FINAL REPORT

National Agricultural Innovation Project

(Indian Council of Agricultural Research)

A Value Chain on Castor and Its Industrial Products

A Value Chain on Castor and Its Industrial Products

Main Castor Mustard Research Station

Sardarkrushinagar Dantiwada Agricultural University
Sardarkrushinagar-385506 Distt. Banaskantha Gujarat

Component-
II 2012

2012
 1

“A Value Chain on Castor and Its Industrial Products”

, ,
, ,
, ,
. , ,
,
, -
, .
, 2009
2012 2000
Gangudara, Chodungari,
Kamali, Matpur Garamadi ( )
15.7 23.9 , ,
. 2011 2012 Gangudara, Chodungari, Kamali, Matpur
Kasalpura
, 37.6 .

GCH ,
.

, -
12 HAS
hydrolic > ,

ricinoleate ,
,
 2

LLE ricinoleate

LLE ricinoleate

N-undecenylethanolamine N,N-diundecenylethanolamine
. N-undecenylethanolamine UDA
ethanolamine

N,N-diundecenylethanolamine UDA ethanolamine

micellar
UDA Quats, N,N-Dimethyl diethanolamine
diundecenoate dimethylsulphate
sodium bisulphate monohydrate
Quats
octanol . octanol
.
Deoiled
.
ricin Deoiled

Deoiled ricin
 3

Executive Summary
The project entitled “ A Value Chain on Castor and Its Industrial Products” under NAIP
component II was undertaken by Sardarkrushinagar Dantiwada Agricultural University,
Sardarkrushinagar (Consortia lead Centre), Indian Institute of Chemical Technology, Hyderabad
(CSIR, Institute) and Jayant Agro Organics Ltd.; Mumbai (Private sector), Royal Castor Products,
Siddhpur (Private sector). SDAU, Sardarkrushinagar, the lead centre, is most prestigious research
station engaged in castor agro-research and development. This centre has been credited to
develop six castor hybrid, two castor varieties and production/protection technology for castor
cultivation.
After base line survey of six districts of north Gujarat, in three years two thousand four hundred
demonstrations comprising about 2000 under irrigated and 400 under rainfed conditions
demonstrating different agro-techniques were conducted on farmer’s field during 2009-2012.
Through field demonstration: Total 465 farmers’ field demonstrations were conducted during
2009-10. The yield level of selected villages viz. Gangudara, Chodungari, Kamali, Matpur, and
Garamadi (rainfed) was 19-21, 23-25, 31-33, 33-34 and 6-8 q/ha, respectively. Through the agro
technological demonstration, the results indicated that the range of increase in seed yield of castor
in different selected villages was 15.7 to 23.9 percent. On an average, the magnitude of increase
in yield over present level was 34 percent which was 11.8 per cent more than targeted yield.
During 2011-12 total 672 demonstrations were conducted. The yield level of selected villages viz.
Gangudara, Chodungari, Kamali, Matpur, and Kasalpura was 19-21, 23-25, 31-33, 33-34 and 35-
40 q/ha, respectively. On an average, the magnitude of increase in yield over present level and
targeted yield was 37.6 per cent, respectively.
For value addition in the harvesting and processing it was found that The local sickle, improved
sickle and secator were evaluated for efficient harvesting of castor crop (variety: GCH-7) and
minimum losses. The average harvesting capacity of castor spike was found 65.90 kg/hr for
secator followed 52.99 and 51.24 kg/hr for improved sickle and local sickle respectively. The
higher percent losses were observed for improved and local sickles as compared to secator. Solar
dryer is more suitable for drying of castor crops drying was found 6 to 7 days earlier as compared
to traditional drying method. On the basis of demonstration of farmer's field single groove planter
was found most suitable for sowing castor crop sown at fixed crop geometry.
In order to specific to value chain, various esters were prepared and evaluated with 12 HAS. The
product was made with great efforts, the hydroxyl value of final product was Zero (High hydrolic
stability) and viscosity of > 42. The technical specification of the ester developed was finalized.
Enrichment of Methyl Ricinoleate from Castor Oil Methyl Esters:
 4

Using liquid paraffin as a medium, the selectivity in enrichment of methyl ricinoleate from castor
oil methyl esters is good but due to the closer densities of liquid paraffin and aqueous methanol
the contamination of liquid paraffin with the solute was to the extent of 2.5-3.5% which was
determined by TLC and column chromatography. Therefore, the experiments using liquid
paraffin as medium in enrichment of methyl ricinoleate by LLE is not satisfactory.
The method of using refined vegetable oil as medium in enrichment of methyl ricinoleate by
LLE, the selectivity is good and the contamination of oil with solute is less than 0.8% as
determined by TLC and column chromatography. Efforts are on at further minimizing the
contamination. Standardization of up-scaling experimental conditions are in progress. Efforts are
on to explore the possibilities of separation of solute from extract using solvent resistant thin film
composite reverse osmosis membranes. Using the enriched methyl ricinoleate various derivatives
are planned to prepare and compare the properties with respect to the CME. Experiments are in
progress to standardize the experimental conditions.
Further upscaling experiments are being conducted for the enrichment of methyl ricinoleate from
castor oil methyl esters. Adsorbents like celite will be tried in reducing the vegetable oil
contamination in the extract. Centrifugation is another option to be explored in minimizing the
vegetable oil contamination. Thin film composite RO membranes will be explored in separation
of the solute from the solvent of the extract in liquid-liquid extraction process. Efforts are on in
increasing the conjugation in the dehydrated products and methodology for evaluation of
conjugated fatty acid esters in the products by HPLC and Silver ion Thin layer chromatography.
Design and fabrication of Liquid-liquid extraction set-up is under progress.
Preparation of UDA-based Surfactants: Optimized conditions for exclusive preparation of N-
undecenylethanolamine and N, N-diundecenylethanolamine. N-undecenylethanolamine was
prepared by taking 1:1 molar ratio of UDA and ethanolamine and heating the reaction mixture at
170 °C for 2 hrs. The structure of the compound was confirmed by NMR, IR and mass. The cmc
and surface tension at cmc was determined following Kruss Tensiometer. The cmc value was
found to be 3.08×10-4 mM and surface temsion at cmc, is 30.7 mN/m. N,N-
diundecenylethanolamine was prepared by taking 3:1 molar ratio of UDA and ethanolamine and
heating the reaction mixture at 170 °C for 2 hrs. Attempts to determine the micellar properties of
this compound failed as the compound is almost insoluble in water.
UDA-based ester quats, N, N-dimethyl diethanolamine diundecenoate dimethylsulphate was
prepared by esterification in presence of 5% sodium bisulphate monohydrate at 120 °C under
stirred conditions. The cmc value of the ester quat was found to be 3.0 × 10 -2 mM/L and surface
tension at cmc, is 25.46 mN/m. Four UDA-based surfactants are synthesized and evaluated for
their surface properties using surface tension and fluorescence probing techniques. Influence of
 5

the presence of unsaturation and also its location in the hydrophobic chain on surface properties
of four different ester quats are also studied.
Value added products based on the 2-octanol like phthalate, maleate, fumarate, sebacate, adipate,
benzoate and these can be used as plasticizers in PVC and resins for various applications. 2-
octanol is co-product of the castor industry and based on its such value added products will earn
good returns to the stakeholders. Based on the estimation, the 2-octanol based esters as
plasticizers will be cheaper than the existing products based on 2-ethyl hexanol and isononanol.
Developed process technologies for esters based on 2-octanol will be able to replace petroleum
derived products thus increasing the value of the castor plant & indirectly benefit the farmers due
to increased demand.
Deoiled castor cake is also a co-product of castor industry and it has rich content of protein. Apart
from this it also comprises of other constituents. One of the constituents of castor cake is found
very toxic. Due to this the deoiled castor is not used as foodstuff for live stock in spite of rich
amount of protein. The developed process of extraction and isolation shows the protein from
castor deoiled cake is free from toxic component i.e. ricin. Hence such isolated protein can be
used for industrial applications like adhesive and bio-film and can be partially or fully replaced
by soy protein isolate as this is being used in the food products. Also could be considered for feed
purpose after satisfactory trials
Value addition in castor cake: Among, Fifty one castor genotypes analysed, the protein content
varied from 19.93 to 30.81%. Maximum protein content was noted in GP-415 (30.81%)
genotype. Thirty six castor genotypes were analysed for protein isolation from cake. The protein
isolated from different genotype varied from 11.05to 19.35%. Among all the genotypes, GP-422
(19.35 %) recorded maximum isolated protein content. Thirty seven castor cake samples were
analysed for crude ricin ranging from 1.03-1.92 % in the different DOC samples. GP-420 (1.03
%) showed lowest toxic constituents and GP-460 (1.92%) had the highest toxic constituents.
After the series of treatments for detoxification, resulted in traces or undetectable levels of toxic
constituents were observed. Eighteen castor genotypes were analyzed for lignin and cellulose
content of stem by chemical method. The lignin and cellulose content was noted in the range of
14.1 to18.8 and 34.9 to 45.7% respectively.

Key Words: Castor, Value addiction, Value Chain, Ricinolic acid, Ricin, castor
derivatives
 6

Part-I: General Information of Sub-project

1. Title of the sub-project: “ A Value Chain on Castor and Its Industrial Products”
2. Sub-project code:
3. Component: 2 (Production to Consumption System)
4. Date of sanction of sub-project: February 18, 2009
5. Date of completion: June 30, 2012
6. Extension if granted, from: Nil
7. Total sanctioned amount for the sub-project: 393.00 lakh
8. Total expenditure of the sub-project:
9. Consortium leader: S. D. Agricultural University, Sardarkrushinagar 385 506
Dr. K. Sreedharan, Vice Chancellor
S. D. Agricultural University, Sardarkrushinagar 385 506
Phone: 02748 278457 Phone: 02748 278457
E-mail: vc@sdau.edu.in
website: http://www.sdau.edu.in
10. List of consortium partners:
Name of CPI/ CCPI Name of organization and Duration Budget
with designation address, phone & fax, email (From-To) (Lakhs)
CPI Dr. P. S. Patel, Main Castor-Mustard Research
Research Scientist Station, SDAU, March 1, 2009
(C&M) S. K. Nagar (Gujarat) to June 30, 266.127/-
Phone: 02748 278457 2012.
pspatel8181@gmail.com
CCPI1 Dr. R.B.N. Prasad, Centre for Lipid Research, March 1, 2009
Director Indian Institutes of Chemical to June 30, 61.8384
Technology, Hyderabad, (AP) 2012.
CCPI2 Dr. Subhash V. M/s.Jayant Agro-Organics Ltd.
40.88430/-
Udeshi. 38 Marol Co-op. Ind. Estate
March 1, 2009 (39.2112/-
Director – Technical Off M. V. Rd, Sakinaka,
to June 30, sanctioned
Andheri(E), Mumbai-400059
2012. letter dated
Tel: 022-40271300 – 314-15
on Feb. 18,
Fax: 022-40271399:
2009)
subhash.udeshi@jayantagro.com
CCPI 3 Dr. Subhash Polara M/s Royal Castor Products Limited
Director, At. Khali, Mehsana – Sidhpur
March 1, 2009
Royal Castor Product Highway, Sidhpur-384151, Dist –
to June 30,
Limited. Patan, Gujarat. 24.9096
2012.
Phone : 02767 – 222905-06,
Fax:02767- 221833 E-mail :
polarasubhash@royalcastor.in
CPI-Consortia Principal Investigator; CCPI-Consortia Co-Principal Investigator
 7

11. Statement of budget released and utilization partner-wise (in Lakhs):

CPI/ CCPI Total budget Fund released Fund utilized

Name, sanctioned (up to closing date) (up to closing
designation date)
& address)
CPI Dr. P. S. 266.127/- 208.75116/- 143.07207/-
Patel,
Research
Scientist
CCPI1 Dr RBN 61.8384/- 51.15588/- 41.91817/-
Prasad,
Director, IICT

CCPI2 Dr. Subhash 40.88430/- 23.73524/- 23.49770/-

V Udeshi. (39.2112/- as
Director – per sanctioned
Technical letter dated on
Feb. 18, 2009)

CCPI 3 Mr. Subhash 24.9096/- 17.43336/- 19.67142/-

Polara
Total 393.7593/- 301.0756/- 228.1594/-
CPI-Consortia Principal Investigator; CCPI-Consortia Co-Principal Investigator
 8

Part-II: Technical Details

1. Introduction
Castor (Ricinus communis L) is a non edible oil seeds crop having high industrial
importance due to presence of unique fatty acid, ricinoleic acid. India is the world leader
in castor seed and oil production and contributes about 55 % of world castor area and
70% of world castor production. In India, Gujarat state holds the first ranks with regards
to area (52 %), production (80 %) and productivity (1833 kg/ha, 2009-10). Other
important states are Rajasthan and Andhra Pradesh. The crop is grown mainly under
irrigated condition in Gujarat and Rajasthan. The castor crop productivity is low due to
various biotic and a biotic factors amongst these wilt caused by Fusarium oxysporium is
the major constraints beside this partial/improper adoption of recommended technology
also led to low productivity of castor.
The adoption of recommended production/protection technologies, are essential to
increase productivity of castor. At present recommended technologies are being adopted
partially or not adopted like application of recommended dose of fertilizer, application of
sulphur, irrigation schedule , spacing and harvesting etc.
The castor seeds produce after harvesting is not properly cleaned and dried, packing
material used are mostly gunny bags and also contains foreign materials like iron nails,
dust, stone etc., such poor quality produce gets less prices for farm produce. The
improved technology for drying cleaning, grading and bulk packaging will improve the
quality of raw material for industrial supply and increase the farmer’s income.
Castor plant grows in tropical, sub-tropical and warm temperate regions, preferring a dry
environment. It is cultivated both as an annual and a perennial, the size of plant and yield
of beans per acre showing very large variation according to cultivation. Castor oil is
obtained by pressing or pressing followed by solvent extraction. Oil content of the beans
averages 45-55%. Pharmaceutical grade oil is highly quality oil derived solely from the
first pressing of beans and account for only a very small percentage of total sales.
India is now the most important producer and its share of world castor oil production has
increased from 46.7 % in 1990 to 64.4 % in 1995. The other castor producers in the rest
of world are Brazil and China. Castor oil is unique in having three reactive functional
groups such as double bond, hydroxyl group and carboxylic group. Pyrolysis of castor oil
or recinoleic acid in the presence of alkali yields 2-octanol and sebacic acid. These
 9

oleochemicals are precursors for industrially important plasticizers, surface coatings and
perfumery chemicals.
The residue left behind after extraction of oil is called as deoiled cake or meal. Such cake
is predominantly consisting of proteins, minerals, fibers, etc. However this cake is not
consumed by animal owing to contents of the toxic compounds. Therefore it’s being used
as manure. Since some chemical or heat treatments over come the effect of toxin
henceforth it would be consumed by both poultry and animals. Moreover, the amino acid
profile of the deoiled castor cake is same as soy cake, but difference in their proportions.
The castor deoiled cake contains about 32 % proteins whereas in soy deoiled cake 47 %.
Soy protein isolate or concentrate are being used in various industries such as food,
pharmaceutical, adhesive, furniture, etc. The similar applications can be achieved except
food and pharmaceutical by using castor protein isolate and concentrate following the
same methodologies, which is used for isolation of protein from soy deoiled cake.

2. Overall Sub-project Objectives

1. Production: To increase farmer’s income and castor productivity through
popularization of latest high yielding castor hybrid and its agronomic practices
and innovative farming.
2. Processing: To develop post harvest handling and processing technologies to
improve quality of produce and reduce losses.
3. By-product value addition: To develop products from castor cake (by products of
castor oil extraction) for higher benefit of castor oil extraction units and farmers.
4. Specific to value chain: To develop higher generation castor oil based derivatives
for promotion of export and benefit of all stakeholders.

Sub-project Technical Profile
Output Deliverables Targets
To prepare the Esters like
DCP, DCS, DCM, DCF,
DCA and CB with high (10-12 M)
purity (>99%) and light
color appearance
Performance evaluation of
DCP and DCS against the
(12-14 M)
DEHP and DINP in PVC
formulation
Performance evaluation of
DCM , DCF, DCA and CB
against existing plasticizers
(14-20 M)
(esters) based on 2EH and
isonanol in PVC formulation
and other resins
To prepare and obtain
maximum conversion of 2-
octanol into symmetrical (22-25 M)
(DCE) and asymmetrical
(CGE) ethers
To extract and isolate protein
from deoiled castor cake:
Optimization of the process
parameters for extraction and
isolation of the proteins: (1-12 M)
Comparison studies for film
and adhesive based on CPI ,
SPI and a combination of
CPI and SPI
Trial batch of the proteins
extraction and isolation (20-24 M)
using Ultrafiltration Process
In a proposed investigation, the 2-octanol obtained from alkali fusion of ricinoleic acid, and
protein enriched deoiled castor cake are used to develop value added products.
10
Achievements
Processes have been standardized to prepare DCP,
DCS, DCM, DCF, DCA & CB with consistent quality
>99% conversion of PAN/SA/MAN/FA/AA/BA was
achieved
Completed work as per targeted
Results indicate that DCP & DCS can replace
partially/completely DEHP and DINP in PVC
formulations
Performance evaluation work is delayed as per the
target owing to some practical problems.
Enough quantity of esters are prepared for
performance evoluation
Prepared refined Dicapryl ether alongwith co-product
2-octene which can be used for diluents, surfactants,
etc.
Capryl Gycidyl Ether is under preparation and this
will have application in reactive diluents and
intermediate for specialty surfactants
97 % of protein extractability of protein was achieved
62 % protein isolated from extract
No ricin toxic constituent was found in CPI
No loss of protein on neutralization of extract with
acid and followed by drying. Could be Castor protein
concentrate
Process optimization work was completed as per
target.
The proteins isolation on large scale was delayed
owing to some practical problems (lack of filtration
media)
Carried out large size batch of protein extraction from
DCC using optimized process parameters
97 % of protein extractability of protein was achieved
Protein enrichment in concentrate using UF found 4-5
time more than initial
No ricin was detectable in CPI & this protein could be
a source of animal/poultry/fish feed after proper trials
 11

3. Baseline Analysis
 In six districts of SDAU, Jurisdiction farmer’s income is very less. After
NAIP demonstration and training programme farmers’ income increases 27
per cent under uses of different production technology viz., intercropping,
High yielding variety, drip irrigation system uses.
 Farmer’s maximum losses in harvesting technique. After NAIP project
implementation farmers preferred improved sickle and secator uses.
 The castor crop sowing method was mainly traditional but after NAIP project
progress farmers adopted castor planter that found more suitable.
 Earlier the maximum farmers were sowing of existing variety but after NAIP
progress they sown hybrid high yielding variety of castor.
 12

Research Achievements
5.1 Research Achievements of Main Castor Mustard Research Station, SDAU,
Sardarkrushinagar

Improved agro techniques developed for castor cultivation were demonstrated at farmers
field viz.-
Wilt resistant variety: Propagation of newly recommended wilt resistant hybrid
GCH 7.
Drip Irrigation: Drip irrigation system is demonstrated and created awareness to
apply irrigation at requiring intervals.
Sulphur application: Sulphur is essential element for oil synthesis and seed yield
and oil content increases with sulphur application.
Proper stage and means of harvesting: Spikes should be harvested when ½ of the
total capsules appear yellow, harvesting at this stage minimize the shattering losses.
When spikes are cut with sickle, some of the dry capsules shatter and results in low
yield. Using the secater is effective tool for harvesting, which reduce the
harvesting losses.
Intercropping with castor: Irrigated castor is planted at wider spacing and takes
240-270 days for complete harvesting. Pulses and cotton crop are recommended
as intercropped in castor. This practice is beneficial to farmers to increase income
per unit area.
Results of field demonstration:
In 2009-10, farmers’ field demonstrations were conducted in five selected villages to
demonstrate the recommendation practices. At the time of implementation of project,
present yield level of the villages was surveyed. The yield level of selected villages viz.
Gangudara, Chodungari, Kamali, Matpur, and Garamadi (rainfed) was 19-21, 23-25, 31-
33, 33-34 and 6-8 q/ha, respectively. Considering the present yield level the target for
increased the yield level for different villages were fixed. The results indicated that the
range of increase in seed yield of castor in different selected villages was 15.7 to 23.9
percent. On an average, the magnitude of increase in yield over present level was 34
percent which was 11.8 per cent more than targeted yield (Table 5.1).
 13

Table 5.1: Average yield, expected yield and actual yield of five selected villages

Village Present yield Targeted yield Actual yield Increase over

status received (q/ha) present yield
(q/ha)
(q/ha) (%)

Gangudara 19-21 23-25 28.18 20.0

Chodungari 23-25 28-30 28.78 20.8

Kamali 31-33 35-37 40.73 12.5

Matpur 33-34 38-40 42.50 16.4

Ratanpur 32-35 40-42 49.38 23.9

Garamadi 6-8 10-12 11.54 15.7

25 30 (20 %) 34.0
 14

Field demonstration on demonstration of varietal response:

About 148 farmers were selected to demonstrate the response of newly released wilt resistant and high yielding hybrid GCH 7 in five
selected villages. The results indicated that the magnitude of increase in seed yield under GCH 7 was varied from 17.5 to 33.9 per
cent in different villages over local hybrids/varieties (Table 5.1.1). On an average GCH 7 produced 23.2 per cent higher seed yield
and31.0 per cent higher net returns over local one.

Table 5.1.1: Demonstration of varietal response

Name of village Yield (kg/ha) Total income (Rs/ha) Cost of Net income (Rs/ha) % higher
cultivation over local
GCH 7 Local GCH 7 Local GCH 7 Local
(Rs/ha) yield

Gangudara 2212(24) 1825 (25) 61936 51100 21733 40203 29367 21.2

Chodungari 2878 (39) 2150 (25) 80597 60200 26031 54566 34169 33.9

Matpur 3656 (18) 3050(25) 102368 93800 31847 70521 61720 19.9

Kamali 3506(25) 2985 (25) 98168 83580 30086 68082 53493 17.5

Garamadi 926 (42) 750 (25) 25928 21000 11840 14088 9160 23.5

2636 2152 49486 37782 (31.0) (23.2)

 15

Field demonstration on demonstration of varietal response:

About 281 farmers were selected to demonstrate the response of sulphur on castor in five selected villages. The results indicated that
the magnitude of increase in seed yield with sulphur application was varied from 16.2 to 27.4 was recorded with sulpuur application
over control (Table 5.1.2). On an average application of sulphur recorded 21.1 per cent higher seed yield and 27.9 per cent higher net
returns over control field.

Table 5.1.2: Demonstration of response of Sulphur

Name of Yield (kg/ha) Total income (Rs/ha) Cost of cultivation Net income (Rs/ha) % higher
(Rs/ha) yield over
village without S
With S Without S With S Without S With S Without S With S Without S

Gangudar 2818 (76) 2212(24) 78904 61936 22380 21733 56524 40203 27.4
a

Matpur 4250(73) 3656 (18) 119000 102368 32140 31847 86860 70521 16.3

Kamali 4073 3506(25) 114044 98168 30373 30086 83671 68082 16.2
(100)

Garamadi 1154(32) 926 (42) 32312 25928 12620 11840 19692 14088 24.6

3074 2575 61687 48224 21.1

(27.9%)
 16

Field demonstration on demonstration of drip irrigation system:

Under this project, Ratanpur village is selected to demonstrate drip irrigation method in castor crop. The results indicated that application of water
through drip system recorded 29.2 percent higher yield over flood irrigation system (Table 5.1.3).

Table 5.1.3: Demonstration of response of drip irrigation system:

Name of Yield (kg/ha) Total income Cost of cultivation Net income(Rs/ha) % higher over flood
village (Rs/ha) (Rs/ha) yield
Drip Flood Drip Flood Drip Flood Drip Flood
Ratanpur 4938 3823 138264 107044 31289 27200 106975 79844 29.2
(10) (10)

Field demonstration on demonstration of Intercropping:

Under this project 10 demonstrations on intercropping system were conducted in Danta and Kamali villages. Results indicated that intercropping
of castor with pulse as well as cotton found beneficial in respect of generate additional income. Results indicated that intercropping of castor with
urd bean and cotton 10.68 and 76.1 per cent higher net income as compared to sole castor and cotton, respectively (Table 5.1.4).

Table 5.1.4: Demonstration of response of Intercropping:

Name Yield Yield Castor + Total income Cost of cultivation Net income(Rs/ha) % Income
of (kg/ha) Urd bean (kg/ha) CEY (Rs/ha) (Rs/ha) higher over
village Castor Castor Urd (kg/ha) Cotton Inter cropping Castor Inter cropping Castor Inter cropping castor /cotton
sole bean sole sole sole sole

Danta 4389 4464 475 4973 122885 139235 31026 35655 94900 105033 10.68
(4)
13.3 %
Cotton Cotton Castor Cotton Intercropping Cotton Intercropping Cotton Intercropping
sole sole sole sole
Kamali 3660 3148 2253 5963 120780 166960 36863 47182 83918 119778 76.4
(6)
62.9 %
In 2010-11, farmers’ field demonstrations were conducted in all the districts falls under
the jurisdiction of SDAU, Sardarkrusinagar (Table 5.1.5).

Table 5.1.5: District wise selected villages and No. of farmers

Sr. Name of village No. of Sr. Name of village No. of

No. farmers No. farmers
Selected Selected
District: Banaskantha District: Sabarkantha
1 Gangodara 57 1 Dhamadi 64
2 Chodungari 40 2 Laloda 78
3 Undai 40 3 Mahadevpura 46
Total 137 Total 188
District: Kutchh District: Patan
1 Kamali 208 1 Matpur 78
2 Motidhau 30 2 Ruvavi 22
3 Kherava 38 3 Kanni 29
4 Sunok 27 4 Mithidhariyal 36
5 Shankhalpur 34 5 Ruppur 36
6 Garamadi 68
Total 337 Total 269
District: Kutchh District: Gandhinagar
1 Amardi 40 1 Tintoda 52
2 Nakhtrana 48
3 Kanakpur 28
4 Virani 20
Total 136
Grand total 1112
Total village 22

In this project, 1112 farmers’ field demonstrations were conducted during 2010-11 in
selected villages. The yield level of selected villages viz. Gangudara, Chodungari,
Kamali, Matpur, and Garamadi (rainfed) was surveyed and found 19-21, 23-25, 31-33,
33-34 and 6-8 q/ha, respectively. Looking to the present yield level, the target was fixed
for increasing yield level for different villages. The results indicated that the range of
increase in seed yield of castor in different selected villages was 25.8 to 51.1 percent
(Table 5.1.6). On an average, the magnitude of increase in yield over present level and
targeted yield was 37.6 per cent, respectively.

17
 18

Table 5.1.6: Present yield, expected yield and actual yield of selected villages

S. Village Baseline Actual received Increase

No. yield
status yield (q/ha) over Baseline yield status (%)
(q/ha) 2009-10 2010-11 2009-10 2010-11 Mean

1 Gangudara 19-21 28.18 32.25 40.9 61.3 51.1

2 Chodungari 23-25 28.78 31.60 19.9 31.7 25.8

3 Kamali 31-33 40.73 42.20 27.3 31.9 29.6

4 Matpur 33-34 42.50 45.10 26.9 34.6 30.8

5 Garamadi 6-8 11.54 12.25 64.9 36.1 50.5

23.7 30.35 32.68 36.0 39.1 37.6

(32.52)
 19

Demonstration on yield of GCH 7

Primary survey was made to know the present productivity of each selected villages. The
figures indicated that the productivity of selected villages was ranging from 27 to 35 q/ha
with average value of 30.26 q/ha. The result obtained in the demonstrations indicate that
by adoption of improved wilt resistant and high yielding hybrid GCH 7 recorded 12.32 to
46.38 per cent higher seed yield over existing hybrid/varieties (Table 5.1.7). On an
average 28.10 per cent productivity was increased.

Table 5.1.7: Demonstration of yield of GCH 7 over local cultivar

Name of the Productivity % Name of Productivity %

village (q/ha) higher the village higher
(q/ha) over
over local
Local GCH local Local GCH
cultivar 7 cultivar 7

Undai 29.00 36.21 24.86 Dhamadi 31.00 36.03 16.23

Motidhau 31.00 39.25 26.61 Laloda 34.50 39.45 14.35

Kherava 33.50 37.64 12.36 Mahadevpura 30.50 38.45 26.07

Shankhalpur 27.50 35.62 29.53 Ruvavi 31.50 37.25 18.25

Sunok 31.50 38.65 22.70 Kanni 30.50 36.84 20.79

Amardi 30.50 42.25 38.52 M. ghariyal 28.00 39.45 40.89

Nakhtrana 29.00 40.52 39.72 Ruppur 29.50 38.00 28.81

Kanakpur 30.50 39.65 30.00 Tintoda 27.50 38.95 41.64

Virani 29.00 42.45 46.38

Mean 30.26 38.62 28.10

 20

Demonstration on intercropping

Under this project 28 demonstrations on intercropping system were conducted in Kamali village during 2010-11. Results clearly
indicated that intercropping of castor in cotton found beneficial in respect of generate additional income (Table 5.1.8). On an average
intercropping of castor with cotton gave 50.79 and 58.76 per cent higher cotton equivalent yield and net income as compared to sole
cotton, respectively.

Table 5.1.8: Demonstration on intercropping

Year Cotton Yield Castor + Urd CEY Total income Cost of cultivation Net income(Rs/ha) % Income
sole bean (kg/ha) (kg/ha) higher
(Rs/ha) (Rs/ha) over
Cotton Castor Cotton Inter Cotton Inter Cotton Inter castor
cropping sole cropping /cotton
sole sole cropping sole

2009-10 3660 (6) 3148 2253 5266 183000 263291 35900 42850 147100 220441 49.86
(43.88)

2010-11 3440 (28) 3052 2541 5441 172000 272027 35900 42850 136100 229177 68.39
(58.17)

Mean 3550 3100 2397 5353 177500 267669 35900 42850 141600 224809 58.76
(50.79)

Pest observed/leaf –
Cotton: - Jassid 5.25, Thrips 11, Aphids 7 and White fly 10 Castor: - Jassid 3.5, Thrips 7.0, Aphids 2.0 and White fly 8
 21

In 2010-11, farmers’ field demonstrations were conducted in all the districts falls under the
jurisdiction of SDAU, Sardarkrusinagar (Table 5.1.9).

Table 5.1.9: List of villages selected for demonstrations during 2011-2012

Sr. Name of village No. of Sr. Name of village No. of

No. farmers No. farmers
Selected Selected

District: Banaskantha District: Sabarkantha

1 Gangodara 50 1 Kheroj 40
2 Chodungari 40 2 Kalwan 36
3 Kasalpura 40
Total 130 Total 76
District: Mehsana District: Patan
1 Kamali 160 1 Matpur 80
2 Badharpura 34
3 Maghapura 32
Total 160 Total 146
District: Kutchh District: Gandhinagar
1 Koday 20 1 Halisa 25
2 Nakhtrana 20 2 Jakhora 25
3 Rapar 20 3 Patelpura 25
4 Paliyad 25
Total 60 Total 100
Total village 16
Grand total 672

Total 672 demonstrations were conducted during 2011-12 in selected villages. At the
time of implementation of project, present yield level of the villages was surveyed. The yield
level of selected villages viz. Gangudara, Chodungari, Kamali, Matpur, and Kasalpura was 19-
21, 23-25, 31-33, 33-34 and 35-40 q/ha, respectively. Looking to the present yield level, the
target was fixed for increased the yield level for different villages. The results indicated that the
range of increase in seed yield of castor in different selected villages was 25.8 to 51.1 percent in
2010-11, but in 2011-12 it was not increased due to chilling injury (due to climatic change). On
an average, the magnitude of increase in yield over present level and targeted yield was 37.6 per
cent, respectively (Table 5.1.10).
 22

Table 5.1.10 : Present yield, expected yield and actual yield of five selected villages

Village Present Actual received Increase

yield status yield (q/ha) Over Present status (%)
(q/ha)
2010-11 2011-12 2010-11 2011-12 Mean

Gangudara 19-21 32.25 22.51 61.3 12.5 36.9

Chodungari 23-25 31.60 18.47 31.7 -24.24 3.73
Kamali 31-33 42.20 36.74 34.70 8.43 21.6
Matpur 33-34 45.10 35.83 34.6 3.28 18.9
Kasalpura 35-40 45.30 39.83 43.70 16.53 30.11
29.4 39.29 30.67 41.2 3.3 22.24

Demonstration on varietal response

About 148 farmers were selected to demonstrate the response of newly released wilt resistant and
high yielding hybrid GCH 7 in five selected villages. The results indicated that the magnitude of
increase in seed yield under GCH 7 was varied from 0.38 to 29.10 per cent in different villages
over local hybrids/varieties (Table 5.1.11). On an average GCH 7 produced 18.67 per cent
higher seed yield and 42.85 per cent higher net returns over local one.

Table 5.1.11 : Demonstration on varietal response

Name of Yield (kg/ha) Total income Cost of Net income %

village (Rs/ha) cultivation (Rs/ha) increase
(Rs/ha) in yield
GCH 7 Local GCH 7 Local GCH Local over
7 locally
grown
cultivars
Gangudara 2251 1825 67530 51100 21733 45797 29367 23.34
Chodungari 1847 1840 55410 51520 26031 29379 25489 0.38
Matpur 3583 3050 107490 93800 38572 68918 55228 17.47
Kamali 3674 2985 110220 83580 38223 71997 45357 23.08
Kasalpura 3983 3085 119490 92550 43714 75776 48876 29.10
3067 2619 58373 40863 (18.67)
 23

Demonstration on drip irrigation system

Chodungari village was selected to demonstrate drip irrigation method in castor crop. The results
indicated that application of water through drip system recorded 7.28 percent higher yield over
flood irrigation system (Table 5.1.12). The yield is decreasing of castor crop due to chilling
injury.

Table 5.1.12 : Demonstration on drip irrigation system

Name of Yield (kg/ha) Total income Cost of Net %

village (Rs/ha) cultivation income(Rs/ha) increase
(Rs/ha) over
Drip Flood Drip Flood Drip Flood Drip Flood flood
yield
Chodungari 1844 1720 55320 51600 30228 27200 25092 24400 7.28

Demonstration on Intercropping

Ten demonstrations on intercropping system were conducted in Chodungari and Gangudara

villages. Results clearly indicated that intercropping of castor with ground nut found beneficial in
respect of generate additional income. Results indicated that intercropping of castor with ground
nut 72.01 and 79.21 per cent higher net income as compared to sole castor in Chodungari and
Gangudara, respectively (Table 5.1.13).

Table 5.1.13: Demonstration on Intercropping

Name Yield Yield Castor + Total income Cost of Net %

of (kg/ha Ground nut (Rs/ha) cultivation income(Rs/ha) Income
village ) (kg/ha) (Rs/ha) higher
Castor Casto Casto Inter Casto Inter Casto Inter over
sole r Grou r sole croppin r sole croppi r sole cropping castor
nd g ng sole
nut
Chodun 2200 1400 1100 66000 95500 35195 42510 30805 52990 72.01
gari
Gangu 2175 1325 1185 65250 97725 34241 42182 31009 55573 79.21
Dara
 24

5.1.13 Value addition to the by-products of the castor

Objective: - To determine protein content in castor cake of different genotypes

Techniques used: - Determination of Total Protein content by Micro-Kjeldahl Method

Results and discussion: - Fifty one castor germplasm genotypes were analysed for protein
content. The protein content was in the range of 19.93 to 30.81% (Table 5.1.13). Maximum
protein content was noted in GP-415 (30.81%) genotype.

Table 5.2.1: Nitrogen and Protein content in cake of castor germplasm

Sr. Protein Sr. Sample

Sample Name N% N% Protein %
No. % No. Name
1 GP – 401 4.37 27.31 26 GP – 437 3.36 21.00
2 GP – 402 4.65 29.06 27 GP – 440 3.64 22.75
3 GP – 407 4.24 26.50 28 GP – 444 3.92 24.50
4 GP – 408 3.64 22.75 29 GP – 445 4.34 27.12
5 GP – 409 3.92 24.50 30 GP – 447 4.45 27.81
6 GP – 411 4.84 30.25 31 GP – 460 4.20 26.25
7 GP – 412 4.09 25.56 32 GP – 461 3.92 24.50
8 GP – 413 3.83 23.93 33 GP – 463 3.36 21.00
9 GP – 414 3.69 23.06 34 GP – 466 4.76 29.75
10 GP – 415 4.93 30.81 35 GP – 467 3.64 22.75
11 GP – 416 4.25 26.56 36 GP – 471 4.84 30.25
12 GP – 417 4.49 28.06 37 GP- 473 4.64 29.00
13 GP – 419 4.06 25.37 38 GP – 478 4.37 27.31
14 GP – 420 4.22 26.37 39 GP – 480 4.27 26.68
15 GP – 421 3.22 20.12 40 GP – 481 4.88 30.50
16 GP – 422 3.92 24.50 41 GP – 482 3.92 24.50
17 GP – 423 3.83 23.93 42 GP – 487 4.25 26.56
18 GP – 424 4.45 27.81 43 GP -488 3.73 23.31
19 GP – 425 4.36 27.25 44 GP – 489 3.79 23.68
20 GP – 426 4.20 26.25 45 GP – 490 4.29 26.81
21 GP – 427 3.75 23.44 46 GP – 491 4.25 26.56
22 GP – 428 3.50 21.80 47 GP – 492 3.90 24.37
23 GP – 429 3.66 22.88 48 GP – 493 4.11 25.68
24 GP – 431 3.76 23.54 49 GP – 494 4.17 26.06
25 GP – 435 4.25 26.56 50 GP – 495 3.19 19.93
51 GP – 496 4.09 25.56
 25

Objectives: To develop protein estimation and extraction method from castor cake.
Techniques used:- Rebeca Marnoch and Levente L.Diosady (2006) Production of Mustard
protein isolates from Oriental Mustard seed (Brassica juncea L.) JAOCS, 83(1): 65-69

Results and discussion:

Thirty six castor genotypes were analysed for protein isolation from cake. The protein content of
different genotype was in the range of 11.05to 19.35% (Table 5.1.14). Among all the genotypes,
GP-422 (19.35 %) recorded maximum protein content.

Table 5.1.14: Protein isolation and extraction from castor cake.

Sr. Sample Name Protein (%) Sr. Sample Protein (%)

No. No. Name

1 GP-401 13.70 19 GP-434 16.82

2 GP-402 11.05 20 GP-435 17.53
3 GP-407 13.57 21 GP-437 17.22
4 GP-408 14.01 22 GP-440 18.86
5 GP-409 12.90 23 GP-441 11.27
6 GP-411 11.89 24 GP-442 16.51
7 GP-412 14.13 25 GP-444 13.38
8 GP-413 13.52 26 GP-445 15.46
9 GP-414 12.10 27 GP-460 14.35
10 GP-415 15.20 28 GP-447 17.48
11 GP-424 11.26 29 GP-461 12.65
12 GP-427 12.18 30 GP-462 17.08
13 GP-430 13.90 31 GP-463 16.09
14 GP-425 16.30 32 GP-466 15.38
15 GP-428 12.42 33 GP-467 15.02
16 GP-429 13.20 34 GP-471 17.93
17 GP-422 19.35 35 GP-473 12.44
18 GP-423 11.23 36 GP-476 15.56
 26

Objectives: To estimate different toxic constituents in cake of various castor genotypes and its
detoxification .
Techniques used: H.L.Craig et.al., 1952 Preparation of toxic Ricin filed July 3,
Results and discussion:
Thirty seven castor cake samples were analysed for crude ricin. The toxic constituents content was in
the range of 1.03-1.92 % in the different DOC samples. GP-420 (1.03 %) showed lowest toxic
constituents and GP-460 (1.92%) had the highest toxic constituents (Table 5.1.15). After the series of
treatments for detoxification, namely soaking 3 hours in 0.5 M NaOH ,and 0.5 M Ca(OH)2,, heated in
water bath and autoclaving, resulted in traces or undetectable levels of toxic constituents were
observed.
Table 5.1.15: Crude ricin content before and after detoxification

Before Detoxification Crude Ricin After treatment

Sample Name
content Ricin content%
DOC-1 1.09 Trace
DOC-2 1.44 Trace
DOC-3 1.65 Trace
DOC-4 1.04 Trace
DOC-5 1.14 Trace
DOC-6 1.58 Trace
DOC-7 1.29 Trace
DOC-8 1.30 Trace
GP-401 1.64 Trace
GP-402 1.40 Trace
GP-407 1.64 Trace
GP-408 1.07 Trace
GP-409 1.80 Trace
GP-415 1.57 Trace
GP-417 1.67 Trace
GP-419 1.71 Trace
GP-416 1.85 Trace
GP-420 1.03 Trace
GP-421 1.60 Trace
GP-422 1.69 Trace
GP-424 1.72 Trace
GP-425 1.66 Trace
GP-427 1.03 Trace
GP-428 1.37 Trace
GP-429 1.39 Trace
GP-430 1.69 Trace
 27

GP-434 1.72 Trace

GP-435 1.27 Trace
GP-437 1.48 Trace
GP-440 1.42 Trace
GP-441 1.06 Trace
GP-442 1.01 Trace
GP-444 1.17 Trace
GP-445 1.08 Trace
GP-447 1.68 Trace
GP-460 1.92 Trace
GP-461 1.48 Trace

Objectives: To determine Lignin and Cellulose content of castor stem from different castor
genotypes

Techniques used: Official Methods of Analysis of the AOAC Lignin (35)-Official Final Action
Direct Method

Results and discussion

Eighteen castor genotypes were analyzed for lignin and cellulose content of stem by chemical
method. The lignin and cellulose content was noted in the range of 14.1 to18.8 and 34.9 to 45.7%
respectively (Table 5.1.16).

Table 5.1.16: Determination of lignin and cellulose by chemical method

Genotypes % Lignin % Cellulose Genotypes % Lignin % Cellulose

Geeta 18.8 39.1 GCH-4 14.6 38.2
GAUCH-1 16.3 40.7 VP-1 16.6 40.3
VI-9 17.0 40.8 GCH-2 19.2 36.8
SKP-84 14.4 40.1 JI-96 15.7 35.0
GCH-2 17.7 44.3 GC-3 16.8 34.9
48-1 15.9 41.8 SH-72 17.3 38.4
SKI-215 15.7 37.1 GC-2 16.5 41.7
GCH-7 17.2 45.7 JP-65 17.3 42.2
GCH-5 14.1 41.2 JI-35 18.7 44.1
 28

Summary

Field demonstration: Total 465 farmers’ field demonstrations were conducted. The yield level of
selected villages viz. Gangudara, Chodungari, Kamali, Matpur, and Garamadi (rainfed) was 19-
21, 23-25, 31-33, 33-34 and 6-8 q/ha, respectively. Through the agro technological
demonstration, the results indicated that the range of increase in seed yield of castor in different
selected villages was 15.7 to 23.9 percent. On an average, the magnitude of increase in yield over
present level was 34 percent which was 11.8 per cent more than targeted yield. During 2011-12
total 672 demonstrations were conducted. The yield level of selected villages viz. Gangudara,
Chodungari, Kamali, Matpur, and Kasalpura was 19-21, 23-25, 31-33, 33-34 and 35-40 q/ha,
respectively. On an average, the magnitude of increase in yield over present level and targeted
yield was 37.6 per cent, respectively.

Value addition in castor cake: Among, Fifty one castor genotypes analysed, the protein content
varied from 19.93 to 30.81%. Maximum protein content was noted in GP-415 (30.81%)
genotype. Thirty six castor genotypes were analysed for protein isolation from cake. The protein
isolated from different genotype varied from 11.05to 19.35%. Among all the genotypes, GP-422
(19.35 %) recorded maximum isolated protein content. Thirty seven castor cake samples were
analysed for crude ricin ranging from 1.03-1.92 % in the different DOC samples. GP-420 (1.03
%) showed lowest toxic constituents and GP-460 (1.92%) had the highest toxic constituents.
After the series of treatments for detoxification, resulted in traces or undetectable levels of toxic
constituents were observed. Eighteen castor genotypes were analyzed for lignin and cellulose
content of stem by chemical method. The lignin and cellulose content was noted in the range of
14.1 to18.8 and 34.9 to 45.7% respectively.
 29

5.2. POST HARVEST TECHNOLOGIES

Objectives: Development of post harvest processing improving oil recovery in extraction of oil
from castor seed and in-plant study of castor oil extraction industry for energy efficiency.
Activity 1:
 Improved sickles, hand operated cutting tool will be evaluated for efficient harvesting the
castor spikes. The losses occurs at different stage will be measured and technology
developed / suggested to reduce losses. The harvested castor spikes will be dried under
different drying methods viz., natural drying, solar drying and mechanical drying.
 The economically efficient drying methods will be suggested to the growers
Activity 2:
The different available hand and power operated castor decorticators will be studied.
Efficient castor decorticator will be standardized for the uniform size of castor seed for
prominent castor genotypes of North Gujarat.
Activity 3:
The different secondary processing equipments like pre seed cleaner cum aspirator,
cleaner cum grader and destroyer will be used to improve the quality of raw material.
The cleaned and graded produce will be packed in different size / quality of packaging
material.
Activity 4:
 Existing oil extraction plants (two each of small and medium capacity) of the region will
be evaluated for time -motion operation and energy audit.
 The energy audit study will identify the aspects of where and how energy is used and
converted from one form to another, opportunities for reduction in energy loss ;
evaluation of the technical and economic viability of the energy conservation measures
proposed
 Recommendations will be generated on above aspects.
After completion of experimental part in each activities, the analysis of data will be
carried out.
 30

Study on different harvesting tools for higher cutting efficiency & minimum losses
Achievements:
The local sickle, improved sickle and secator were evaluated for efficient harvesting of castor
crop (variety: GCH-7) and minimum losses. The average harvesting capacity of castor spike was
found 65.90 kg/hr for secator followed 52.99 and 51.24 kg/hr for improved sickle and local
sickle respectively (Table 5.2.1). The higher percent losses were observed for improved and local
sickles as compared to secator.

Table 5.2.1 Harvesting of castor spikes (Area: 1 ha)

Harvesting Losses
Types of Times Weight of Average during
Sr. Percentage
harvesting Harvested Capacity capacity harvesting
No (Hours) spike (kg) of losses
devices (Kg/hr)
(Kg/hr) (kg)

1 Local 25.25 1570.70 62.21 51.24 63.62 4.05

sickle 23.14 1325.75 57.30 62.34 3.94
21.04 941.91 44.76 54.35 5.77
26.38 939.39 35.60 41.69 4.43
22.44 1264.31 56.34 59.09 4.67
2 Improved 27.35 1578.28 57.70 52.99 63.31 4.01
Sickle 25.25 1110.10 43.97 35.67 3.21
23.14 1045.95 45.20 48.91 4.67
16.83 1111.11 66.02 41.35 3.72
19.64 1022.72 52.07 44.10 4.31
3 Secator 21.04 1598.48 75.97 65.90 52.22 3.27
18.93 1146.46 60.56 31.65 2.76
23.14 1116.16 48.23 32.11 2.88
14.73 1098.48 74.57 23.88 2.17
18.23 1279.48 70.18 28.60 2.23
Study on tractor drawn castor planter
 31

Title of experiment: Performance-evaluation of tractor drawn castor planter

Achievements:
A) Castor seed sowing by tractor drawn castor planter
Plot size: 10.60 m (width) X 51 m (length) Plot area: 540.6m2
Diesel consumption: 3.01 lit / ha. (0.1622 lit for 540.6 m2 area)
Germination, %: 4 plants / sqm. ; 76 plants / 100 sqm
B) Manually sowing method:
Nos. of labours required: 5 labours for 1 hectare sowing (in 8 hours).
Cost for manual sowing: Rs. 500 / ha. (Rs.100/lab our)
Economic benefit with mechanized sowing:
(i) Fuel consumption: 3.01 lit / ha Cost of fuel: 3.0 x 42.00=126.00
(ii) Operating cost including tractor driver & skilled labour charges
For 1 hectare sowing using tractor drawn planter 2.77 hrs (3 hrs) is required the expenditure for
labours is Rs. 150/- considering Rs.200/- day per skill lab our

Expenditure under mechanized sowing per hectare Expenditure under manual sowing
Per hectare
Cost of fuel: 3.0 x 42.00 = Rs. 126.00 Cost for manual sowing: Rs. 500
Labour cost = Rs. 150.00 (Rs. 100 / labour)
--------------------------------------------------------
Total Rs. 276.00 (excluding seed saving cost)

In manually sowing method double seeds are sown at crossed marked point. Therefore, the
seeds require in double quantity which also increase the cost of sowing.

Benefit by mechanized sowing: Rs. (500-276) = Rs. 224.00 per hectare

 The castor planter was tested for single, double and triple groove rollers (pvc) for sowing
of castor seeds (variety: GCH7). Single groove roller (pvc) was found more suitable to
maintain row to row and plant to plant distance.
 The purchased tractor drawn castor planter is also found satisfactory to maintain the
depth of sowing.
 Single groove roller is found satisfactory to maintain the depth of sowing and plant to
plant distance.
 32

Study on to standardize the hand and power operated castor decorticators for the uniform
size of castor seed for prominent castor genotypes of North Gujarat.
The performance testing of power operated castor decorticator was done. The uncleaned castor
capsules were found slightly higher. Therefore the upper sieve size was replaced with suitable
size of hole. The castor decorticator was tested in field condition. The cleaning efficiency and
broken percentage was found 82 to 89% and 1.2 to 4.2% respectively (Table 5.2.2).
Table-5.2.2: Performance of purchased modern castor decorticator
Total weight Unthresh
Sr. Unthreshe Cleaned Cleaned Breakage Breakage
of sample, ed seed,
no d seed, % seeds, kg seed. % seeds, kg seed, %
kg kg
1 1.437 0.092 6.41 1.284 89.35 0.059 4.17

2 1.230 0.151 12.27 1.035 84.14 0.043 3.51

3 1.610 0.148 9.19 1.426 88.57 0.035 2.17

4 1.362 0.238 17.47 1.115 81.86 0.054 3.96

5 1.105 0.128 11.58 0.967 87.51 0.026 2.35

6 1.395 0.138 9.89 1.241 88.96 0.016 1.15

Average 1.143 0.149 10.98 1.178 86.73 0.039 3.41

 33

Study on solar drying of castor spikes under low cost poly solar dryer
Low cost poly solar dryer: Low cost poly solar dryer for drying the castor spikes was installed.
The dryer was tested for temperature and humidity controlled under no load condition. The
performance data are as per under (Table 5.2.3). The experiment was conducted in first week of
December-2010, to dry the freshly harvested castor spikes in low cost poly solar dryer and open
space sun drying. The material was dried earlier 5 to 6 days in low cost ploy solar dryer at 30%
humidity and 36 to 37O C whereas the outside ambient temperature was 22 to 25O C. Using low
cost poly solar dryer, the farmers can dry their harvested crops earlier and get benefit of
immediate market price. Traditional drying of castor spike in open space on pakka floor.
Table 5.2.3 Performance evaluation of low cost poly solar dryer under no load condition
Date & Time Humidity Temp. inside Outside Temp Outside Humidity
the dryer (oc) (ambient), (oc) (%)
14-07-2010
8:30 (A.M.) 20 49 32 64
11:30 (A.M.) 20 55 35 50
15:00 (P.M.) 20 53 41 27
17:30 (P.M.) 20 51 36 55
15-07-2010
8:30 (A.M.) 30 47 31 58
11:30 (A.M.) 30 52 36 47
15:00 (P.M.) 30 55 41 32
17:30 (P.M.) 30 57 39 33
16-07-2010
8:30 (A.M.) 40 39 33 68
11:30 (A.M.) 40 45 37 32
15:00 (P.M.) 40 48 39 44
17:30 (P.M.) 40 51 38 34
17-07-2010
8:30 (A.M.) 50 41 31 80
11:30 (A.M.) 50 44 37 44
15:00 (P.M.) 50 52 39 42
17:30 (P.M.) 50 50 38 47
19-07-2010
8:30 (A.M.) 60 39 32 70
11:30 (A.M.) 60 42 34 61
15:00 (P.M.) 60 55 40 41
17:30 (P.M.) 60 52 38 49
20-07-2010
8:30 (A.M.) 70 36 35 51
by Tractor drawn castor planter
11:30 (A.M.) 70 39 37 46
15:00 (P.M.) 70 45 40 41
17:30 (P.M.) 70 41 36 45
 34

21-07-2010
8:30 (A.M.) 80 34 32 62
11:30 (A.M.) 80 36 38 48
15:00 (P.M.) 80 40 39 36
17:30 (P.M.) 80 39 37 41

Summary

 After base line survey of six districts of north Gujarat, in three years time two thousand
four hundred demonstrations comprising about 2000 under irrigated and 400 under
rainfed conditions demonstrating different agro-techniques were conducted on farmers’
field during 2009-2012.
 Visited farmer's field & gave suggestion for plant protection measures for insect-pests
and disease management and adoption of new latest high resistant variety.
 Farmer’s field days in villages till 2009 to 2012 in Kuttch and Banskantha, Patan district
villages and provided the castor production technology.
 Solar dryer is more suitable for drying of crops drying was found 6 to 7 days earlier as
compared to traditional drying method.
 On the basis of demonstration of farmer's field single groove planter was found most
suitable for sowing castor crop sown at fixed crop geometry.
 Fifty one castor genotypes were analyzed for protein content in castor cake which ranges
from 19.93 (GP 495) to 30.81% (GP 415).
 Thirty seven genotypes analyzed for ricin content in castor cake which ranged from 1.03
(GP 420) to 1.92 % (GP 460). After detoxification only trace ricin content was found.
 Eighteen genotypes were analyzed for cellulose and lignin content. The cellulose ranged
from 39.4-45.7% and lignin between 14.1 -19.2% with lowest in GCH 5 & GC 3 and
highest in GCH 2 & GCH 7, respectively.
 35

5.3 Research Achievement of RCPL, Sidhapur

Objective: To make various ester based on castor oil

12 H.S.A. was starting molecule having following properties
ACID VALUE : 180.06
HYDROXYL VALUE: 158.00
IODINE VALUE : 2.86
COLOUR : 5 (Gardner)
Esterification of 12 H.S.A. with Higher alcohol (Octanol)
Experimental set up:
1. 5 liter round bottom flask was attached with condenser and dean and stark assembly and
agitator.
2. The reaction mass was heated by heating metal.
Reaction condition and Inputs:
1. 1 Kg 12-H.S.A.
2. 780 gm octanol
3. 0.2 %catalyst
4. Temperature 120˚C
5. Time 4 hr
The 2-EH esters are not good in color which were prepared by H2SO4 or other acid catalyst.
Also they have lower viscosity, so they are not also useful as lubricants or hydraulic fluids. The
hydroxyl group also neutralize by some acid molecule. The acidity of the esters also become as
near by1.0 and the H.V. of the esters also nil. If the acidity of the sample is more then it becomes
rancid and the odor of the sample is bad. The acid catalyst is also difficult to neutralize. If the
neutralize materials with strong base then there may be the possibility of the saponification of the
2-eh esters and soap formation.
Trial for various catalysts for Esterification
1. Technique Used : Few Esterification Catalyst procured from the market :
2. Maharastra Organo metallic catalyst Pvt Ltd ( OM – 06 )
3. Navdup Chemicals Pvt Ltd. (NC – 07 )
4. Amrit Chemicals ( AC – 08 )
Preparation of the different esters with other catalyst
(1) 12 H.S.A + OCTANOL + OM – 06
(2) 12 H.S.A + OCTANOL + NC – 07
(3) 12 H.S.A + OCTANOL + AC – 08
 36

1ST STAGE ESTERIFICATION REACTION

Analysis of the Data: 1st Stage Reaction
12 H.S.A. + OCATANOL + OM – 06
SR NO. A.V. H.V. I.V. COLOR VISCOSITY@ 40
1 0.5 101.6 2.4 2.8 35.88
2 1.0 99.2 2.10 2.9 34.66
3 0.98 98.9 2.6 2.8 35.11

12 H.S.A + OCTANOL + NC – 07
SR NO. A.V. H.V. I.V. COLOR VSICOSITY@40
1 1.8 95.6 2.9 2.9 33.70
2 1.0 96.2 1.8 2.9 34.15
3 0.6 95.7 2.2 2.8 33.12

12 H.S.A + OCTANOL + AC – 08
SR NO. A.V. H.V. I.V. COLOR VISCOSITY@40
1 1.5 93.2 2.6 2.8 32.10
2 1.2 94.6 2.8 2.75 33.02
3 0.99 94.7 2.4 2.8 33.69
 37

RESULTS AND DISCUSSION:

1st Stage Reaction

Catalyst seems to be effective and acid value is considerably reduced.

Color of the product is approximately 3G meaning acceptable
Viscosity is bit on lower side
Hydroxyl Value is higher side which has to be reduce
Reduction in the HV may result in the reduction of Viscosity.

2nd Stage Reaction

2nd Stage Reaction: Comments:

All the Catalyst are effective for the esterification

The final products seems clear and transparent
Viscosity of the products has reduced
Hydroxyl value is reduced as desired.
 38

Hydroxyl Value of the reaction product reduces the hydrolitical properties of the products. The
reaction product react these hydroxyl Value with Acetic Acid as.

ETHYL ESTER (WITH –OH) + ACETIC ACID

ETHYL ESTER (WITHOUT –OH) + H2O

SR NO. A.V. H.V. I.V. COLOR VISCOSITY@ 40

1 1.6 2.6 2.4 3.8 30.92
2 1.97 3.2 2.10 3.9 29.66
3 2.3 3.9 2.6 3.8 31.11
4 3.0 3.6 3.00 4.0 31.00
5 2.6 2.9 2.79 3.6 30.88
6 2.88 3.4 2.88 3.9 29.66

Further Viscosity Enhancement : -

Products can be trans-estrified to make bigger molecule , Various experiments have been
planned.
Using some higher Acids for Esterification to eliminate the HV
Reacting the hydroxyl value with higher molecular weight fatty acids.
Addition of Viscosity improver in additive package.
Reaction of Octyl 12 – H.S.A ( with hydroxyl value ) with Butyric acid
2nd Stage Reaction after Reaction of Octyl 12 – H.S.A (with hydroxyl value ) with Butyric acid

SR NO. A.V. H.V. I.V. COLOR VISCOSITY@ 40

1 0.41 NIL 2.4 3.0 33.91

2 0.38 NIL 2.8 2.9 33.10

3 0.35 NIL 2.6 3.0 33.05

4 0.45 NIL 2.5 3.0 33.20

Addition of one more reaction step to enhance the viscosity:

Target to achieve higher viscosity to the level of above 42 cst @ 40 Degree C / above 8 cst
@100 Degree C.
Mechanism :- To improve viscosity we have modified the reaction steps as follow :-
After 1stage reactions we have added condensation reaction as given below :-
 39

Now the reaction steps can be as given below :-

1st Stage Reaction

12 H.S.A. + OCATANOL + CATALYST
↓
Octyl 12-HSA
2nd Stage reaction :-
Condensation reaction :-
12-OHS +12-OHS -- Mixture of 12-OHS + Dimer + 2EH
rd
3 Stage reaction :-
Reduction of Hydroxyl value :-
Mixture of 12-OHS + Acetic Acid - Final product ( with nil –OH value)
Detailing of second stage reaction :-
Second stage reaction was controlled by way of recovery of the product 2EH
Final results of the products is as given below:-43.8-48.6 @40 degree C and 8.4 to 9.6 @1000C
Tentitive Specification
TYPICAL PHYSICO – CHEMICAL PROPERTIES
SR. NO. PROPERTIES LIMITS

1. VISCOSITY@40ºC 42 MIN

2. VISCOSITY@100ºC 8 MIN

3. VI 162 MIN

4. CLOUD POINT ºC - 20 MIN

5. POUR POINT ºC - 25 MIN

6. FLASH POINT ºC 200 MIN

7. ACID VALUE (MAX.) 0.5 MAX

8. COLOR 3.0 – 3.5 MAX

9 BIODEGRADABILITY HIGHLY BIODEGRADABLE

 40

5.4. Research Achievement: Indian Institute of Chemical Technology, Hyderabad

OBJECTIVES

Process development for the enriched methyl ricinoleates from castor oil methyl esters
Comparison of properties of the derivatives manufactured through enriched methyl
ricinoleates and castor methyl esters.
Preparation of first generation products/advanced derivatives utilizing enriched methyl
ricinoleates
Use of undecenoic acid for high value derivatives (wax esters, surfactants and lubricants)
development
METHODOLOGIES OF RESEARCH
Enrichment of methyl ricinoleate from castor oil fatty acids: Methyl ricinoleate was
enriched from crude castor oil fatty acid methyl esters by employing liquid-liquid
extraction concept using aqueous methanol and refined non-hydroxy vegetable oils like
sunflower oil. In addition, liquid paraffin was also explored as a medium in place of
refined vegetable oils for the enrichment.
Preparation of UDA-based Surfactants: Preparation of undecenoic acid-based mono
and diethanolamides were conducted in a solvent-free medium during this period.
Different reaction conditions like molar ratios of substrates, temperature and reaction
time were optimized for the preparation mono and diethanolamide.

O O
0 0 0
OH 130 C,150 C, 170 C OH +
n OH + H2N n
1:2 NH
UDA ETHANOLAMINE

OH
n N

O
n

Looking at the insolubility of diethanolamide, it was decided to phosphorylate the hydroxyl

functionality.
 41

O O
O
( )7 ( )7
1. (H3PO4)n ,CHCl3 /H2O
N N
OH ( )7 O P ONa
( )7
2. NaOH in ethanol
O O
ONa

Another undecenoic acid-based surfactant, N-methyldiethanolamide diundecenoate were also

carried out and evaluated for their surfactant properties.

O
O
HO
5% NaHSO4.H2O 8 O
8
OH + N
N
HO 120 °C O
UDA N-methyl Di ethanolamine 8
O
Ester

O O

O O
DMS,DCM
N N+
Room tmep -
O O MeSO4
O O

Direct and indirect phosphorylation of UDA was also carried out to synthesize two new
surfactants.

Upscaling studies for the Enrichment of Methyl Ricinoleate from Castor Oil Methyl Esters
using Refined Sunflower Oil as a Medium

In continuation of the earlier work, efforts are mad to minimize the vegetable oil contamination
by increasing the residence time for the separation of the extract and raffinate. The vegetable oil
contamination in the enriched methyl esters were evaluated as follows.
Castor oil methyl esters (1.5 kg) and refined sunflower oil (3 kg) are thoroughly
mixed in a 20 lit plastic container. Castor oil methyl esters were cooled to 20oC and 10% aq.
methanol (9 lit) was added and mixed vigorously. Then the mixture was taken in to the jacketed
glass tubular separator (20 lit) and the temperature (20oC) was maintained by using Julabo
circulator. The mixture was allowed to stand for 30 min till the two layers were separated. The
upper layer (aq. methanol) was removed and concentrated by distilling out the solvent in to 10
lit glass rota evaporator at 80 to 90oC under reduced pressure. The raffinate was again treated
with another 9 lit aq. methanol and the extract was dried as above (extract-1). Finally the
 42

raffinate was extracted with anhydrous methanol at 50oC (extract-2). The samples 1 and 2
obtained are analyzed by GC. Extract was found to contain 96.2% of Ricinoleic acid with 85%
yields. The weights of the samples are given in Table 5.4.1.
Table 5.4.1: Weight of the Extracts and Raffinate
Sample Name Weight (kg)

Extract-1 (Aq.Methanol) 1.16

Extract-2 (Hot Methanol) 0.24

Raffinate 3.02

Determination of Purity of Enriched Methyl Ricinoleate Fraction Employing Column

Chromatography: The enriched methyl ricinoleate may contain small amounts of sunflower oil in
addition to non-hydroxy fatty acids. Hence the purity of enriched methyl ricinoleate (1.9 g) was
determined employing silica gel column chromatographic method using gradient elution of
hexane and ethyl acetate solvent system. The composition of the sample is given in Table 5.4.2,
which reveals that the purity of methyl ricinoleate is up to 97.8% and traces of sunflower oil is
associated with methyl ricinoleate
Table 5.4.2: Column Chromatographic Separation of Enriched Methyl Ricinoleate

Fraction Composition (wt%)

Refined Sunflower Oil (TG) 0.9%

Non Hydroxy Methyl Esters 1.3%

Methyl Ricinoleate 97.8%

Studies for the Enrichment of Methyl Ricinoleate by LLE using Liquid Paraffin as
Medium

The following experiments were conducted and evaluated for the enrichment of methyl
ricinoleate from castor oil methyl esters by LLE using liquid paraffin as medium instead of
sunflower oil. Significant number of experiments were carried out for with heavy paraffin oil as
the medium using aqueous methanol as the extractant. The extraction conditions like extraction
time, temperature and speed of agitation were optimized at lab scale for maximum enrichment
of methyl ricinoleate from castor oil methyl esters and the experimental data is presented in
Table 5.4.3
 43

Table 5.4.3: Optimization of Process Parameters for the Enrichment of Methyl Ricinoleate
from Castor Oil Methyl Esters by Liquid-Liquid Extraction

Feed Process conditions Analytical results Remarks

CME Paraffi MeO H2 Tim Tem Stirrin Recovere Yield Purity
(g) n H O e p g d MeoH (%) (%)
(g) (g) (g) (min (°C) (rpm) (g)
)
147 295 2160 300 420 20 0 1340 88.77 97.3 1:16
CME:aq.
MeOH(1
0%)
25 50 360 50 30 10 155 387.57 86.01 96.9 “
25 50 360 40 30 20 50 383.65 92.13 95.99* 1:16
25 50 360 40 30 RT 50 394.42 87.64 95.69 1:16
25 50 360 40 60 RT 150 363.25 92.7 94.7 1:16
25 50 180 20 30 10 50 - 69 97.54 1:8
25 50 180 20 60 10 50 - 82.2 97.47 1:8
nd rd
*2 LLE 98.7%; 3 LLE 99.6%
Experimental procedure : A synthetic mixture was prepared by mixing known quantities of
castor oil methyl esters (CME) and heavy paraffin oil. Required amount of aqueous methanol
was added to this mixture and the contents were mildly stirred for a certain period at a particular
temperature. Then the mixture was allowed to settle for phase separation. The extractant phase
was separated and passed through a celite bed to adsorb the finely dispersed droplets of paraffin.
Further methanol and water from the enriched extractant phase was separated by simple
distillation. Finally the extractant was thoroughly dried under reduced pressure. The enriched
CME was analyzed by GC for its purity

Conclusions:
1. Based on the above data, it can be inferred that good results were obtained when the
stirring period increased from 30 min to 60 min.
2. When the volume of the extracting agent (methanol) increased, consequently yields and
conversions increased
The following experimental protocols were employed to avoid/minimize the contamination of
liquid paraffin in extractant and the results of these experiments resulted with good result.
Adsorption method: Extract was passed through a bed of celite to effectively remove the
vegetable oil/liquid paraffin contamination in the enriched methyl ricinoleate (lab scale).
Centrifugal separation: Extract was centrifuged in a batch type centrifuge at 7,000-10,000 rpm
at 15-20oC for 15-20 min. Vegetable oil/liquid paraffin fine globules coalesce at the bottom and
the upper extract is free of contamination.
 44

Employing the above optimized conditions upscaling experiments were conducted as per the
given process flow diagram

FEED

Extraction Super
vessel
CCentrifuge
Rectification
column

Separator

Product

Raffinate

Hot Methanol

Treatment
Equilibrium Studies for the Extraction of Castor Oil Methyl Esters by LLE

Castor oil methyl esters (different concentrations, 0.5 to 5 g) were accurately weighed and taken
in the 250 ml conical flask. Paraffin (5 g) and 10% aq. methanol (16 g) were added to castor oil
methyl esters. The contents were stirred on orbital shaker for 12 hr at room temperature at 100
rpm. After 12 hr, the mixture was transferred into a separating funnel and allowed to settle for 15
min to separate out the two layers. The lower layer (paraffin) was collected in to the sample
bottle and upper layer (aq. methanol extract, cA alc) was collected and dried over sodium sulphate
and analyzed by GC for determination of composition of castor oil methyl esters in both the
phases . KD is the distribution coefficient for the extraction system. The paraffin phase (c A org)
was treated with hot methanol and the extract was also analyzed by gas chromatography for
determination of retained castor oil methyl esters along with paraffin. The results are tabulated as
shown below (Table 5.4.4, 5.4.5. and 5.4.6) and presented in Fig 5.4.1.
 45

Table 5.4.4: Analysis of castor oil methyl esters in the aq. methanol extract
S. No. Weight (g) % Purity
10% aq MeOH 5% aq MeOH
1 0.5 99.45 -
2 1.0 99.36 96.26
3 2.0 97.82 94.76
4 3.0 97.15 93.27
5 4.0 96.39 91.88
6 5.0 95.72 90.29

Table 5.4.5: Distribution of castor oil methyl esters in the organic and aqueous phase
S. No. Weight (g) 10% aq MeOH 5% aq MeOH
cA alc cA org KD cA alc cA org KD
1 0.5 0.49725 0.00275 - -
2 1.0 0.9936 0.0064 0.9626 0.0374
3 2.0 1.9564 0.0436 1.8952 0.1048
4 3.0 2.9145 0.0855 2.7981 0.2019
5 4.0 3.8556 0.1444 3.6752 0.3248
6 5.0 4.786 0.214 22.36 4.5145 0.4855 9.30

Table 5.4.6: Analysis of castor oil methyl esters retained in paraffin (hot methanol extract)

S. No. Weight (g) % Purity

10% aq MeOH 5% aq MeOH
1 0.5 87.83 -
2 1.0 86.11 87.67
3 2.0 85.72 82.34
4 3.0 82.90 79.52
5 4.0 80.55 77.28
6 5.0 81.43 78.59

4
c A alc, g/cc

10% aq MeOH
3
5% ag MeOH

0
0 0.1 0.2 0.3 0.4 0.5 0.6
c A org, g/cc

Fig 5.4.1: Equilibrium data for the LLE system CME in paraffin and aqueous methanol
 46

Conclusions
1. It is inferred from the above equilibrium data that better distribution was obtained in the case of
extraction of CME with 10% aq methanol
2. The distribution coefficient was also high for extraction of CME with 10% aq methanol
compared to extraction of CME with 5% aq methanol
3. Knowledge of the equilibrium data and distribution coefficients are essential for designing a good
extraction system
Upscaling Studies on the Enrichment of Methyl Ricinoleate

The enriched methyl ricinoleate was evaluated by column chromatography for the paraffin oil
contamination and it was observed that the contamination of paraffin oil is to the extent of only 0.5%.
Efforts are on to further minimize the paraffin oil contamination by modifying the speed of centrifugation
for the separation of the extract and raffinate (Table 5.4.7).
Table 5.4.7: Column Chromatographic Separation of Enriched CME fractions
CME: aq. MeOH Sample name % Purity %Yield
1:16 Enriched CME(after extraction) 97.3 80
Enriched CME (after centrifuge) 97.5 -
1:8 Enriched CME (after extraction) 97.4 60
Enriched CME (after centrifuge) 97.8 -
Conclusions
1. Using adsorbents like celite can reduce liquid paraffin contamination in the enriched methyl
ricinoleate (but limited to small scale)
2. Passing the extract in a Pennwalts’ super centrifuge at 15000 G is effectively reducing the liquid
paraffin contamination in the enriched methyl ricinoleate.
3. Using higher amounts of solvent (aqueous methanol) during LLE (1:16) the yield of enriched
methyl ricinoleate is higher to the extent of 85-90% with GC purity of 96-97%.
4. Using lower amounts of solvent (aqueous methanol) during LLE (1:6.5) the yields of enriched
methyl ricinoleate are lower to the extent of 50% with a GC purity of 99%.
Preparation of Ricinoleic-based Derivatives Employing Enriched Methyl Ricinoleate:

1. Hydrogenation of Enriched Methyl Ricinoleate (MR) and Castor oil Methyl Ester (CME): A
number of experiments were carried out (250 g batch) to standardize the experimental conditions for the
preparation of hydrogenated castor oil methyl esters and hydrogenated enriched methyl ricinoleate.
Hydrogenation of CME or MR (250 g scale) was carried out in a 500 ml autoclave using Ni as catalyst.
Optimized conditions were found to be: Temperature, 150oC; Ni catalyst, 0.5%; pressure, 3-4 kg/cm 2 for
obtaining hydrogenated products. The iodine value was reduced to aproximately 5-8 units. The analysis
of hydrogenation products is given in Table 5.4.8.
 47

Table 5.4.8: Iodine and Hydroxyl Values of Castor Oil Methyl Esters, Enriched Methyl Esters and
their Hydrogenated Products

Sample Name Iodine value Hydroxyl value

CME 76.2 162.6
Hydrogenated CME 7.5 162
Enriched MR 84.5 172.1
Hydrogenated MR 7.0 169.8

2. Preparation of Dehydrated Castor Oil Methyl Esters: A number of experiments were carried out
(300 g batch) to standardize the experimental conditions for the preparation of dehydrated castor oil
methyl esters and dehydrated enriched methyl ricinoleate. CME or MR (300 g) was taken in a 500 ml RB
flask and to this 5% Korvi (acidic) earth was added. The reaction mixture was subjected for heating at
160 to 180oC in oil bath for a period of 3 hr. The mixture was stirred by using mechanical stirrer and the
water generated during the reaction was removed under reduced pressure. The product was filtered by
passing through the celite bed to remove the earth. The samples were analyzed by GC and TLC and the
analytical data is given in Table 5.4.9.
Table 5.4.9: Analysis of Dehydrated Castor Oil Samples
Sample Name % of MR Iodine value Conditions

CME 87.6 76.17 -

Dehydrated-CME 15 113.2 3% Earth+3 hrs, 160oC

Dehydrated-CME 10 118.5 5% Earth+3 hrs, 180oC

Dehydrated-CME <1 128.3 5% Earth+2 ml 1% H2SO4, 3 hr, 180oC

Conclusions:
1. Using 1-2 ml of 1% H2SO4 along with 3% korvi bleaching earth at 180 oC for a period of 2 hr is
effective in dehydration of enriched CME having minimum hydroxyl value and maximum iodine value.
2. Experiments using sodium bisulphate and sodium sulphite as a catalyst for the dehydration of enriched
methyl ricinoleate under the similar conditions did not result in good conversions.
3. The extent of conjugation was determined by UV-spectroscopy and it was found between 18-20%.
4. Work is in progress to increase the extent of conjugation in the dehydration products.
5. Efforts are on to separate and identification of the conjugated and non-conjugated fatty acid by HPLC
and silver ion chromatography
PREPARATION OF UDA-BASED SURFACTANTS
1 Preparation of Mono and Diundecenyl Ethanolamides: Preparation of undecenyl ethanolamide was
conducted by taking different ratios of undecenoic acid (UDA) & ethanolamine at 170°C in a solvent-free
medium. Results obtained are outlined in Table 5.4.10.
 48

O O
0
OH 170 C, OH +
n OH + H2N n
1:1, 2:1, 3:1 NH
UDA ETHANOLAMINE

OH
n N

O
n

Table 5.4.10: Optimization of molar ratio of substrate for the formation of undecenyl
monoethanolamide and diethanolamide.

Reaction Time UDA Monomer Dimer

conditions (hrs)
UDA- 1 16.46 81.79 1.74
Ethanolamine 2 7.79 91.11 1.09
1:1,170 °C 3 5.36 84.89 9.74
UDA- 1 16.50 32.84 50.65
Ethanolamine 2 11.08 25.33 63.57
2:1,170 °C
3 9.06 25.88 65.04
1 77.36 0.0 22.63
UDA- 2 73.91 1.58 24.50
Ethanolamine
3 30.31 0.62 69.05
3:1,170 °C

Results obtained indicate that unimolar ratio of substrate is required for the preferential
formation of monoethanolamide, whereas a 3:1 molar ratio of UDA:ethanolamine for
diundecenyl ethanolamide.
1. Condensation of unimolar Ratio of UDA and Ethanolamine: UDA (3 g, 0.0162 m) and
ethanolamine (0.98 g, 0.0162 m) was taken in 100 mL R.B flask stirring at 170 °C for 3
hrs. The progress of the reaction was monitored by TLC and also by injecting in GC after
silylation. After the completion of reaction, reaction mixture was extracted with ethyl
acetate, washed with water and 5% NaHCO3 solution and dried over anhydrous sodium
sulphate and concentrated. The product was solubilized in hexane and the monomer
precipitates out, which was separated by filtration. Hexane soluble part contains
unreacted UDA, dimer and traces of monomer. The isolated yield of monomer is 95%.
Though monomer formation is predominant within 2 hrs, but as the reaction progresses,
there is slow conversion of monomer to dimer.
 49

2. Condensation of 2:1 molar ratio of UDA and ethanolamine: UDA (3 g, 0.0162 m) and
ethanolamine (0.494 g, 0.0081 m) was taken in 100 mL R.B flask stirring at 170 °C for 3
hrs. The reaction was monitored every 1 hr using TLC and GC after silylation. Reaction
mixture was extracted with ethyl acetate and washed with water and 5% NaHCO3
solution and dried over anhydrous sodium sulphate and concentrated. The product was
soluble in hexane partially and the monomer (solid part) was separated by filtration.
Hexane soluble part contains UDA, dimer and traces of monomer. In this case, both
monomer and dimer are formed in equal amount.
3. Condensation of 3:1 molar ratio of UDA and ethanolamine: UDA (3 g, 0.0162 m) and
ethanolamine (0.32 g, 0.0054 m) was taken in 100 mL R.B flask stirring at 170 °C for 3
hrs. The reaction was monitored every 1 hr using TLC and GC after silylation. The
reaction mixture was passed through the basic alumina to get a pure dimer compound.
Isolated yield of dimer is 85%.
4. Optimization of conditions for the preparation of undecenyl ethanolamide: Based on
these results, optimization of different reaction conditions such as temperature, time and
molar ratio of substrates for the predominant formation of undecenyl monoethanolamide
were conducted. Initially, condensation of stoichiometric amounts of UDA and
ethanolamine were conducted at different temperature under stirred conditions.
UDA (3 g, 0.0612 m) and Ethanolamine (0.98 g, 0.0162 m) was taken in 100 mL R.B flask and
stirred at different temperature (90, 110, 130, 150 and 170 0C) for 10 hrs. The progress of
reaction was monitored by TLC and also by GC after silylation. After 10 hrs, the reaction
mixture was extracted with ethyl acetate and washed with 5% NaHCO3 solution and also using
water, dried over anhydrous sodium sulphate and concentrated in the rotavap.
Monoethanolamide of UDA is insoluble in hexane, whereas the diethanolamide has partial
solubility in hexane. The crude product was solubilized in hexane and the monomer separates
out. Hexane soluble part contains unreacted UDA, diethanolamides and traces of
monoethanolamides of UDA. GC results obtained during the progress of reaction are outlined in
Table 5.4.11.
 50

Table 5.4.11: Percentage of conversion of undecenyl mono and diethanolamides during the reaction
between UDA and ethanol amine (1:1, mol/mol) at different period of time.

Reaction conditions Time Ethanolamine UDA Monomer Dimer

(hrs) (%) (%) (%) (%)
1:1, 90 °C 10 28.19 66.68 5.11 -
1:1, 110 °C 10 15.37 50.09 34.53 -
1:1, 130 °C 2 21.77 51.01 27.20 -
4 17.54 45.37 37.08 -
6 11.62 36.98 51.39 -
8 6.77 31.08 60.73 1.4
10 1.42 26.20 69.29 3.07
2 7.72 29.10 62.77 0.79
UDA-Ethanolamine 4 5.33 20.03 73.87 0.87
1:1, 150 °C 6 0.69 10.26 87.14 1.89
8 - 6.93 84.99 8.07
10 - 6.39 80.93 12.66
UDA-Ethanolamine 1 - 16.46 81.79 1.74
1:1, 170 °C 2 - 7.79 91.11 1.09
3 - 5.36 84.89 9.74

Results obtained indicate that the optimum conditions for the exclusive formation of
undecenylethanolamide are: Equimolar ratio of UDA and ethanolamine, 170 °C of temperature and a
reaction time of 2 hrs. The product was characterized by NMR, IR and ESI-MS. Whereas Table 1 shows
that the optimum conditions for the exclusive formation of diundecenylethanolamide are: 3:1 molar ratio
of UDA:ethanolamine, 170 °C of temperature and a reaction time of 2 hrs. Both the products are
characterized by NMR, IR and ESI-MS.
Spectral data of Undecenylethanolamide: IR (neat; cm-1): 3294, 3092, 1643, 1561; 1H NMR (in CDCl3;
ppm): δ 1.15-1.3 (m; 9H), 1.5-1.6 (m, 2H), 1.9 (m, 2H), 2.1 (t, 2H), 3.3 (m, 2H), 3.6 (m, 2H), 4.8-4.9 (dd,
2H), 5.7 (m, 1H), 5.9 (Br.s, 1H); ESI-MS: 228 (M++1), 250 (M++ Na).
Spectral data of N, N-diundecenylethanolamide: IR (neat; cm-1): 3299, 1737, 1641, 1553; 1H NMR (in
CDCl3; ppm): δ 1.2-1.4 (m; 20H), 1.5-1.7 (m, 4H), 2.0 (dd, 4H), 2.15 (t, 2H), 2.3 (t, 2H), 3.5 (dd, 2H),
4.18 (m, 2H), 4.2-4.3 (m, 2H), 4.85-5.0 (dd, 2H), 5.65-5.85 (m, 1H); EI-MS: 393 (M+)..
Both the compounds were taken for the determination of surface properties. However, N, N-
diundecenylethanolamide is found to be insoluble in water. Aqueous solutions of the monoethanolamide
of UDA were prepared by dissolving appropriate amounts in Milli-Q water and surface tension and cmc
were measured using Kruss K100 tensiometer. Variation of surface tension as a function of logarithm of
surfactant concentration is shown in Fig. 1, depicting the effectiveness of the monoethanolamide in
reducing the surface tension of water. The cmc value was found to be 3.08 × 10 -4 mM and surface tension
at cmc, is 30.7 mN/m.
 51

75

70
Monoethanolamide of UDA
65

Surface tension, mN/m

60

55

50

45

40

35

30

-12 -11 -10 -9 -8 -7

ln C

1. Preparation of Mono and Diundecanoylethanolamides: The above optimized conditions were taken
up for the preparation of mono and diundecanoylethanolamide, the saturated analog of UDA.

O O
OH 1700C, OH +
n OH + H2N n
1:1, 3:1 NH
Undecanoic acid ETHANOLAMINE

OH
n N

O
n

Equimolar mixture of UDA (6 g, 0.032 m) and ethanolamine (1.97 g, 0.032 m) was taken in 100 mL R..B
flask and stirred at 170 °C for 2 hrs. The progress of reaction was monitored by TLC as well as by GC
after silylation. The reaction mixture was extracted with ethyl acetate and washed with water followed by
5% NaHCO3 solution, dried over anhydrous sodium sulphate and concentrated in the rotavap. The product
was soluble in hexane partially. Monomer was separated out by filtration. The isolated yield of
monoethanolamide is 96 %.
Spectral data of Undecanoylethanolamide: IR (neat; cm-1): 3300, , 1643, 1456; 1H NMR (in CDCl3; ppm):
δ 0.9 (t, 3H) 1.15-1.3 (m; 12H), 1.5-1.6 (m, 2H), 2.2 (m, 4H), 3.4 (t, 2H), 3.7 (t, 2H), 2.2 (s, 1H), 6.1(s,
1H) ; ESI-MS: 230 (M++1),231(M++2) 252 (M++ Na).
 52

For the preparation of diethanolamide of undecanoic acid, 3:1 molar ratio of UDA (6 g, 0.032 m) and
ethanolamine (0.64 g, 0.01 m) was taken in 100 mL R.B flask and stirred at 170 °C for 3 hrs. After
completion of reaction in 3 hrs, the reaction mixture was passed through the Basic alumina to get a pure
dimer compound. Isolated yield of dimer is 87%.
Spectral data of N, N-diundecanoylethanolamide: IR (neat; cm-1): 3350, 1737, 1641, 1453; 1H NMR (in
CDCl3; ppm): δ 0.9 (t, 6H) 1.2-1.4 (m; 24H), 1.5-1.7 (m, 4H), 2.2-2.5 (dd, 4H), 3.5 (t, 4H), 4.18 (t, 4H),
5.65-5.85 (s, 1H); EI-MS: 398 (M+ +1)..
Both the compounds were taken for the determination of surface properties. However, N, N-
diundecanylethanolamide is found to be insoluble in water. Aqueous solutions of the monoethanolamide
of undecanoic ethanolamide were prepared by dissolving appropriate amounts in Milli-Q water and
surface tension and cmc were measured using Kruss K100 tensiometer. Variation of surface tension as a
function of logarithm of surfactant concentration is shown in below, depicting the effectiveness of the
-4
monoethanolamide in reducing the surface tension of water. The cmc value was found to be 2.71 × 10
mM and surface tension at cmc, is 37.4 mN/m.

75
undecanioc-ethanolamide(mono-0.6mMol)
70 0.271 Mol/l

65
Avg.Surf.tension mN/M

60

55

50

45

40

35

-7 -6 -5 -4 -3 -2 -1
lnC

2. Preparation of UDA-based Ester Quats: Esterification of N-Methyl diethanolamine with UDA was
carried out in presence of 5% sodium bisulphate monohydrate at 120 °C temperature under stirred
conditions. The esterified product was then quaternized to get the desired product.
 53

O
O
HO
5% NaHSO4.H2O 8 O
8
OH + N
N
HO 120 °C O
UDA N-methyl Di ethanolamine 8
O
Ester

UDA (6.19 g, 0.336 m) and N-methyl diethanolamine (1 g, 0.0084 m) was taken in 100 mL R.B flask
followed by the addition of 5% Sodium bisulphate monohydrate. The reaction mixture was stirred at 120
°C for 4 hrs. The progress of reaction was monitored by TLC. After completion of reaction, the reaction
mixture was extracted with ethyl acetate, washed with 5% NaHCO3 and also with water, dried over
anhydrous sodium sulfate and finally concentrated in the rotavap to get the crude product. The compound
was passed through basic alumina and the structural confirmation of the compound was confirmed by IR,
GC, GC-MS, NMR and ESI-Mass. The isolated yield of diester is 85% based on N-methyl
diethanolamine.
Spectral data of N-Me diethanolamine diundecenate diester: IR (neat; cm-1):3010, 2960,1760,1615,1560,
1456; 1H NMR (in CDCl3; ppm): δ 1.15-1.3 (m; 20H), 1.5-1.6 (m, 4H),2.0 (m, 4H), 2.2 (t, 4H),2.4 (s,3H),
2.7 (t, 4H) 4.2 (t, 4H), 4.9-5.1 (d, 4H), 5.7-5.9 (dd, 2H); ESI-MS: 452(M++1),453(M++2).
O O

O O
DMS,DCM
N N+
Room tmep -
O O MeSO4
O O
N-methyl diethanolamine diundecenoate of was taken in dry DCM followed by the addition of 2 molar
equivalent of anhydrous dimethyl sulphate (DMS). The reaction mixture was kept stirred for 4 hrs at
room temperature using calcium chloride guard tube. After completion of reaction, the organic solvent
was evaporated. The reaction mixture was kept in an ice bath followed by the slow addition of dry diethyl
ether. The solid obtained was separated by filtration. The filtrate was kept further for crystallization. The
combined precipitate was dried and weighed. The quaternized product was characterized by ESI-Mass.
Isolated yield of quats ester is 86%.
Aqueous solutions of the quaternized salt was prepared by dissolving appropriate amounts in Milli-Q
water and surface tension and cmc were measured using Kruss K100 tensiometer. Variation of surface
tension as a function of logarithm of surfactant concentration is shown below, depicting the effectiveness
of the compound in reducing the surface tension of water. The cmc value was found to be 3.0 × 10 -2 mM
and surface tension at cmc, is 25.46 mN/m.
 54

50
UDA_DMS_DIESTER(1mm)-2

45
Avg.Surf.tension mN/M

40

35

30

25

20
-6 -5 -4 -3 -2 -1

lnC

Accordingly, the saturated analog of the above ester quat, N-Methyl diethanolamine diundecanoate was
also synthesized. Esterification of N-Methyl diethanolamine with undecanoic acid was carried out in
presence of 5% sodium bisulphate monohydrate at 120 °C temperature under stirred conditions. The
esterified product was then quaternized to get the desired product.

O
O
HO
5% NaHSO4.H2O 8 O
8
OH + N
N
HO 120 °C O
Undecanoic acid N-methyl Di ethanolamine 8
O
Ester

Undecanoic acid (4.7 g, 0.025 m) and N-methyl diethanolamine (1 g, 0.0084 m) was taken in 100 mL R.B
flask followed by the addition of 5% sodium bisulphate monohydrate. The reaction mixture was stirred at
120 °C for 4 hrs. The progress of reaction was monitored by TLC. After completion of reaction, the
reaction mixture was extracted with ethyl acetate, washed with 5% NaHCO3 and also with water, dried
over anhydrous sodium sulfate and finally concentrated in the rotavap to get the crude product. The
compound was passed through basic alumina and the structural confirmation of the compound was
confirmed by IR, GC,GC-MS,NMR, ESI-Mass. The isolated yield of diester is 87% based on N-methyl
diethanolamine.
 55

Spectral data of N-Me DiEthanolamine diundecanoate: IR (neat; cm-1): 2960,1760, 1560, 1456;
1
H NMR (in CDCl3; ppm): δ 0.9 (t, 6H) 1.15-1.3 (m; 24H), 1.5-1.6 (m, 4H), 2.2 (m, 4H),2.4 (t,4H), 2.8 (t,
4H) 3.6 (s, 3H), 4.2 (t, 4H); ESI-MS: 456(M++1),457(M++2).

O O

O O
DMS,DCM
N N+
Room tmep -
O O MeSO4
O O

N-methyl diethanolamine diundecanoate was taken in dry DCM followed by the addition of 2 molar
equivalent of anhydrous dimethyl sulphate (DMS). The reaction mixture was kept stirred for 4 hrs at
room temperature using calcium chloride guard tube. After completion of reaction, the organic solvent
was evaporated. The reaction mixture was kept in an ice bath followed by the slow addition of dry diethyl
ether. The solid obtained was separated by filtration. The filtrate was kept further for crystallization. The
combined precipitate was dried and weighed. The quaternized product was characterized by ESI-Mass.
Isolated yield of ester quats is 91%.
Aqueous solutions of the N, N-dimethyl Diethanolamine diundecanoate were prepared by dissolving
appropriate amounts in Milli-Q water and surface tension and cmc were measured using Kruss K100
tensiometer. Variation of surface tension as a function of logarithm of surfactant concentration is shown
in Fig 5.4.2, depicting the effectiveness of the monoethanolamide in reducing the surface tension of
water. The cmc value was found to be 0.42× 10 -2 mM and surface temsion at cmc is 22.52 mN/m.

80
N-Me_DMS_Undeca-diester(0.1 mMol)

70
Avg.Surf.tension mN/M

60

50

40

30

20

-9 -8 -7 -6 -5 -4 -3

lnC
 56

In the previous quarter, UDA-based ester quats such as N-methyl diethanolamine diundecenoate
dimethylsulphate and also its saturated counterparts, N-methyl diethanolamine diundecanoate
dimethylsulphate were synthesized and evaluated. To study the effect of double bond and also its
position on the alkyl chain on their surface properties, two more compounds, N-methyl
diethanolamine distearate dimethylsulphate and N-methyl diethanolamine dioleate
dimethylsulphate were synthesized and evaluated during this period. Initially, N-methyl
diethanolamine distearate was prepared by taking stoichiometric amounts of stearic acid and
N-methyl diethanolamine and 5% sodium bisulphate monohydrate and heating the mixture at
120°C temperature under stirred conditions. The product was quaternized with dimethyl sulphate
to get N-methyl diethanolamine distearate dimethyl sulphate.

Briefly, stearic acid (7.163 g, 0.025 m) and N-methyl diethanolamine (1 g, 0.0084 m) was taken
in 100 mL R.B. flask followed by the addition of 5% Sodium bisulphate monohydrate and the
reaction mixture was stirred at 120 °C for 4 hrs. The progress of reaction was monitored by TLC.
After completion of reaction, the reaction mixture was extracted with Ethyl acetate, washed with
5% NaHCO3 and also with water, dried over anhydrous sodium sulfate and concentrated in the
rotavap to get the crude product. The crude mixture was passed through the basic alumina
column to get the pure product (isolated yield is 85%). The structure of the product was
confirmed by IR, GC, GC-MS, NMR and ESI-Mass.

O
O
HO
NaHSO4.H2O 15
O
OH + N
15 HO 120 °C N
O
Stearic N-methyl Di ethanolamine 15
O
Ester

Quaternization of N-methyl diethanolamine distearate was conducted in a R.B flask in Dry DCM
in presence of anhydrous dimethyl sulphate (DMS). The reaction mixture was stirred for 5 hrs at
room temperature using calcium chloride guard tube. After completion of reaction, the organic
phase was evaporated. The reaction mixture was taken in dry diethyl ether and kept in an ice-
bath. A solid product separates out, which was separated and further solubilized in dry ether and
cooled in an ice-bath. This operation was repeated thrice to get pure quaternized product. The
structure of the final quaternized product was confirmed by using TLC and ESI-Mass.
 57

O
O
15
O
DMS,DCM O -
N 15 MeSO4
O +
N
Room tmep
15 O
O 15

Ester O

Aqueous solutions of the compound were prepared by dissolving appropriate amounts in Milli-Q
water and surface tension and cmc was measured using Kruss K100 tensiometer. Variation of
surface tension as a function of logarithm of surfactant concentration is shown in Figure 1. Three
measurements were taken in total for three different solutions of surfactants. The average cmc
and surface tension at cmc of this compound was found to be 14.95 × 10-2 moles/L and 56.59
mN/m respectively.

Di Stearic N-Me-Diethanolamine Ester(1 mM)3rd

72
CMC= 0.212 ST at cmc 55.3

70

68

66
AVg S.F.T mN/M

64

62

60

58

56

54

52
-6 -5 -4 -3 -2 -1 0 1

ln C

Figure 5.4.2. Variation of surface tension as a function of logarithm of surfactant concentration of N-

methyl diethanolamine distearate dimethylsulphate.

Similarly, N-methyl diethanolamine dioleate was prepared by taking stoichiometric amounts of

oleic acid and N-methyl diethanolamine and 5% sodium bisulphate monohydrate and heating the
 58

mixture at 120 °C temperature under stirred conditions. The product was quaternized with
dimethyl sulphate to get N-methyl diethanolamine dioleate dimethyl sulphate.

Briefly, Oleic acid (7.118 g, 0.025 m) and N-methyl diethanolamine (1 g, 0.0084 m) was taken in 100 mL
R.B. flask followed by the addition of 5% Sodium bisulphate monohydrate and the reaction mixture was
stirred at 120 °C for 4 hrs. The progress of reaction was monitored by TLC. After completion of reaction,
the reaction mixture was extracted with Ethyl acetate, washed with 5% NaHCO3 and also with water,
dried over anhydrous sodium sulfate and concentrated in the rotavap to get the crude product. The crude
mixture was passed through the basic alumina column to get the pure product (isolated yield is 80%). The
structure of the product was confirmed by IR, GC, GC-MS, NMR and ESI-Mass.

O
O HO a a O
NaHSO4.H2O
a a OH + N O
N
HO 120 °C a a
Oleic acid
N-methyl Di ethanolamine O
Ester

Quaternization of N-methyl diethanolamine dioleate was conducted in a R.B flask in Dry DCM in
presence of anhydrous dimethyl sulphate (DMS). The reaction mixture was stirred for 5 hrs at room
temperature using calcium chloride guard tube. After completion of reaction, the organic phase was
evaporated. The reaction mixture was taken in hexane and the hexane-insoluble part was separated.
Hexane was removed from the hexane soluble part to get the crude product. The reaction mixture was
taken in dry diethyl ether and kept in an ice-bath. A solid product separates out, which was separated and
further solubilized in dry ether and cooled in an ice-bath. This operation was repeated thrice to get pure
quaternized product. The structure of the final quaternized product was confirmed by using TLC and ESI-
Mass.

O
O
O DMS,DCM MeSO-4
a a
a a O
N +
N
O Room tmep
a a
O
a a
O
Ester O

Aqueous solutions of the compound were prepared by dissolving appropriate amounts in Milli-Q
water and surface tension and cmc was measured using Kruss K100 tensiometer. Variation of
surface tension as a function of logarithm of surfactant concentration is shown in Figure 5.4.3.
Three measurements were taken in total for three different solutions of surfactants. The average
 59

cmc and surface tension at cmc of this compound was found to be 59.6 × 10-2 moles/L and 45.55
mN/m respectively.

Di Oliec N-Me-Diethanolamine ester(2 mM)

70 CMC=0.5596, ST at cmc 45.94

65
AVg S.F.T mN/M

60

55

50

45

-5 -4 -3 -2 -1 0 1
ln C

Figure 5.4.3. Variation of surface tension as a function of logarithm of surfactant concentration of N-

methyl diethanolamine dioleate dimethylsulphate.

Surface properties of all the four ester quats surfactants, namely N-methyl diethanolamine
diundecenoate dimethylsulphate, N-methyl diethanolamine diundecanoate dimethylsulphate, N-
methyl diethanolamine distearate dimethylsulphate and N-methyl diethanolamine dioleate
dimethylsulphate were also determined using fluorescence spectrophotometer using pyrene as
fluorophore.
 60

Figure 5.4.4. Plot of I1/I3 of pyrene against the logarithm of concentration of surfactants.

For fluorescence measurements, the pyrene concentration was held constant at 5.0 μM, and the
surfactant concentration varied over a wide range. Then 3 mL of each solution was placed in a
10-mm rectangular quartz cell, and the spectra were run on a Fluorescence Spectrophotometer
(M/s Varian, Model: Cary Eclipse). Py was excited at 337 nm, and emissions was recorded over
the range of 350 to 500 nm at a scan rate of 120 nm/min. The excitation slit width was set at 20
nm and emission at 2.5 nm. The first and third vibronic peaks of pyrene was measured at 373 and
383 nm. In all cases, the CMC was determined from the inflection point of the plot I1/I3 vs.
concentration of the surfactant. All solutions were aged for 24 h before measurement. The cmc
of the four ester quats was determined and are shown in Table 5.4.12.

A comparative study of surface properties of four ester quats surfactants, namely N,N-dimethyl
diethanolamine diundecenoate dimethylsulphate, N,N-dimethyl diethanolamine diundecanoate
 61

dimethylsulphate, N,N-dimethyl diethanolamine distearate dimethylsulphate and N,N-dimethyl

diethanolamine dioleate dimethylsulphate was made.

Table 5.4.12. Comparative surface properties of the four ester quats.

Compound Name cmc cmc Surface tension

(×10-2 mM/L) (×10-2 mM/L) at cmc
By Fluorescence By Surface (mN/m)
Tensiometer

N,N-Dimethyl diethanolamine 9.67 3.0 25.46

diundecenoate dimethylsulphate
N,N-Dimethyl diethanolamine 1.57 0.42 22.52
diundecanoate dimethylsulphate
N,N-Dimethyl diethanolamine -- 59.6 45.55
dioleate dimethylsulphate
N,N-Dimethyl diethanolamine 9.42 14.95 56.59
distearate dimethylsulphate

3. Phosphorylation of Diundecenyl ethanolamide: N, N-diundecenylethanolamide was

found to be insoluble in water. The hydroxyl group of this compound was derivatized by
phosphorylation using polyphosphoric acid, followed by making sodium salts.

O O
O
( )7 ( )7
1. (H3PO4)n ,CHCl3 /H2O
N N
OH ( )7 O P ONa
( )7
2. NaOH in ethanol
O O
ONa

Procedure: Diundecenylethanolamide (3.7 g, 0.0095 mol) was dissolved in chloroform and poly
phosphoric acid (1.81 ml, 0.011 mol) was added slowly into it. The reaction mixture was
refluxed at 70 °C for 10 min followed by the addition of water (5 ml). The total reaction mixture
was refluxed for 4 hr and the progress of reaction was monitored by TLC. After completion of
the reaction, chloroform was evaporated and the reaction mixture was extracted with ethyl
acetate (EA) and washed with water thoroughly. The organic layer was dried over anhydrous
sodium sulphate and concentrated to get the 3.5 g (78.6%) of phosphate product. The product
was finally converted to its Na-salts by the quantitative addition of ethanolic NaOH (22.18 mL of
0.0148 M of NaOH in ethanol). The ethanol was evaporated from the final product and
 62

crystallized from ether to get 2.8 g (74.6%) of disodium salt of diundecenylethanolamide

phosphate.
The purified compound was taken for the measurement of surface tension using Kruss
Tensiometer. The compound was found to have CMC 3.68 mM and surface tension at CMC 25.6
mN/M.

CMC=3.68 mM
70
SFT=25.6 mN/M
Surface tension (dynes/cm)

60

50

40

30

20
-4 -3 -2 -1 0 1 2

ln C

Figure 5.4.5. Variation of surface tension as a function of logarithm of surfactant concentration of

disodium salt of diundecenylethanolamide phosphate.

In a similar fashion, the hydroxyl group of undecenylethanolamide was also phosphorylated

using polyphosphoric acid, followed by conversion to its sodium salts.

O
O 1. (H3PO4)n , DCM /H2O O
( )7
( )7
NH OH 2. NaOH in ethanol N
H O P ONa

ONa
 63

Procedure: Undecenylethanolamide (2 g, 0.0088 mol) was dissolved in DCM and poly

phosphoric acid (1.71 ml, 0.001 mol) was added slowly into it. The reaction mixture was stirred
at R.T for 10 min followed by the addition of water (5 ml). The total reaction mixture was stirred
for 4 hr and the progress of reaction was monitored by TLC. After completion of the reaction,
DCM was evaporated and the reaction mixture was extracted with ethyl acetate (EA) and washed
with water thoroughly. The organic layer was dried over anhydrous sodium sulphate and
concentrated to get the 1.45 g (53.7%) of phosphate product. The product was finally converted
to its Na-salts by the quantitative addition of ethanolic NaOH (14.2 mL of 0.0094 M of NaOH in
ethanol). The ethanol was evaporated from the final product and crystallized from ether to get
1.2 g (72.7%) of disodium salt of undecenylethanolamide phosphate.
The purified compound was taken for the measurement of surface tension using Kruss
Tensiometer. The compound was found to have CMC 0.552 mM and surface tension at CMC
33.54 mN/M.

UDA Ethanolamide Phospho sodiumsalts(4mmol)2nd

CMC=0.5528 mmolSFT=33.549

70

60
Avg,S.F.T mN/M

50

40

30

20

-5 -4 -3 -2 -1 0 1
ln C

Figure 5.4.6. Variation of surface tension as a function of logarithm of surfactant concentration of

disodium salt of Undecenylethanolamide phosphate.
 64

4. Preparation of Undecenyl Phospho Di Sodium Salts: Direct phosphorylation of

undecenoic acid was also carried out using polyphosphoric acid. Initially UDA was converted to
its methyl ester by the treatment of 2% H2SO4 in methanol. The resulting methyl undecenoate
was reduced to undecenyl alcohol by the treatment of NaBH4, which was finally phosphorylated
and converted to its di-sodium salts.

O O
2%H2SO4 MeOH
OH OMe
UDA

NaBH4 t-BuOH-MeOH

O
OH (H3PO4)n
P
O OH DCM/H2O OH
Undecenyl Phosphate Undecenyl Alcohol

NaOH/EtOH

O
O-Na+
P
O O-Na+

Di sodiumsalts of Undecenyl Phosphate

Procedure: Undecenyl Alcohol (5 g, 0.029 mol) was dissolved in DCM and polyphosphoric
acid (5.68 ml, 0.035 mol) was added slowly into it. The reaction mixture was stirred at R.T for
10 min followed by the addition of water (5 ml). The total reaction mixture was stirred for 4 hrs
and the progress of reaction was monitored by TLC. After completion of the reaction, DCM was
evaporated and the reaction mixture was extracted with ethyl acetate (EA) and washed with
water thoroughly. The organic layer was dried over anhydrous sodium sulphate and concentrated
to get the 6.12 g (83.6%) of phosphate product. The product was finally converted to its Na-salts
by the quantitative addition of ethanolic NaOH (29.78 mL of 0.049 M of NaOH in ethanol). The
ethanol was evaporated from the final product and crystallized from ether to get 3.8 g (52.4%) of
disodium salt of Undecenyl phosphate. The purified compound was taken for the measurement
of surface tension using Kruss Tensiometer. The compound was found to have CMC 1.005 mM
and surface tension at CMC 32.4 mN/M.
 65

Sodium salts of Undecenyl Phosphate(8mmol)1st

CMC=1.005 mmol SFT=32.401

70

60
Avg.S.F.T mN/M

50

40

30

20

-4 -3 -2 -1 0 1 2
ln C

Figure 5.4.7. Variation of surface tension as a function of logarithm of surfactant concentration of

disodium salt of Undecenyl phosphate.

5. Preparation of Di Sodium Salts of 11-Phospho-10-hydroxy Methyl Undecanoate: In

an alternate approach, the side chain double bond of methyl undecenoate was functionalized. The
pathway involves epoxidation of double bond followed by the ring opening by orthophosphoric
acid as outlined in the scheme given below.
 66

OH 2%H2SO4/MeOH OMe

UDA
Reflux Methyl Undecenoate O
O

mCPBA/DCM
R.T

OH
O
O OMe H3PO4 O
OMe
P Toluene, R.T
HO O
OH 11-phospho,10-hydroxy methyl Undecanoate O
10,11-epoxy methyl Undecanoate

Ethanol/NaOH(1 M)

OH
O
O OMe
+ _
P
NaO _ O
ONa
+
Di sodium salts of 11-phospho,10-hydroxy methyl Undecanoate

Procedure: 10,11-epoxy methyl Undecanoate l (10 g, 0.046 mol) was dissolved in Toluene and
orthophosphoric acid (2.61 ml, 0.046 mol) was added slowly into it. The reaction mixture was
stirred at R.T for 2 hr and the progress of reaction was monitored by TLC. After completion of
the reaction, toluene was evaporated and the reaction mixture was extracted with ethyl acetate
(EA) and washed with water thoroughly. The organic layer was dried over anhydrous sodium
sulphate and concentrated to get the 12.28 g (84.28%) of phosphate product. The product was
finally converted to its Na-salts by the quantitative addition of ethanolic NaOH (42.54 mL of
0.0708 M of NaOH in ethanol). The ethanol was evaporated from the final product and
crystallized from ether to get 12.1 g (96.0%) of disodium salt of 11-phospho-10-hydroxy methyl
undecanoate.
The purified compound was taken for the measurement of surface tension using Kruss
Tensiometer. The plot of ln C vs surfactant concentration showed continuous decrease in surface
tension with the increasing concentration of surfactants till 200 mM. This unusual phenomenon
of this surfactant will be looked into by both surface tension and fluorescence probing
techniques.
 67

11-Phospho,10-Hydroxy methylUndecanoate sodium salts(100mM)

70

65

60
Avg.S.F.T mN/M

55

50

45

40

-2 -1 0 1 2 3 4
ln C

Figure 5.4.8. Variation of surface tension as a function of logarithm of surfactant concentration of

disodium salts of 11-phospho-10-hydroxy methyl undecanoate.

SUMMARY

Enrichment of Methyl Ricinoleate from Castor Oil Methyl Esters:

Using liquid paraffin as a medium, the selectivity in enrichment of methyl ricinoleate from castor
oil methyl esters is good but due to the closer densities of liquid paraffin and aqueous methanol
the contamination of liquid paraffin with the solute was to the extent of 2.5-3.5% which was
determined by TLC and column chromatography. Therefore, the experiments using liquid
paraffin as medium in enrichment of methyl ricinoleate by LLE is not satisfactory.
The method of using refined vegetable oil as medium in enrichment of methyl ricinoleate by
LLE, the selectivity is good and the contamination of oil with solute is less than 0.8% as
determined by TLC and column chromatography. Efforts are on at further minimizing the
contamination. Standardization of up-scaling experimental conditions are in progress. Efforts are
on to explore the possibilities of separation of solute from extract using solvent resistant thin film
composite reverse osmosis membranes. Using the enriched methyl ricinoleate various derivatives
 68

are planned to prepare and compare the properties with respect to the CME. Experiments are in
progress to standardize the experimental conditions.
Further upscaling experiments are being conducted for the enrichment of methyl ricinoleate from
castor oil methyl esters. Adsorbents like celite will be tried in reducing the vegetable oil
contamination in the extract. Centrifugation is another option to be explored in minimizing the
vegetable oil contamination. Thin film composite RO membranes will be explored in separation
of the solute from the solvent of the extract in liquid-liquid extraction process. Efforts are on in
increasing the conjugation in the dehydrated products and methodology for evaluation of
conjugated fatty acid esters in the products by HPLC and Silver ion Thin layer chromatography.
Design and fabrication of Liquid-liquid extraction set-up is under progress.
Preparation of UDA-based Surfactants: Optimized conditions for exclusive preparation of N-
undecenylethanolamine and N, N-diundecenylethanolamine. N-undecenylethanolamine was
prepared by taking 1:1 molar ratio of UDA and ethanolamine and heating the reaction mixture at
170 °C for 2 hrs. The structure of the compound was confirmed by NMR, IR and mass. The cmc
and surface tension at cmc was determined following Kruss Tensiometer. The cmc value was
found to be 3.08×10-4 mM and surface temsion at cmc, is 30.7 mN/m. N,N-
diundecenylethanolamine was prepared by taking 3:1 molar ratio of UDA and ethanolamine and
heating the reaction mixture at 170 °C for 2 hrs. Attempts to determine the micellar properties of
this compound failed as the compound is almost insoluble in water.
UDA-based ester quats, N, N-dimethyl diethanolamine diundecenoate dimethylsulphate was
prepared by esterification in presence of 5% sodium bisulphate monohydrate at 120 °C under
stirred conditions. The cmc value of the ester quat was found to be 3.0 × 10-2 mM/L and surface
tension at cmc, is 25.46 mN/m. Four UDA-based surfactants are synthesized and evaluated for
their surface properties using surface tension and fluorescence probing techniques. Influence of
the presence of unsaturation and also its location in the hydrophobic chain on surface properties
of four different ester quats are also studied.
 69

5.5 Research Achievement: Jayant Agro Organic Limited, Mumbai

The ultimate goal of the project is to develop value added products from deoiled castor cake and
2-octanol based on the techno-commercial processes. The intended value added products from
the deoiled castor cake-high protein and 2-octanol are as under:
Deoiled castor cake based value added products:
Extraction of the protein from the deoiled castor cake and /or deoiled castor cake-high
protein by using an alkaline solution of the sodium hydroxide
o Optimization of the pH of alkaline solution for the maximum protein extractability
from said raw materials.
o Optimization of the solid to liquid ratios for the maximum protein extractability
Isolation of the protein from the alkaline extract by precipitation process
o Optimization of the iso-electric point (pH) for maximum protein precipitation and
the yield.
Preparation of the bio-film and the adhesives based on the CPI, SPI and a combination of
CPI and SPI.
o The comparative studies of bio-film and adhesives.
Scale up of the processes for commercialization.
2-Octanol based value added products
 To carry out the esterification reactions using anhydrides like phthalic, maleic, etc. and
carboxylic acids such adipic, benzoic, etc. to develop products, which will add the value.
Also, compare the properties & performance of such developed products with existing
commercial products based on 2-ethyl hexanol.
 To carry out an etherification reactions to from symmetrical and asymmetrical ethers
using 2-octanol and epichlorohydrin respectively.
 To optimize the reaction parameters like temperature, mole ratios, and catalyst
concentration.
 To purify both symmetric and asymmetric ethers by distillation and these will be tested
for their applications, and/or will be evaluated their performance by outside parties.
 Scale up the processes for commercialization.
 70

5.5.1 Deoiled castor cake based value added products:

The aim was to obtain protein isolate from deoiled castor cake after extraction and isolation as it is
described in the objective of the research work and prepare the adhesive and bio-film. The research work
observation and results as under:
 The protein extraction process was developed for deoiled castor cake by using alkaline solution of
sodium hydroxide. Experimentally, the effect of ratio of cake to liquid such as 1:10,
1:15,1:20,1:25 and 1:30 wt/v, and effect of pH of solution like 7,9,11, and 13 on protein
extraction were evaluated for process optimization. 1:10 wt/v, a ratio of cake to liquid and pH 13
of solution were optimized for protein extraction.
 Maximum extractability of protein found more than 97 % based on the total protein present in
castor cake.
 Attempts have been made to obtain the castor protein isolate (CPI) from alkaline extract of
protein using iso-electric point. For castor protein isolation, experimentally tested protein
precipitation at 3, 3.5, 4.0, 4.5 and 5.0, and 4.5 pH gave maximum precipitation of protein from
its alkaline extract.
 Low recovery of protein from alkaline extract followed by precipitation using iso-electric point
(pH-4.5) was obtained. This is due to lack of specific filtration medium. In this studies we used
Whatman filter paper number 42.
 When iso-electric point (pH) precipitation process used for main extract and washing separately,
the recovery of protein increased by 8-9 %. However, dark colour CPI was found
 Efforts have been made to obtain protein by neutralization of the alkaline extract using both
phosphoric acid and citric acid, separately and subsequently sun-dried in tray at ambient
temperature. The colour of protein isolate was improved.
 Efforts are being made to prepare bio-film & adhesive based on CPI, SPI, and a mixture of CPI
and SPI. The comparison study will be carried out for such bio-films & adhesives.
 Efforts will be made to increase the recovery castor protein isolate.
5.5.2 Octanol based value added products
2-octanol is a secondary alcohol and has different chemical properties in relation to 2-ethyl hexanol and
1-octanol. It undergoes similar chemical reactions as other alcohols follow such as esterification,
dehydration, etherification, ethoxylation, sulfation, etc. Hence, the derivatives, which are being
industrially manufactured based on the 2-ethyl hexanol, and the similar derivatives can be produced using
2-octanol. The production of 2-octanol is entirely dependent on the demand of sebacic acid and price of
the raw material (castor oil). By adding value to the 2-octanol by converting it to value added products
will improve the economics of the sebacic acid production and thus increase the usage & thus indirectly
benefit the castor plant growing farmers by increasing demand for the castor seeds & oil.
 71

Aim was to prepare 2-octanol based esters and ether, optimize process parameters, and study comparison
between existing 2-ethyl hexanol and/or isononanol esters and ethers. The following ester and ether were
prepared using 2-octanol.
5.5.3 Esters based on 2-octanol
Dicapryl Phthalate (DCP):
 Phthalic esters based on 2-octanol could be prepared by esterification using p-TSA, organo-
metallic catalysts, TBM, etc and also by trans-esterification using dimethyl phthalate and sodium
methoxide and a mixture of sodium methoxide and calcium hydroxide.
 The synthesis of DCP using Insocat-TBM resulted in poor conversion, and dark colour ester was
obtained. When the esterification of PAN was carried out for six hours in the presence of solvent
(toluene) using same catalyst and 2-octanol only 80% conversion of PAN was found with dark
coloured ester product.
 Synthesis of DCP based on 2-octanol by trans-esterification using DMP, sodium methoxide and a
mixture of sodium methoxide and calcium hydroxide also resulted in poor conversion and dark
colour of ester.
 Both organo-metallic catalysts, namely SV CAT 100 and FASCAT 2001 were superior to other
catalysts and were used in the synthesis of DCP as described in earlier reports. Henceforth, in the
synthesis of DCP for scale up study and further industrial utilization, these two catalysts can be
employed. Mole ratio of 2-octanol to PAN was 2.42 and reaction temperature 220 deg C were
optimized. When organo-metallic catalysts were used > 99 % conversion of PAN was obtained
with light colored ester appearance. The loading of catalyst was increased by five fold (0.1 % to
0.5% based on weight of PAN) and the reaction time significantly decreased.
 Remarkable and appreciable results were observed when the bleached DCP was tested for both
compact and foam layers evaluations against DEHP and DINP in PVC formulations. The results
were incorporated in earlier report.
Dicapryl sebacate (DCS):
 Based on the synthesis of DCP and its reaction parameters, the synthesis of DCS was carried out
using sebacic acid (SA), 2-octanol and, organo-metallic catalyst (FASCAT-2001) at 220 deg C.
The loading of catalyst was 0.5 % based on the weight of SA. > 99 % conversion of SA was
found with light appearance of the ester.
 Remarkable and appreciable results were observed when the bleached DCS was tested for both
compact and foam layers evaluations against DEHP and DINP in PVC formulation. The results
were incorporated in earlier report.
 72

Dicapryl maleate (DCM):

Synthesis of DCM was carried out using maleic anhydride (MAN), 2-octanol and
catalysts such as p-TSA and FASCAT 2001. When p-TSA was used as catalyst at 120
deg under vacuum, a poor conversion of MAN was found with dark colour of ester.
When FASCAT-2001 was used as catalyst and the reaction carried out 220 deg C, > 99
% conversion of MAN was found. The synthesized DCM can be used as anionic
surfactant after sulfonation with sodium bisulfite. The synthesized sulfonated ester can be
used in place of sodium dioctyl sulfosuccinate. Efforts are being made to prepare sodium
dicapryl sulfo succinate.
5.5.4 Synthesis of Dicapryl adipate (DCA) and capryl benzoate (CB)
Syntheses of DCA and CB were carried out using the same parameters as optimized in
case of DCP and DCS syntheses. >99 % conversion of the adipic acid was obtained when
the reaction was carried out using 2-octanol and FASCAT-2001 at 220 deg C.
>98 % conversion of benzoic acid was found when the reaction was carried out using the
same reaction parameters as described earlier.
5.5.6 Ethers based on 2-octanol
Capryl glycidyl ether (CGE):
Synthesis of CGE was carried out using 2-octanol, sodium hydroxide, epichlorohydrin
and TBAB (Tetra butyl ammonium bromide) as a phase transfer catalyst at 40-42 deg C.
In the synthesis of asymmetrical ethers maximum conversion was obtained about 87 %.
The un-reacted reactants such 2-octanol and epichlorohydrin need to be distilled off and
reused in another batch for synthesis. The maximum conversion could be expected using
sodium caproxide instead of 2-octanol and sodium hydroxide.
Dicapryl ether (DCE)
Synthesis of symmetrical ethers based on 2-octanol alone could be possible in the
presence of acid catalysts at lower temperature (130- 140 deg C), and / or using 2-octanol
and 2-octene in the presence of acidic resin at lower temperature.
The products were developed under NAIP-JAOL Project are shown in Fig 5.5.1, Fig 5.5.2 and
Fig 5.5.3.
 73

2-OCTANOL BASED DERIVATIVES

Surfactants
(Anionic and non ionic)

PAN & Cat. DCP Plasticizer: Flooring, cable,

CE/SCS/SCES wire, film and sheet

SA & Cat.
DCS Plasticizer: Medical
Ethoxylation /Sulfation
applications

Adipic acid & Plasticizer: Flooring,

2-octanol Esterification Cat. DCA cable, cling and film

ECH &PTC DCM / Plasticizer and

MAN & Cat.
surfactants
Acid cat. DCF (on further rxn.)

Dehydration BA & Cat. CB Plasticizer and

Etherification
emollient

2-octene DCE CGE PAN, 2EH & Plasticizer: Flooring,

Cat. COP cable, wire, film and sheet

Solvent
Plasticizer and surfactants
(on further rxn.)

Other derivatives

NAIP

Fig 5.5.1: Products developed based on 2-octanol under NAIP-JAOL Project

COMPACT LAYERS – SUMMARY OF FOAM LAYERS – SUMMARY OF

RESULTS RESULTS
Property DCS DCP DINP DEHP
Rheology at Property DCS DCP DINP DEHP
-- -- 0 0
low shear rate
Rheology at
Rheology + 0 0 0
higher shear + 0 0 0
rate
Paste ageing 0/- - 0 0 Paste ageing 0 0 0 0
Air Release + 0/+ 0 0
Efficiency ++ 0/+ 0 + Yellow Index - 0/- 0 0
Gloss - 0 0 0
Transparency - + 0 0
Cell Quality - 0 0 0
Yellow Index - 0/- 0 0
Exudation -- 0 0 0
Surface Quality - - 0 0
Odour 0 0 0 0
Weight Loss at
- 0 0 0/-
70° C Cell Density + 0 0 0
Thermal
0 0 0 0
Stability
Expansion rate + + 0 0
Water pick up 0/+ + 0 0

+: Better 0: Good -: Less desired

NAIP

Fig 5.5.2: Castor protein isolate (CPI) (spray dried), CPI based adhesive and curing effect at
different time at 120 deg C
 74

IMPACT & COMPARISON:

PHOTOGRAPHS OF NAIP-JAOL UNDER DEVELOPED PRODUCTS BASED ON
DEOILED CASTOR CAKE

Ricin Testing

DCC

Before loading
Note: Detection limits 5 nano gram/ ml

CPI
JAOL NAIP

Fig 5.5.3: Comparison study for ricin testing for deoiled castor cake and castor protein isolate
 75

Summary:

Under this project developed value added products based on the 2-octanol like phthalate,
maleate, fumarate, sebacate, adipate, benzoate and these can be used as plasticizers in PVC and
resins for various applications. 2-octanol is co-product of the castor industry and based on its
such value added products will earn good returns to the stakeholders
Based on the estimation, the 2-octanol based esters as plasticizers will be cheaper than the
existing products based on 2-ethyl hexanol and isononanol.
Developed process technologies for esters based on 2-octanol will be able to replace petroleum
derived products thus increasing the value of the castor plant & indirectly benefit the farmers due
to increased demand
Deoiled castor cake is also a co-product of castor industry and it has rich content of protein.
Apart from this it also comprises of other constituents. One of the constituents of castor cake is
found very toxic. Due to this the deoiled castor is not used as foodstuff for live stock in spite of
rich amount of protein. The developed process of extraction and isolation shows the protein from
castor deoiled cake is free from toxic component i.e. ricin. Hence such isolated protein can be
used for industrial applications like adhesive and bio-film and can be partially or fully replaced
by soy protein isolate as this is being used in the food products. Also could be considered for
feed purpose after satisfactory trials
 76

4. Innovations
Esterification process developed without formation of byproducts & of high
purity based on agro-based raw-material replacing petrochemicals.
Castor based esters evaluated as plasticizers for PVC in place of petrochemical
based esters & results found encouraging.
New source of protein from castor seeds identified and developed process for its
extraction & isolation.
Identified and demonstrated on laboratory scale development of adhesive based
on the castor protein.
Identified and demonstrated on laboratory scale development of biofilm based on
the castor protein.
7. Process/ Product/Technology Developed

S. No. (Process/Product/Technology Adoption/ Validation/ Responsible

Developed Commercialization, etc. Partner

1 Developed products based on 2- Some the products were validated and JAOL, Mumbai
octanol such as Dicapryl others have been sent for validation.
phthalate, Dicapryl sebacate, Approached local manufacturers of
Dicapryl maleate, Dicapryl plasticizers for commercialization of
fumarate, Dicapryl adipate,the process technologies based on the
Dicapryl ether, Capryl glycidyl research carried out under NAIP-
ether, 2-octene, etc. project
2 Developed process technology for Bench scale process developed and the JAOL, Mumbai
extraction and isolation of the scale up operation is essentially to be
protein from deoiled castor cake done for either adoption or
commercialization by interested protein
and protein based products
manufacturers
3 Developed adhesive formulation Developed castor protein based JAOL, Mumbai
for industrial applications (wood) adhesive and has given to local
using castor protein adhesive manufacture for performance
evaluation in applications against the
existing soy protein based adhesive.
The valuable feed back from them yet
to be received.
 77

Patents (Filed/Granted)

Title of Patent Inventor(s) (Name & Address) Filed / Published Responsible

/ Granted Partner
(No./Date)

“Preparation of Esters Dr. Subhash V. Udeshi. Under process JAOL,

from 2-octanol” Mumbai
M/s. Jayant Agro-Organics Ltd.
38 Marol Co-op. Ind. Estate Off M.
V. Rd, Sakinaka, Andheri(E),
Mumbai-400059 India.

Dr. Kishor D. Ambawade

M/s. Jayant Agro-Organics Ltd.

38 Marol Co-op. Ind. Estate Off M.
V. Rd, Sakinaka, Andheri (E),
Mumbai-400059 India.

8. Linkages and Collaborations

S. No. Linkages developed Date/Period From-To Responsible Partner

(Name & Address of

Organization)

Nil

9. Status on Environmental and Social Safeguard Framework

India is major producer of castor and castor related products such as castor oil, castor oil based
oleochemicals and deoiled castor cake. Products developed under this project, are agro-based
materials which replace petroleum derived products. The petroleum products emit carbon
dioxide during their manufacturing and thus increase the global warming. Also lead to fossil
reserves depletion. Our products being agro-based are from renewable resource and thus non-
depleting. Further there is balancing of the carbon dioxide as the castor plant absorbs CO2 from
the atmosphere. The farming also creates rural employment and leads to social harmony. Further
the technology is based on energy saving principles. All in all there is improvement in Health,
Environment and Economy for all sections of society.

10. Constraints, if any and Remedial Measures Taken

It was realized that coordination was poor among the partners.

 78

11. Publications (As per format of citation in Indian Journal of Agricultural Sciences)

A. Research papers in peer reviewed journals-Not Applicable as under patenting

S. Authors, Title of the paper, NAAS Responsible

No. Ratings Partner
Name of Journal, Year, Vol. & Page No.

1. Patel, R.M. Prajapati, T.R. and Patel, P.S. (2010). 2.9 SDAU
Yield advances in castor through adaptation of
recommended package of practices on farmer’s field.
Journal of Oilseeds Research. 27 (sp. issue): 312-315

2. M.K. Patel, Jignasa V. Modh, Jignesh P. Patel and 2.9 SDAU

P. S. Patel (2010) Journal of Oil Seed Research 155N
0970-2776 Vol. 27 (Special issue) P. 302-303

B. Books/ Book chapters/ Abstracts/ Popular articles, Brochures, etc.

S. No. Authors, Title of the papers

Name of Book/ Seminar/ Proceedings/Journal, Publisher, Year, Page No.

1. Papers presented: “A simple method for the enrichment of methyl ricinoleate from
castor oil methyl esters by LLE, K.V.S.A. Rao, P. Vijayalakshmi, D. Pramod Reddy
and R.B.N. Prasad presented at National Symposium on “Research and development
in castor: present status and future strategies” during October 22-23, 2010,
Hyderabad

12. Media Products Developed/Disseminated

S. CD, Bulletins, Brochures, No. of Copies Distribution Responsible

No. etc. (Year wise) Partner

Nil
 79

13. Meetings/Seminars/Trainings/Kisan Mela, etc. organized-Not Applicable

S. Details of Duration No. of Budget Organizer

No. Meetings/Seminars/ Personnel
Trainings, etc. (From-To) Trained (`) (Name & Address)

1. Training of 100 4 days 100 20000/- Main Castor

farmers of Mustard Research
Shankhalpur and station SDAU SK
Matpur villages Nagar

2. Castor production 3 Days 150 20000/- Main Castor

technology and its Mustard Research
derivatives station SDAU SK
Nagar

3. Castor production 2days 60 5000/- Main Castor

technology and its Mustard Research
derivatives station SDAU SK
Nagar

14. Participation in Conference/ Meetings/Trainings/ Radio talks, etc.

S. Details of Duration Budget Participant

No. Meetings/Seminars/
(From-To) (`) (Name & Address)
Trainings/Radio talk,
etc.(Name &Address)

Nil

15. Foreign Trainings/Visits:

S. Name, Visit/Training/Seminar Dates of Follow up Total Cost

No. its Place, Organization Seminar (`)
Designation, and Duration (From- Delivered and Action

Address of To) Report

Submitted on
the Person Return

Nil
 80

16. Performance Indicators

S.
Indicator Total No.
No.
1 No. of production technologies released and/or adopted 5
2 No. of processing technologies released and/or adopted 4
Number of technologies/products commercialized based on NAIP
3 Nil
research
4 No. of new rural industries/entreprises established/ upgraded Nil
5 No. of product groups for which quality grades developed and agreed 1
Total no. of private sector organizations (including NGOs) participating
6 2
in consortium
7 No. of farmers involved in consortia activities Approx. 2200
8 Total number of farmers’ group developed for marketing and processing Nil
Number of patent/intellectual property protection applications filed
9 1
based on NAIP research
Number of patents/intellectual property protections granted/published
10 Nil
based on NAIP research
11 Number of scientists trained overseas in the frontier areas of science Nil
12 Number of scientists trained overseas in consortium-based subject areas Nil
13 No. of scientists participated in conference/seminar etc. abroad Nil
14 Success stories Nil
Baseline Final
15 Incremental employment generated (person days/year/HH)
Nil
Baseline Final
16 Increase in income of participating households (` per annum)
Nil
17 Number of novel tools/protocols/methodologies developed 2
18 Publications
Articles in NAAS rated journals -
Articles in other journals 2
Book(s) Nil
Book chapter(s) Nil
Thesis Nil
Popular article(s) (English) Nil
Newspaper article(s) Nil
Seminar/Symposium/Conference/Workshop Proceedings 1
Technical bulletin(s) 2
Manual(s) Nil
CDs/Videos Nil
Popular article(s) in other language -
Folder/Leaflet/Handout Nil
8 Quarterly
Report(s) reports were
submitted
Success stories Nil
 81

17. Employment Generation (man-days/year)

S. No. Type of Employment Generation Employment Responsible

Generation Partner
up to End of
Sub-project

No direct employment generated

18. Assets Generated

(i) Equipment

Sr. Name of the equipments with manufacturers Date of Quantit Cost (`)
No. name, model purchase y (Nos.)
1 Centro fix vertical autoclave 23.03.2010 One 84375/-

2 Tractor Drawn Castor Umiya 26.03.2010 One 29925/-

planter
3 Power Operator Castor Umiya 26.03.2010 One 35438/-
Decorator
4 Farm track Tractor 45 DB (42HP) 27.03.2010 One 467000/-
5. Field Crop Solar Dryer 23.03.2010 One 166375/-
6 Gel Documentation System 27.03.2010 One 742000/-
7 Vertical Electrophoresis 27.03.2010 One 171260/-
8 BD instrument make BDI 54 A 29.03.2010 One 105000/-
hybridation incubator
9 Ultra filtration membrane 8200 UF 29.03.2010 One 226966/-
10 Horizontal Electrophorosis BMH 8 5.06.2010 One 79985/-
11 Electrical digital AX-200 15.11.2010 One 66700/-
12 Electrical digital Balance AX-200 15.11.2010 One 66700/-
13 Thermogravimetric analyzer TG/DTA/6300 3.12.2010 One 1359064/
Exstar -
14 Digital Camera DSCH-1S 31.12.2010 13950/-
15 Tissue Homogenizer PRO 250 31.12.2010
159600/-
16 Ricin Estimation kit LCC USA Make 6.01.2011 One 1694925/
Cat. No.P-12 -
SRS optimalt USA One 57750/-
Mo. MPA 100
17 Electroquip vacuum oven POE 7071 6.01.2011 One
18 Digital melting point EIE Make 6.01.2011 One 174000/-
apparatus
19 Pessurize oil extractor - 7.01.2011 One 1511096/
-
 82

20 Universal testing machine - 7.01.2011 One 264600/-

21 Computers HP-8000 & 7000 31.12.2010 Three 108150/-
series
22 21. Laser printer HP(L)CP 1215 24.02.2011 one 20909/-

23 Air screen seed pre-cleaner - 24.3.2011 One 797850/-

with aspirator/ Air screen
cleaner cum grader/ Destoner/
Specific Gravity Separator

24 Fluorescence - 40392 One 987000/-

Spectrophotometer (IICT,
Hyderabad)
25 Differential Scanning - 29-03-2010 One 1200000/-
Calorimeter (IICT, Hyderabad)

(ii) Works

S. No. Particulars of the Work, Year of Quantity Total Responsible

Name and Address of Work Done (Nos.) Cost Partner
Agency Awarded the
Work (`)

Nil

(iii) Revenue Generated

(Details may be given on revenue generated in the sub-project viz., sale of seeds, farm produce,
products, patents, commercialization, training, etc.)

S. No. Source of Revenue Year Total amount Responsible

(`) Partner

Nil

(iv) Livestock

(Details of livestock procured/produced in the sub-project)

S. No. Details of Year of Nos. Total Responsible

Livestock Procurement/Production Cost (`) Partner
(Breed, etc.)

Nil
 83

19. Awards and Recognitions

S. No. Name, Award/ Institution/ Society Responsible Partner

Recognition Facilitating (Name
Designation, (with Date) & Address)
Address of

the Person

Nil

20. Steps Undertaken for Post NAIP Sustainability

 Under NAIP-II project provided high yielding Castor seed for production and get
maximum return to the farmers in irrigated as well as rainfed areas. Therefore, the field
demonstration of improved farm technologies should be continued.
 The technologies developed are of much use and will be considered as a base for further
research and scaling up of technology.
More than 2000 farmers were trained through the interventions of NAIP-II for improved agro-
technologies and post harvest practices developed by university. Regular interaction between
farmers and scientists will be made under different programs conducted by university. For
ensuring smooth supply of quality seed to the farmer’s the centre is producing breeder seed as
per the indent of state agencies and national agencies. All the seed production sites are regularly
monitored by castor scientist for maintaining good crop vis-à-vis quality seed production. The
industry is working on value addition of castor cake and development of derivatives from castor
oil. Due to integrated intervention castor cake is included in Fertilizer Control Order.
21. Possible Future Line of Work

 If castor growing areas provide high yielding varieties than easily increases castor
production in rainfed as well as irrigated condition.
 In undeveloped areas gives the farmers training programme for new technology adoption.
 Provide knowledge about new innovation in production technology.
 Large scale manufacturing of the esters and the protein is likely to be taken by
commercial organizations, which will indirectly benefit the farmers due to increase in
demand for the castor seeds.
 84

22. Personnel

(Staff of Lead Centre & Partner-wise, their Name, Designation, Discipline and Duration)

Research Management (CL) From – To (DD/MM/YYYY)

1.
2.
3.
Scientific (CPI, CCPI, others)
5. Dr. P. S. Patel, CPI & Research Scientist, Plant March 1, 2009 to June 30, 2012
Breeding and Genetics
6. Dr. R. M. Patel, CCPI, Agronomy (Agriculture) March 1, 2009 to June 30, 2012
7. Dr M.K. Patel, CCPI, Bio-chemistry
8. Dr. S. Shah, CCPI, Bio-chemistry Jan, 11, 2012 to June 30, 2012
9. Dr. S. H. Suthar, CCPI, (Post Harvest March 1, 2009 to June 30, 2012
Technology )
10. Dr. S. R. Vyas, CCPI, (Bio-Chemistry) March 1, 2009 to June 30, 2012
11. Dr. Subhash V. Udeshi, (Director) CCPI March 1, 2009 to June 30, 2012
12. Dr. RBN, Prasad, CCPI March 1, 2009 to June 30, 2012
13.
Technical
14. NIL
15.
Contractual
16. Mr. Mukesh Kumar Man, Senior Research May 28, 2010 to June 30, 2012
Fellow
17. Mr. Bedse Ramchandra, Senior Research Fellow July 15, 2011 to June 30, 2012
18. Mr. Chirag Patel, Senior Research Fellow September 11, 2011 to June 30,
2012
19. Dr. Kishor D. Ambawade, Research Associate July 6, 2009 to June 30, 2012
 85

23. Governance, Management, Implementation and Coordination

A. Composition of the various committees (CIC, CAC, CMU, etc.)

S. No. Committee Name Chairman Members

(From-To) (From-To)
1. CIC

2. CAC

3. CMU

B. List of Meetings organized (CIC, CAC, CMU, etc.)

S. No. Details of the meeting Date Place & Address

1. CIC
2. CAC
Ist CAC
IInd CAC
IIIrd CAC Dec 23, 2009 2, Arti society,
Near atma jyoti ashram,
Baroda- 390 011, Gujarat.
IVth CAC May 5, 2010 Jayant Agro Organics Ltd
Akhandanad , 34, Marol, Coop
Industrial Estate, OFF M VRoad
Skainaka, Andheri, `Mumbai
Vth CAC Oct 10, 2010 Lipid Sciences and Technology,
Indian Institute of Chemical Technology,
Hyderabad 500 007
VIth CAC Jun 7, 2011 Royal Castor Products Ltd., Industrial Area,
Khali Char rasta
Sidhpur, District: Banaskantha, Gujarat.
VIIth CAC Jan 5, 2012 Jayant Agro Organics Ltd
Akhandanad , 34, Marol, Coop
Industrial Estate, OFF M VRoad
Skainaka, Andheri, Mumbai
 1

Part III : Budget and its Utilization (SDAU: S. K. Nagar )

Sanction Letter No. _F. No. (5) 2007-NAIP

Total Sub-project Cost : 387.0685/-
Sanctioned/Revised Sub-project cost (if applicable): 393.7593/-
Date of Commencement of Sub-project :July 2009
Duration: From: July 2009_to June 30, 2012
Funds Received in each year
I Year : 1,4411560/- II Year : 37,66154/- III Year : 26,97402/- Total fund received 29872616/-Total expenditure 14307207/-

Expenditure Head-wise:
Sanctioned Heads Funds Funds Released Expenditure Incurred Total Balance as Requirement of Remarks
Allocated 1st Year 2nd Year 3rd Year 1st Year 2nd Year 3rd Year Expenditure on date additional
(*) funds
A. Recurring
Contingencies
(1) TA 41901 74252 24847 141000
(2) Workshops 45461 48214 5000 98675
(3) Contractual 212080 810878 618024 1640982
Services/RA/SRF
(4) Operational costs 818644 1366629 730102 2915375
Sub-Total of A (1-4) 14411560 3766154 2667610 1118086 2299973 1377973 4796032
B. HRD Component
(5) Training - 7500 46915 54415
(6) Consultancy - - - -
Sub-Total of B (5-6) - 7500 46915 54415
C. Non-Recurring
(7) Equipment 2121624 6153336 - 2173145 6261486 - 8434631
(8) Furniture 498000 - - 49800 - - 49800
(9) Works (new 500000 - - - 494962 494962
renovation)
(10) Others (Animals, 51521 156049 494962 - 47899 - 47899
Books, etc.)
Sub-Total of C (7-10) 12280000 6309385 494962 2222945 6309385 494962 9027292
D. Institutional 43488 385980 - 429468
Charges*
Grand Total 16634505 10075539 3162572 3384519 9002838 1919850 14307207 6538117
(A+B+C+D)
* Institutional charges will be 10% of the recurring contingencies for the Lead Consortium and 5% for Consortia Partners.
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Part III : Budget and its Utilization (IICT, Hyderabad)

Sanction Letter No. _F. No. (5) 2007-NAIP

Total Sub-project Cost : 387.0685/-
Sanctioned/Revised Sub-project cost (if applicable): 393.7593/-
Date of Commencement of Sub-project :1st March, 2009
Duration: From: March 01, 2009 to June 30, 2012
Funds Received in each year
I Year : 3522060/- II Year : 462012/- III Year 1131516/- Total fund received 4669758/-

Expenditure Head-wise:
Sanctioned Heads Funds Funds Released Expenditure Incurred Total Balance as on Requirement
Allocated (*) 1st Year 2nd Year 3rd Year 1st Year 2nd Year 3rd Year 4th Year Expenditure date of additional
funds
A. Recurring
Contingencies
(1) TA 35000 25000 40155 44283 15155 44580 0 104018 -3863
(2) Workshops 0 0 0 2000 0 0 0 2000 -2000
(3) Contractual 187200 218400 600000 210658 319200 271200 134400 935458
Services/RA/SRF 70142
(4) Operational costs 2.75 2.07751 4.37479 2.07751 4.12479 1.22159 1.74992 9.17381 2849
Sub-Total of A (1-4) 4.972 4.51151 10.77634 4.64692 7.46834 4.37939 3.09392 19.58857 67128
B. HRD Component
(5) Training
(6) Consultancy
Sub-Total of B (5-6)
C. Non-Recurring
(7) Equipment 3000000 0 0 2000000 191563 0 24000 2167563 832437
(8) Furniture -
(9) Works (new renovation)

(10) Others (Animals,

Books, etc.)
Sub-Total of C (7-10) 3000000 0 0 2000000 191563 0 24000 2167563 832437
D. Institutional Charges*
24860 10861 0 9801 37342 18254 0 65397 24206
Grand Total (A+B+C+D)
3522060 462012 0 2474490 975739 456193 285392 4191817 923771
* Institutional charges will be 10% of the recurring contingencies for the Lead Consortium and 5% for Consortia Partners.
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Budget and its Utilization (JAOL: Mumbai)

STATEMENT OF EXPENDITURE (Final)
Sanction Letter No.: F. No. 1(5)/2007-NAIP
Total Sub-project Cost
Sanctioned/Revised Sub-project cost (if applicable)
Date of Commencement of Sub-project July 6, 2009
Duration: From March 1, 2009 to June 30, 2012
Funds Received in each year
I Year: 6.48795/- II Year: 10.54048/- III Year: 6.70681/- Total amount received: 23.73524 Total expenditure:
Expenditure Head-wise:
Funds Funds Released Expenditure Incurred Requirement
Total Balance as
Sanctioned Heads Allocated st nd rd st nd rd of additional Remarks
1 Year 2 Year 3 Year 1 Year 2 Year 3 Year Expenditure on date
(*) funds
A. Recurring Contingency
1. T.A. 1.75 0.03288 0.29014 0.43055 0.75357
2. Workshops 0.00
3. Contractual Services 9.594 2.05291 2.77768 4.66989 9.50048
4. Operational Costs 26.00 1.42320 4.23413 3.03012 8.68745
Sub-Total of A (1-4) 37.344 3.50899 7.30195 8.13056 18.9415
B. HRD Component
5 (a) National Training 0.00 0.00 0.00 0.00 0.00
5 (b) International Training 0.00 0.00 0.00 0.00 0.00
6. Consultancy 0.00 0.00 0.00 0.00 0.00
Sub-Total of B (5-6) 0.00 0.00 0.00 0.00 0.00
C. Non-Recurring Contingency
7. Equipments 0.00 0.00 0.00 0.00 0.00
8. Furniture (Work Tables, etc.) 0.00 0.00 0.00 0.00 0.00
9. Works (New/Renovations) 0.00 0.00 0.00 0.00 0.00
10. Others (Animals, Books, etc.) 0.00 0.00 0.00 0.00 0.00
Sub-Total of C (7-10) 0.00 0.00 0.00 0.00 0.00
Total (A+B+C) 37.344 3.50899 7.30195 8.13056 18.9415
D. Institutional charges 1.8672 0.61540 0.61540 0.61540 1.8462
Grand Total (A+B+C+D) 39.2112 6.48795 10.54048 6.70681 4.12439 7.91735 8.74596 20.7877 2.94754
during 01.04.2012 to 30.06.2012 the expenditure as consultancy: Rs 93600 and other operating maintenance charges: Rs 154417 and Closing balance
Rs 23141
3rd year figures are till March 31st 2012.
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SDAU: S. K. Nagar (Budget and its Utilization)

STATEMENT OF EXPENDITURE (Final)
(Period from July 2009 to June 2012)
Sanction Letter No. _F. No. (5) 2007-NAIP Funds Received in each year:
Total Sub-project Cost : Rs. 387.0685/-__ I Year : Rs. 1,4411560/-
Sanctioned/Revised Sub-project cost (if applicable) `__393.7593/-___ II Year: Rs. 37,66154/-
Date of Commencement of Sub-project ___July 2009___ III Year: Rs. 26,97402/-
Duration: From _July 2009_to __June 30, 2012__ (DD/MM/YYYY)
Total expenditure: Rs. 14644232/-
Expenditure Head-wise:
Sanctioned Heads Funds Funds Released Expenditure Incurred Total Balanc Requirement Remarks
Allocated Expenditure e as of additional
(*) st nd rd th st nd rd th on funds
1 Year 2 Year 3 Year 4 Year 1 Year 2 Year 3 Year 4 Year
date
2009-10 2010-11 2011-12 2012-13 2009-10 2010-11 2011-12 2012-13
A. Recurring
Contingencies
(1) TA 42500 75000 42500 - 41901 74252 24847 2289 143289 - - -
(2) Workshops 50000 50000 50000 - 45461 48214 5000 3000 101675 - - -
(3) Contractual 435600 976800 1267200 - 212080 810878 618024 197694 1838676 - - -
Services/RA/SRF
(4) Operational costs 1341500 2758000 1229000 - 818644 1366629 730102 94157 3009532 - - -
Sub-Total of A (1-4) 1869600 3859800 3850200 - 1118086 2299973 1377973 297140 5093172 - - -
B. HRD Component
(5) Training 75000 150000 100000 - - 7500 46915 - 54415 - - -
(6) Consultancy - - - - - - - - - -
Sub-Total of B (5-6) 75000 150000 100000 - - 7500 46915 - 54415 - - -
C. Non-Recurring
(7) Equipment 11680000 - - - 2173145 6261486 - 8434631 - - -
(8) Furniture 50000 - - - 49800 - - 49800 - - -
(9) Works (new 500000 - - - - - 494962 - 494962 - - -
renovation)
(10) Others (Animals, 50000 50000 50000 - 47899 - 94157 47899 - - -
Books, etc.)
Sub-Total of C (7-10) 12280000 50000 50000 - 2222945 6309385 494962 295340 9027292 - - -
D. Institutional Charges* 186960 385980 385020 - 43488 385980 - 39885 469353 - - -
Grand Total (A+B+C+D) 14411560 4445780 4385220 - 3384519 9002838 1919850 337025 14644232 - - -
* Institutional charges will be 10% of the recurring contingencies for the Lead Consortium and 5% for Consortia Partners.
5