans esterification ............................................................................ 18
List of Annexures

No. Content
1.1 National Policy on Biofuels- 2018
1.2 Note on Used Cooking Oil
1.3 Handling & Dispoal of Used Cooking Oil
1.4 Note on Repurposed Used Cooking Oil
2.1 GC analysis profile of RBD Palm Stearin
2.2 Analysis of Bottom Layer- Alkali Transesterification
2.3 GC analysis profile of Used Cooking Oil
2.4 Analysis of Bottom Layer- Lipase Transesterification
2.5 GC analysis profile of Palm Fatty Acid Distillate
2.6 Analysis of Bottom Layer- Acid Transesterification
 Biodiesel Association of India

1 INT RODUCT IO N

1.1 Introduction

Biodiesel is a mono- alkyl ester of long chain fatty acids derived from vegetable oils or
animal fat. Biodiesel is an alternative to diesel fuel and is categorised as clean fuel due to
its inherent properties as well as non- toxic & biodegradable in nature. The fuel can be
made from rapeseed, soya bean, sunflower, jatropha curcas, karanja, palm stearin, used
cooking oil, waste vegetable oil & acid oils. The National Biofuel Policy 2018 launched by
the Government of India is promoting the use of Biodiesel for use as automotive fuel or
for blending with High Speed Diesel obtained from local Refineries in order to completely
eliminate or reduce SO2 pollution levels, particulate matter & NO2 levels.
Biodiesel manufacturing capacity in India is steadily increasing at approximately 10%
per annum and is produced by Large biorefineries as well as by the Small and Medium
sector units. It is observed that there are different processes in use and some of these are
water pollution generating while others are low pollution processes.
The Central Pollution Control Board (CPCB) has published the Final Document on Revised
Classification of Industrial Sectors under Red, Orange, Green and White Categories on 29th
February 2016. Biodiesel as a product and its manufacturing process is not mentioned in
the Revised Classification of Industrial Sectors, 2016. State PCBs therefore are classifying
Biodiesel manufacturing activity in Red category irrespective of the manufacturing
process adopted by the individual units.
The Biodiesel Association of India strongly feels that the categorization of Biodiesel must
be done on the basis of manufacturing process. The Zero-discharge units whose process
of manufacturing generates no effluent that exceeds limits as classified by CPCB must be
categorized as Orange. For this purpose, they have approached Aditya Environmental
Services Private Limited (AESPL) to study the different processes used for Biodiesel
manufacturing and comment on categorization as per the Central Pollution Control
Boards classification system.
Report of AESPL is presented herein.

1.1.1 Objective of Study

Main objective of study is

 To study pollution potential of different Biodiesel manufacturing processes
 To categorize Biodiesel manufacturing activity based on CPCBs classification
system

1.1.2 Biodiesel Manufacturing in India

There are quite a few units involved in Biodiesel manufacturing all over India. The
Statewise Major Biodiesel manufacturing units are as mentioned below:

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 Biodiesel Association of India

Table 1.1 Statewise major Biodiesel manufacturing units

Sr.
Company Name Location Year Category Process Feedstocks Remarks
No.
Rajasthan
Low FFA Oils (RBD
Palm Stearin, Used By Product (Crude Glycerol sold in
Rajputana Acid Esterification /
1 Jaipur 2018 Red Cooking Oil (UCO), Market to Refinery Units for
Biofuels Ltd Trans-Esterification
Animal Tallow) conversion to Refined Glycerine)
FFA<2.0
Low FFA Oils (RBD
By Product (Crude Glycerol sold in
Kotiar Biofuels Abu Road, Trans-Esterification, Palm Stearin, UCO,
2 2019 Orange Market to Refinery Units for
Ltd Rajasthan Dry Wash Animal Tallow
conversion to Refined Glycerine)
FFA<2.0
By Product (Crude Glycerol sold in
Enzymatic Process,
3 Wash well Bhilwara 2015 Orange Animal Tallow / Fat Market to Refinery Units for
Dry wash
conversion to Refined Glycerine)
Low FFA Oils (RBD
By Product (Crude Glycerol sold in
Mangla Petro Oil Trans-Esterification, Palm Stearin, UCO,
4 Jaipur 2018 Orange Market to Refinery Units for
Industries Dry Wash Animal Tallow
conversion to Refined Glycerine)
FFA<2.0
Gujarat
Low FFA Oils (RBD
By Product (Crude Glycerol sold in
Yamuna Bio Trans-Esterification, Palm Stearin, UCO,
5 Vadodara 2015 Orange Market to Refinery Units for
Industries Ltd Dry Wash Animal Tallow
conversion to Refined Glycerine)
FFA<2.0
Low FFA Oils (RBD
By Product (Crude Glycerol sold in
Ruchi (Pilot Trans-Esterification, Palm Stearin, UCO,
6 Gujarat 2012 Orange Market to Refinery Units for
Plant) Dry Wash Animal Tallow
conversion to Refined Glycerine)
FFA<2.0
Maharashtra
Monopoly By Product (Crude Glycerol sold in
Acid Esterification /
7 Innovations Pvt Khopoli 2014 Red Multi-Feedstock Market to Refinery Units for
Trans-Esterification
Ltd conversion to Refined Glycerine)

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 Biodiesel Association of India

By Product (Crude Glycerol sold in

Munzer Bharat New Acid Esterification /
8 2019 Red Multi-Feedstock Market to Refinery Units for
Pvt Ltd Mumbai Trans-Esterification
conversion to Refined Glycerine)
Karnataka
By Product (Crude Glycerol sold in
EcoGreen Fuels Trans-Esterification, Low FFA Oils (RBD
9 Bangalore 2012 Red Market to Refinery Units for
Pvt. Ltd Dry Wash Palm Stearin, UCO)
conversion to Refined Glycerine)
Andhra Pradesh
Kaleesuwari
Andhra Acid Esterification / Crude Glycerol refined in Inhouse
10 Refinery Private 2008 Red Multi-Feedstock
Pradesh Trans-Esterification Glycerine Plant
Limited
Andhra Acid Esterification / Crude Glycerol refined in Inhouse
11 Bio Max 2009 Red Multi-Feedstock
Pradesh Trans-Esterification Glycerine Plant
Universal Andhra Acid Esterification / Crude Glycerol refined in Inhouse
12 2008 Red Multi-Feedstock
Biofuels Pradesh Trans-Esterification Glycerine Plant
Southern Biotech Andhra Acid Esterification / Crude Glycerol refined in Inhouse
13 2007 Red Multi-Feedstock
Ltd Pradesh Trans-Esterification Glycerine Plant
Southern Biotech Andhra Acid Esterification / Crude Glycerol refined in Inhouse
14 2010 Red Multi-Feedstock
Ltd Pradesh Trans-Esterification Glycerine Plant
15 Elite Oil Ltd Kakinada 2018 N.A.
By Product (Crude Glycerol sold in
Acid Esterification /
16 Yantra Fintech Chennai 2010 Red Multi-Feedstock Market to Refinery Units for
Trans-Esterification
conversion to Refined Glycerine)
Chhattisgarh
By Product (Crude Glycerol sold in
Trans-Esterification,
17 CREDA Raipur 2008 N.A. Jatropha Oil Market to Refinery Units for
Dry Wash
conversion to Refined Glycerine)
West Bengal
By Product (Crude Glycerol sold in
Emami Biotech Acid Esterification /
18 West Bengal 2009 Red Low FFA Oils Market to Refinery Units for
Pvt Ltd Trans-Esterification
conversion to Refined Glycerine)
Uttar Pradesh

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 Biodiesel Association of India

By Product (Crude Glycerol sold in

Kissan Agro Acid Esterification /
19 Noida 2012 Red Multi-Feedstock Market to Refinery Units for
Industries Ltd Trans-Esterification
conversion to Refined Glycerine)
By Product (Crude Glycerol sold in
Muzaffar Acid Esterification /
20 Al Noor 2015 N.A. Animal Tallow / Fat Market to Refinery Units for
nagar Trans-Esterification
conversion to Refined Glycerine)
Haryana
By Product (Crude Glycerol sold in
BioD Industries Bawal, Acid Esterification /
21 2019 Red Multi-Feedstock Market to Refinery Units for
Ltd Haryana Trans-Esterification
conversion to Refined Glycerine)

Observation from above table:

 Units using Low Free Fatty Acid (FFA%) Oils- RBD Palm Stearin, Animal Fat and Used Cooking Oil as feedstocks are categorized as
ORANGE by respective SPCB’s
 Units using High Free Fatty Acid (FFA%) feedstocks are categorized as RED by respective SPCB’s

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 Biodiesel Association of India

1.1.3 Policy for Promotion of Biodiesel Use

The Ministry of Petroleum and Natural Gas issued a revised policy on Biofuels vide
notification no. P-13032(16)/18/2017-CC dated 4th June 2018 as “National Policy on
Biofuels- 2018” (attached herewith as Annexure 1.1).
The Goal of the policy is to enable the availability of biofuels in the market; thereby
increasing its blending percentage. Currently the ethanol blending percentage in petrol
is around 6.0% in 2018- 19 as reported by the Ministry of Peroleum and Natural Gas and
biodiesel blending percentage in diesel is less than 0.1%. An indicative target of 20%
blending ethanol in petrol and 5% blending of biodiesel in diesel is proposed by 2030 in
the Policy set by Ministry of Petroleum and Natural Gas. This goal is to be achieved by-
a. Reinforcing ongoing ethanol/ biodiesel supplies through increased domestic
production
b. Setting up Second Generation (2G) bio refineries
c. Development of new feedstock for biofuels
d. Development of new technologies for conversion to biofuels
e. Creating suitable environment for biofuels and its integration with the main fuels
1.1.3.1 Policy initiatives of Govt of India - Specific to Biodiesel B100

To encourage production of Biodiesel in the country, the Ministry of Petroleum & Nautral
Gas (MoPNG) announced a Biodiesel Purchase Policy, in October 2015. Under this policy;
the Oil Marketing Companies (OMC’s) are to purchase Biodiesel (B100) meeting the fuel
quality standard prescribed by the Bureau of Indian Standards (BIS) for blending with
H.S. Diesel to the extent of 5% at identified purchase centres across the country.
In its meeting held on 16th January 2015, the Cabinet decided to allow the direct sale of
Biodiesel (B100) by private Biodiesel manufacturers through their authorized dealers
and Joint Ventures (JVs) of Oil Marketing Companies (OMCs) authorized by MoPNG to all
consumers.
On 10th August 2015, the Government allowed direct sale of Biodiesel (B100) to Bulk
Consumers such as the Indian Railways, State Road Transport Corporations, etc. by
amending the Motor Spirit and High Speed Diesel (Regulation of Supply, Distribution and
Prevention of Malpractices) Order, 2005. Oil Marketing Companies also started selling
blended Biodiesel on 10.08.2015 from selected Retail Outlets (petroleum pumps) in the
country.
Later, the MoPNG issued a Gazette notification No. GSR 728 (E) on 29th June 2017 for
amending the Motor Spirit and High Speed Diesel (Regulation of Supply, Distribution and
Prevention of Malpractices) Order, 2005 which states that the Central Government may
permit the direct sale of biodiesel (B100) for blending with high speed diesel to all
consumers, subject to the conditions given in the notification.
The IS 15607 Biodiesel (B100) — Fatty Acid Methyl Esters (FAME) — Specification has
been amended in March 2016 with Scope as follows:
“This standard prescribes the requirements and methods of sampling and tests for
biodiesel (B100)- fatty acid methyl esters (FAME) for use in compression ignition engines
designed for using as stand-alone fuel and as a blend stock for diesel fuel. B100 stand-
alone can also be used for heating applications and industrial engines.”

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 Biodiesel Association of India

BIS has amended IS: 1460 (Automotive Diesel Fuel Specification) in December 2017 as
follows:
“Bio-diesel (Fatty Acid Methyl Ester, FAME) conforming to IS 15607 may be blended up
to 7 percent (v/v) with automotive diesel fuel.”
Presently biodiesel blended Diesel is being sold from nearly 6,000 Retail Outlets in the
country by the OMCs as on 2019. (Source – Biodiesel Association of India)
MoPNG has issued the National Biofuel Policy-2018 in which an indicative target of 5 %
blending of biodiesel in diesel is proposed by 2030.
It has been stated in the Policy that in house produced Used/ Waste Cooking Oil (UCO/
WCO) offers potential to be a source of biodiesel production. However, the same is
marred by diversion of UCO to edible stream through various small eateries/vendors &
traders and focus will be laid upon laying down the stringent norms for avoiding the entry
of UCO in food stream and developing a suitable collection mechanism to augment its
supply for biodiesel production.

1.1.4 Specifications for Biodiesel:

The Bureau of Indian Standards (BIS) has issued standards for Biodiesel (B100) Fatty
Acid Methyl Esters (FAME) Specification- IS 15607- 2016 as below:
Table 1.2 Specification of Biodiesel as per IS 15607- 2016

Sl. No. Characteristic Requirement

1. Density at 150C. g/m3 860-900
2. Kinematic viscosity at 400C, cSt 3.5 -5.0
3. Flash point (PMCC) 0C, Min 101
4. Sulphur, mg/kg, Max 10.0
5. Carbon residue (Ramsbottom), percent by mass, Max 0.05
6. Sulphated ash, percent by mass, Max 0.02
7. Water content, mg/kg, Max 500
8. Total contamination, mg/kg, Max 24
9. Copper corrosion, 3 h at 500C, Max 1
10. Cetane No., Mm 51
11. Acid value, mg KOH/g, Max 0.50
12. Methanol, percent by mass, Max 0.20
13. Ester content, percent by mass, Min 96.5
14. Monoglycerides content, percent by mass, Max 0.7
15. Diglyceride content, percent by mass, Max 0.2
16. Triglyceride content, percent, percent by mass, Max 0.2
17. Free glycerol percent by mass, Max 0.02
18. Total glycerol, percent by mass, Max 0.25
19. Phosphorous, mg/kg, Max 4.0
20. Sodium + Potassium, mg/kg, Max 5
21. Calcium + Magnesium, mg/kg, Max 5
22. Iodine value, g iodine/100 gm, Max 120
23. Oxidation stability, at I 100C, H, Min 8
24. CFPP. 0C Max
a) Summer 18

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 Biodiesel Association of India

b) Winter 6
25. Linolenic acid methyl ester. Percent m/m, Max 12
26. Polyunsaturated (≥ 4 double bonds) methyl ester 1
percent m/m, Max

1.1.5 Uses of Biodiesel

 Switching from petroleum diesel fuels to high blend levels of biodiesel (B50 to
B100) significantly reduced PM emissions from diesel vehicles (U.S. Dept of Energy
Report, November 2016 – DOE/GO-102016-4875).
 As per studies conducted by the Argonne National Laboratory, greenhouse gas
emissions for B100 are 74% lower than those from petroleum diesel.
 The main benefit of biodiesel is that it can be described as ‘Carbon Neutral’. This
means that the fuel produces no net output of carbon in the form of carbon
dioxide.
 Biodiesel is rapidly biodegradable and completely non-toxic. Biodiesel has a higher
flash point than fossil diesel.
 According to a report by the National Renewable Energy Laboratory (NREL-USA),
biodiesel produce 78.5% fewer carbon dioxide emissions than petroleum diesel.
 Biodiesel is fully compatible with the emission control catalysts and filters that
reduce NOx and PM emissions from diesel engines. The effects are feedstock neutral
for biodiesel.
 The NOx reduction due to biodiesel blends used in boilers is independent of the type
of biodiesel used. For every 1% B20 biodiesel added, NOx decreases by 1%.

1.2 Feedstocks Used for Biodiesel Manufacturing

Fractions of Palm oil are the most widely used feed stocks for making commercial
biodiesel in many countries. The oil palm is suitable for tropical regions, with hot and
humid climate, high precipitation and its availability is well distributed throughout the
year.
Palm stearin is the solid fraction obtained during fractionation of palm oil at controlled
temperatures. Due to its low FFA Content, Moisture% & absence of any requiremnent for
pre-treatment; RBD Palm Stearin is the most widely converted feedstock to Biodiesel.
Some of the other key feedstocks that are readily available for conversion in India include
Animal Tallow, PFAD (Palm Fatty Acid Distillate), Non-edible Fractions of Vegetalbe Oils
such as Soyabean, Castor, Cottonseed & Used Cooking Oil.

1.2.1 Used cooking Oil application for Biodiesel Manufacturing

As per the National Policy on Biofuels- 2018, The Government of India has emphasized
on the use of indigenous feedstock for biodiesel production and identified Used Cooking
oil (UCO) as a potential source of biodiesel production. However, the same is marred by
diversion of UCO to edible stream through various small eateries/ vendors & traders.
Focus will be laid upon laying down the stringent norms for avoiding the re-entry of Used

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 Biodiesel Association of India

Cooking Oil back into the food stream and developing a suitable collection mechanism to
augment its supply for biodiesel production.
Used Cooking Oil (UCO) can be converted to Fatty Acid Methyl Esters (FAME), which has
fuel properties similar to crude based diesel and hence called Biodiesel. Thus, UCO is a
major source for the production of biodiesel.
As per the Food Safety & Standards Authority of India (FSSAI) notification - Used Cooking
Oil (UCO) with Total Polar compounds (TPC) more than 25% is hazardous for human
health. However, the UCO collection mechanism is in its nascent or developing stages in
India which needs to be encouraged by all stakeholders. There is little doubt that the
collection and subsequent conversion of the Used Cooking Oil to Biodiesel has huge
potential in India.
FSSAI has published several notifications (attached herewith) & a Gazzette dated 24th
October, 2017 stipulating the restrictions on re-use of Used Cooking Oil; clearly stating
that “Vegetalbe Oil having developed Total Polar Compound more than 25% shall not be
used”.
Guidelines laid down by the Food Safety & Standards Authority of India (FSSAI) on:
 Background note on Used Cooking Oil - Annexure 1.2
 Handling & Dispoal of Used Cooking Oil (Note no. 6/2018) – Annexure 1.3
 FSSAI launches RUCO (Repurposed Used Cooking Oil) on 10th August, 2018 which
is celebrated as World Biofuel Day – Annexure 1.4
 Cabinet approves National Policy on Biofuels- 2018 (Note dated 16th May, 2018).
The policy encourages setting up of supply chain mechanisms for biodiesel
production from non-edible oilseeds, used cooking oil & short gestation crops

1.2.2 End Note- UCO use and Pollution Potential

Handling and disposal of Used Cooking Oil is a huge problem. Considering this, an
assessment was taken up to study pollution potential during manufacture of Biodiesel
from UCO by various processes and findings are presented in the report below.

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 Biodiesel Association of India

2 B IOD IES EL MA NUFACT U RING

PROC ESS US ING U S ED CO OK ING OIL

2.1 Methodology adopted

Transformation of vegetable oil / used cooking oil into biodiesel can be done using-
Thermal cracking or pyrolysis, dilution or blending & the most economically efficient
process i.e. transesterification.
Lab scale transesterification reactions were carried out. Analysis of available feedstocks
has been done & results presented below. Also, Bottom layer generated during
transesterification process is analysed & results presented below.

2.2 Process details

2.2.1 Thermal cracking or Pyrolysis

Pyrolysis refers to the chemical change caused by the application of thermal energy in the
absence of air or nitrogen. The process involves conversion of the complex structure of
hydrocarbons into its simplest structure with or without a catalyst.
Generally; alumina, zeolite or redmud are used as catalysts in the thermal cracking
process for biodiesel production. The process will take place at a temperature above
250OC and upto 350OC.
The feedstock for conversion to biodiesel is taken into the reactor. Once the reactor is
loaded with the feedstock & catalyst; heat is then applied to the reactor. The feedstock
gets vaporized and reaches the condenser through a vertical column. The condenser cools
down the vapor converting it into its liquid form which is then collected in a receiver tank.
The condensate has a lower viscosity, flash point, and pour point as compared to diesel
fuel and has equivalent calorific value.
The biofuel generated from this process can be used directly in a diesel engine without
any modifications.
Disadvantages:
The processed vegetable oil contains acceptable amounts of sulfur, water and sediments
and gives low copper corrosion values but unacceptably high content of ash, carbon
residue and pour point. Additionally, this method is also not feasible due to its excessively
high heat generation requirement thereby making the process uneconomical for large
scale production.

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 Biodiesel Association of India

Figure 2.1 Process flow diagram- Thermal cracking or Pyrolysis

2.2.2 Dilution or Blending

The dilution of vegetable oils can be accomplished with materials such as diesel fuels,
solvent or ethanol. Dilution results in the reduction of viscosity and density of vegetable
oils. The addition of 4% ethanol to diesel fuel increases the brake thermal efficiency,
brake torque and brake power, while decreasing the brake specific fuel consumption.
Since the boiling point of ethanol is less than that of diesel fuel, it could assist the
development of the combustion process through an unburned blend spray.
Disadvantages:
This method is uneconomical due to the direct use of vegetable oil in the process. Further,
the use of ethanol which has a very low flash point makes the final product unsafe for
direct use or storage.

2.2.3 Transesterification

The feedstock oil is chemically reacted with an alcohol in the presence of a catalyst to
produce Biodiesel.
Transesterification reaction involves the formation of monoalkyl esters by a catalyzed
reaction of the triglycerides in the feedstock oil with a simple monohydric alcohol. The
reaction conditions generally involve a trade-off between reaction time and temperature;
as reaction completeness is the most critical fuel quality parameter. Purity of Methyl
Ester obtained from above process is approx. > 98%.

Detailed process of Simple Transesterification is as below:

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 Biodiesel Association of India

Among all these techniques, the transesterification is an extensive, convenient and the
most promising method for the reduction of viscosity, density and other properties of the
vegetable oils.
The transesterification process is done using Acid or Alkali catalyst or Lipase enzyme.
2.2.3.1 Alkali catalyst transesterification process:

The alkali catalyst transesterification process is a single step process due to which
reaction time is less than acid catalyst process.
- The alkali catalyst such as hydroxides or methoxides is added to the monohydric
alcohol to form sodium-hydroxide or sodium- methoxide;
- Simultaneously; the oil (feedstock) is heated in a separate vessel and mixed with
the catalyst-alcohol mix (sodium hydroxide or sodium methoxide). The reactor is
kept closed to prevent the loss of alcohol.
- The above mixture is then heated upto ~65°C with reaction time of 1 to 2 hours.
- After completion of the reaction; two distinct layers are formed- methyl ester as
top layer and the glycerol layer in the bottom. The glycerol layer is separated from
reactor by gravity separation.
- Excess alcohol from the ester & crude glycerol is recovered & reused in the next
batch of transesterification.
- The total time required to complete reaction is 6 to 8 Hrs.
- No process water requirement or effluent generation from process
It is a well known fact that Alkaline catalysts are less corrosive than Acidic compounds
and hence industrial processes usually favor alkaline catalysts such as alkaline metal
alkoxides and hydroxides as well as sodium or potassium carbonates.
Reaction:
Triglyceride + CH3OH KOH (0.8%) CH3(CH2)n COOCH3 + C3H8O3 + CH3(CH2)nCOOH

Stoichiometric reaction is as below,

850 kg + 192 kg KOH (0.8%) 833 kg + 92 kg + 98 kg + 19 kg
Oil (Palm (Methanol) (Methal Ester) (Glycerol) (Free/ Excess (Fatty Acid)
Stearin) Methenol)

Top layer Bottom layer

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 Biodiesel Association of India

Process flow diagram:

Figure 2.2 Process flow diagram- Alkali catalyst Trans esterification

Figure 2.3 Layer formation during Alkali catalyst Trans esterification

Feedstock taken for conversion: RBD Palm Stearin (RBD PS)
Typical Specifications of RBD Palm Stearin are as given below. GC analysis profile is
attached as Annexure 2.1.
Table 2.1 Feedstock analysis- RBD Palm Stearin

Sr. No. Parameters Unit Results Standard

1 Free Fatty Acid % 0.15 0.5 Max
2 Iodine Value --- 31.65 30-50
3 Melting Point OC 54.5 --

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 Biodiesel Association of India

4 Moisture % 0.25 0.5 Max

5 Colour --- Passes ---

Material Balance:
The typical material balance considering batch size of 100 kg input for biodiesel is as
below:
Mass balance for Alkali Trans-Esterification
(Basis: 100 kg/ batch Input)
Input quantity (kg/batch) Output quantity (kg/batch)
Triglyceride 100.00 Crude Methyl Ester 98.00
Methanol 22.58 Free/ Excess 11.52
Alkali Trans-
Methanol
esterification
Alkali Catalyst 0.75 Crude Glycerol 11.57
(0.75% of Triglyceride unreacted Fatty Acid 2.24
Weight)
123.33 123.33
Crude Methyl Ester 98.00 Excess Methanol 4.90
Drying of Methyl
recovered
Ester under
Biodiesel 93
Vaccum
98.00 98.00
Note: During alkali catalyst trans esterification; the bottom layer (containing crude
glycerol, unreacted fatty acid) is entirely organic in nature and is utilized for manufacture
of Refined Glycerine.
Chemical Analysis of Bottom layer:
Bottom layer generated during alkali catalyst transesterification is analyzed & results
were presented in Annexure 2.2.
In the alkali catalyst process; the bottom layer which is formed primarily consists of crude
glycerol, excess methanol and unreacted fatty acids. There is No Effluent generation
during alkali transesterification process.
Table 2.2 Analysis of Bottom Layer generated during Alkali Transesterification

Test Parameter Result Unit Method

pH 9.75 -- IS:3025 (Part-11): RA2017

Methanol Content 4.80 ppm GCMS-Headspace

Glycerol Content 52.10 % By Titration

Free Fatty Acid 1.01 Mg of KOH/gm By Titration

Total Fatty Matter 35.2 % By Gravimetry

MONG Content 11.0 % By Calculation

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 Biodiesel Association of India

Observation:
During this process of of Alkali Catalyst transesterification process, no effluent or
hazardous waste is generated.
2.2.3.2 Lipase enzyme transesterification process:

The Lipase enzyme transesterification process is similar to the Alkali catalyst process.
The only difference in the process is reaction time & temperature.
- The Lipase Enzyme- Alcohol mixture is slowly added to feedstock oil in the reactor
while maintaining the atmospheric temperature of 40°C.
- Alcohol dosing is done continuously for a period of 24 Hrs into reactor to ensure
complete breakdown of Free Fatty Acid (FFA) content in oil.
- The reaction temperature is increased upto 50°C to eliminate the Lipase enzyme.
- After completion of the reaction; two distinct layers are formed- methyl ester as
top layer and the crude glycerol layer in the bottom. The glycerol layer is separated
from reactor by gravity separation.
- Excess alcohol from the ester & crude glycerol is recovered & reused in next batch
of transesterification.
- The total time required to complete reaction is 30 to 32 Hrs.
The advantage of Lipase enzyme transesterification process is as below
i. Feed Stock Flexibility
- Enzyme works independent of FFA% in Oil
- Acid esterification & Alkali Trans-esterification takes place simultaneously
ii. Improved Glycerol content
- Lower amount of salts & colour compared to chemical process
- Higher content of Glycerol
iii. Lower Energy Consumption
- Lower reaction temperature at 40°C
- No need to dry the feedstock
- Replacing 2 step process of Acid & alkali catalyst reaction (single ‘’One Pot’’
reaction).
iv. Pollution free process
- Entirely replaces Sulphuric acid in the acid catalyst process
- Eliminates traces of sulphur in methyl ester & Glycerol phase
- No water requirement in process & no effluent generation from process

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 Biodiesel Association of India

Reaction:
Triglyceride + CH3OH Lipase (0.3%) CH3(CH2)n COOCH3 + C3H8O3 + CH3(CH2)nCOOH

Stoichiometric reaction is as below,

850 kg + 192 kg Lipase (0.3%) 833 kg + 92 kg + 98 kg + 19 kg
(Used Cooking (Methanol) (Methal Ester) (Glycerol) (Free/ Excess (Fatty Acid)
Oil) Methenol)

Top layer Bottom layer

Process flow diagram:

Figure 2.4 Process flow diagram- Lipase enzyme Trans esterification

Figure 2.5 Layer formation during Lipase enzyme Trans esterification

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 Biodiesel Association of India

Feedstock taken for conversion: Used Cooking Oil (UCO)

Typical Specifications of Used Cooking Oil are as given below. GC analysis profile is
attached as Annexure 2.3.
Table 2.3 Feedstock analysis- Used cooking oil

Sr. No. Parameters Unit Results Standard

1 Free Fatty Acid % 1.05 2.0 Max
2 Iodine Value --- 60 55-90
3 Melting Point OC 12 --
4 Moisture % 1 1.5 Max
5 Colour --- Passes ---
Material Balance:
The typical material balance considering batch size of 100 kg input for biodiesel is as
below:
Mass balance for Lipase enzyme Trans-Esterification
(Basis: 100 kg/ batch Input)
Input quantity (kg/batch) Output quantity (kg/batch)
Triglyceride 100.00 Crude Methyl Ester 98.00
Methanol 22.58 Free/ Excess 11.52
Lipase Trans-
Methanol
esterification
Lipase Enzyme 0.75 Crude Glycerol 11.57
(0.75% of Triglyceride unreacted Fatty Acid 2.24
Weight)
123.33 123.33
Crude Methyl Ester 98.00 Excess Methanol 4.90
Drying of Methyl
recovered
Ester under
Biodiesel 93
Vaccum
98.00 98.00
Note: During Lipase catalyst trans esterification; the bottom layer (containing crude
glycerol & unreacted fatty acid) is entirely organic in nature and is utilized for manufacture
of Refined Glycerine.
Chemical Analysis of Bottom layer:
Biodiesel generated from Lipase enzyme transesterification is analyzed & results were
presented in Annexure 2.4.
In this process; the bottom layer which is formed primarily consists of crude glycerol,
excess methanol and unreacted fatty acids. There is No Effluent generation during the
Lipase Enzyme transesterification process.

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 Biodiesel Association of India

Table 2.4 Analysis of Bottom Layer generated during Lipase transesterification

Test Parameter Method Unit Result

pH IS:3025 (Part-11): RA2017 -- 8.34

Methanol Content GCMS-Headspace ppm 5.34

Glycerol Content By Titration % 48.0

Free Fatty Acid By Titration Mg of KOH/gm 0.835

Moisture Karl Fischer % 3.5

Total Fatty Matter By Gravimetry % 35.0

MONG Content By Calculation % 11.5

Observation:
During this process of Lipase Enzyme transesterification process; no effluent or
hazardous waste is generated.
2.2.3.3 Acid catalyst transesterification process:

The acid catalyst transesterification process is a two step process.

i) Acid addition ii) Neutralization with alkali
- The high Free Fatty Acid (FFA) content oil is treated with an acid catalyst (such as
Sulphuric Acid (H2SO4) resulting in the breakdown of FFA into ester.
- Simultaneously, the alkali catalyst is added to the monohydric alcohol to form
sodium-hydroxide or sodium- methoxide. The ester obtained from step no. 1 is
neutralized with the alkali catalyst-alcohol mixture;
- The reactor is kept closed to prevent the loss of alcohol.
- The above mixture is then heated upto ~65°C with reaction time of 1 to 2 hours.
- After completion of the reaction; two distinct layers are formed- methyl ester as
top layer and the glycerol layer in the bottom. The glycerol layer is separated from
reactor by gravity separation.
- Excess alcohol from the ester & the bottom layer (crude glycerol) is recovered &
reused in the next batch of transesterification.
- The total time required to complete reaction is 8 to 10 Hrs.
The acid-catalyzed transesterification must be carried out in the absence of water in
order to avoid the competitive formation of carboxylic acids which reduces the yield of
the alkyl esters.
Reaction:
CH3 (CH2)nCOOH+ CH3OH H2SO4 (3-4%) CH3(CH2)n COOH + H2O + Unreacted fatty acid/ UNSAP/ salts

Stoichiometric reaction is as below,

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 Biodiesel Association of India

265.5 kg + 64 kg H2SO4 (3-4%) 252.94 kg + 35.04 kg + 16.29 kg + 25.23 kg

(Fatty Acid) (Methanol) (Methyl Ester) (Free/ Excess (water) (Unreacted Fatty
Methenol) acid/ UNSAP/ polar
matter/ salts etc

Top layer Bottom layer

Process flow diagram:

Figure 2.6 Process flow diagram- Acid catalyst Trans esterification

Feedstock taken for conversion: PFAD (Palm Fatty Acid Distillate)

Typical Specifications of Palm Fatty Acid Distillate are as given below. GC analysis profile
is attached as Annexure 2.5.
Table 2.5 Feedstock analysis- Palm Fatty Acid Distillate

Sr. No. Parameters Unit Results Standard

1 Free Fatty Acid % 84.21 70 Min
2 Iodine Value --- 52.26 50-55
3 Mineral Acidity Absent Nil Abdsent
4 Moisture % 0.25 1.0 Max
5 Colour --- Passes ---
6 UNSAP % 1.22 2.0 Max
Material Balance:
The typical material balance considering batch size of 100 kg input for biodiesel is as
below:

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 Biodiesel Association of India

Mass balance for Acid Trans- Esterification OR Fischer Esterification

(Basis: 100 kg/ batch Input)
Input quantity (kg/batch) Output quantity
(kg/batch)
Fatty Acids (PFAD) 100.00 Crude Methyl 95.27
Ester
Methanol 24.10 Free / Excess 12.72
Methanol
Acid Catalyst (H2SO4) 4.00 Acid Trans- Water (Formed 6.13
(4% of Fatty Acid esterification during Reaction)
Weight) Unreacted Fatty 13.50
Acid / UNSAP /
Polar Matter /
Salts etc
Methanol loss 0.48
128.10 128.10
Crude Methyl Ester 95.27 Excess Methanol 3.81
Drying of Methyl
recovered
Ester under
Biodiesel 91.46
Vaccum
95.27 95.27
Note: During the acid transesterification process, the bottom layer (containing water
generated from the reaction as well as glycerol, unreacted fatty acid/ Unsaponifiable/ Polar
matter & salts) has pH< 2 and is utilized for the manufacture of Refined Glycerine.
Chemical Analysis profile:
Bottom layer generated from acid catalyst transesterification is analyzed & results were
presented in Annexure 2.6.
The bottom layer generated during acid catalyst transesterification process with PFAD as
feedstock is analysed & results are presented below:
Table 2.6 Analysis of water generated during Acid transesterification

Parameter Unit Result Test method

pH -- < 1.0 IS3025 (part 11) (RA 2017)

BOD mg/l < 10 IS3025 (part 44) (RA 2014)

COD mg/l 85000 IS3025 (part 58) (RA 2017)

Water content % 32.9 Karl fisher

Acidity as H2SO4 % 11.9 Titration method

Oil & Grease % 1.12 Gravimetry

Chloride mg/l 69 IS 3025 (Part-32)

Sulphate mg/l 39300 IS 3025 (Part-24)

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 Biodiesel Association of India

Above results shows that the reaction water generated during acid transesterification has
high COD values mainly due to glycerol & methanol interference. Reaction water
generated during process needs further treatment.
Observations:
During process of Acid Catalyst transesterification, effluent & salts are generated during
reaction.
During Acid Catalyst transesterification, high amount of sulfur is generated due to
addition of acid catalyst.
From the above results it is seen that water generated during acid catalyst reaction needs
to be treated before disposal thereby making the use of an ETP mandatory.

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 Biodiesel Association of India

3 EVALUAT ION OF CAT EG O RIZAT ION

3.1 Evaluation of Categorization as per CPCB guideline

The pollution index has been calculated considering the Biodiesel manufacturing plant
capacity of 100 TPD by following only the Alkali catalyst transesterification process &
Lipase Enzyme transesterification process.

3.1.1 Water requirement & Effluent generation

Fresh water requirement:

Fresh Water is used for Domestic, Cooling & Boiler operations. No fresh water is required
in reaction process.
The total water requirement is as below:
Domestic- 2.0 cmd
Cooling & Boiler operations- 5.0 cmd
Effluent generation:
Effluent generation is mainly from domestic use and cooling & Boiler blowdown. There
is no effluent generation from alkali & lipase transesterification process.
Total effluent generation is as below:
Domestic sewage- 1.0 cmd
Cooling & Boiler operations- 1.2 cmd
As per Water pollution scoring methodology our waste water falls into score as below:
W1- Score based on types of expected criteria water-pollutants present in industrial
processes waste waters
W15- Waste water generated from the physical unit operations / Score- 12
processes and which is polluted due to presence of TDS (total dissolved
solids) of inorganic nature and of natural origin like fresh-water RO
rejects, boiler blowdowns, brine solution rejects etc.
W17- Waste water from cooling towers and cooling-re-circulation Score- 10
processes
W1= 22

W2- Score based on huge discharges of any kind- Not applicable.

W2= 0

Hence, Overall Water Pollution Score

W = W1+W2
W = 22 + 0
W = 22

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 Biodiesel Association of India

The total water pollution score is 22.

3.1.2 Fuel requirement & emission

To complete reaction, desired temperature is maintained in reactor by providing steam

from diesel fired boiler. The proposed boilers considered are as below-
2 nos. of 850 kg/ Hr fired boiler
HSD- 4800 lit/ day
2 nos. of 600 kg/Hr fired boiler
Since HSD is having low content of Sulphur & particulate matter, the pollutant emissions
are low.

Considering above,
As per Air Pollution Scoring methodology, our air pollution scenario falls into score as
below:
A1 = Score based on types of expected criteria Air Pollutants present in the emissions.
Group A1D- Presence of criteria air pollutants having prescribed 15
standard from 51 to 250 mg/Nm3
A1 15

A2 = Score based on consumption of fuels and technologies required for air pollution control
A2= 0

Hence, Overall Air Pollution Score

A = A1+A2
A = 15 + 0
A = 15
The total Air pollution score is 15.

3.1.3 Hazardous waste generation

Hazardous waste generated from project is mainly contaminated containers, waste oil
generated from equipment handling & maintenance.

Considering above,
As per Hazardous Waste Generation Scoring methodology, our hazardous waste falls into
score as below:
HW4- Recyclable HW, which are easily recyclable with proven 10
technologies

The total Hazardous waste score is 10.

From the above calculations the overall pollution score for Industries
manufacturing Biodiesel from simple Alkali catalyst Transesterification & Lipase
Enzyme Transesterification will be as below:

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 Biodiesel Association of India

Total score= W + A + HW
= 22 + 15 + 10
= 47

As per the CPCB “Guidelines of Revised Classification of Industrial Sectors, 29th February
2016” if the Pollution Index scores from 30 to 59, then the industry should be categorized
as ORANGE category.

From above calculations, total score is 47 hence it is concluded that Industries

manufacturing Biodiesel from simple Alkali catalyst Transesterification & Lipase
Enzyme Transesterification falls under ORANGE category.

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 Biodiesel Association of India

4 CO NC LUS IO N

4.1 Conclusion

 The primary feedstock which is used cooking oil/ Waste cooking oil is currently
considered to be a health hazard if consumed by humans.
 By reprocessing the UCO into Biodiesel; an alternate use is created which acts as
a substitute for fossil fuel with a carbon neutral impact on the environment.
 The transesterification method is a well-accepted, universal & environmentally
safe method of making Biodiesel which is a cleaner and environment-friendly fuel.
 Biodiesel being bio-degradable, it is safe to produce and store due to high flash
point (> 101OC).
 The alkali catalyst & Lipase enzyme transesterification reaction does not generate
any Hazardous waste/ Effluent generation / Residue generation from the process
& gives maximum yield of Biodiesel as compared to acid catalyst
transesterification.
 There is no water requirement in the entire process hence there is no waste water
generation during Alkali catalyst Transesterification & Lipase Enzyme
Transesterification.
 From the above report, it is concluded that Industries manufacturing Biodiesel
from simple Alkali catalyst Transesterification & Lipase Enzyme
Transesterification falls under ORANGE category.

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