American Journal of Oil and Chemical Technologies: Volume 2. Issue 5. May 2014
Petrotex Library Archive
American Journal of Oil and Chemical Technologies
Journal Website: http://www.petrotex.us/2013/02/17/317/
Nonedible deoiled Castor cake: A potential source for Bio ethanol.
Minal Deshmukh1,Dr.A.B.Marathe2
1
Department of Petrochemical engineering ,Maharashtra Institute of Technolgy,Pune,India.
Principal,H.V.P.M. Collage of engineering ,Amaravati,india.
2
Abstract:
The starch hydrolysis process of nonedible deoiled castor bean cake by acid or enzymatic combination of cellulase,
amylase and pullulanase was analyzed and followed by fermentation with saccromycess cervesse. Ethanol from
fermented substrate was separated by vacuum distillation upto 550C and 75mmHg .The 32.5g/l glucose content are
obtained by chemical treatment which resulted 16ml of ethanol. The sugar content obtained by saccrification with
Calcium Carbide and enzymes gives 69.5g/l of reducing sugar which results 30ml of ethanol. The enzymatic
treatment is considered as bettert saccrification treatment due to possibility of side reactions by chemical treatment
or detoxification of castor cake. Gas chromatography showed the bio ehanol distillate as 84% pure.
Keyword: Sachrification, nonedible deoiled castor cake, vacuum distillation, bioethanol.
1.
Introduction
In India,the castor seed production is large as compared to other countries. Hence, the availability of nonedible
deoiled cake is in vast quantity as shown in table (1)In the castor seed processing and solvent extraction plants, the
castor deoiled cake is generated as waste. On an average basis 72.5 to 77% of total deoiled castor cake biomass
production is sold out. Rest 23% to 27% remains unused which gradually goes on decay. It is reported that out of
sold biomass, approximately 74% is used as organic manure and 26% is used for any other unorganized use like
energy generationr.[2]
Sr.N0.
1
2
3
Details
Generation
per
Annum(MT)
Consumption per
Annum (MT)
Surplus Available
per Annum(MT)
Castor De Oiled cake
509994MT
369745MT
to
392695MT
96134MT to102100MT
Castor oil mills in Gujrat producing deoiled cake are facing problems of bulk storage and disintegration.If not
used, it increases fire hazard and subsequent adds to risk to be covered under insurance premium. It also generates
green house gases like methane and hence lead to further damage of ozone layer. The solvent extracted cake
although rich in protein can not be directly used as cattel feed because of its toxicity. However it can be used as
fertilizer. The cake is highly poisonus due to ricin content and hence can not be processed as livestock unless
detoxified. Depletion in petroleum resources and global warming necessiate the importance of alternative renewable
energy sources including biofuels like bioethanol and biodiesel.[2]
On other hand Castor bean cake ( CBC) is a potential feed stock for bioethanol due to its high concentration of
starch[1]. This study is intended towards the need of treating the CBC by chemical and enzymatic treatments for
Authors /American Journal of Oil and Chemical Technologies 5 (2014) 45-47
producing bioethanol. Biodiesel is produced by estrification of triglycerides of vegetable oils by ethanol in presence
of catalyst. In biodiesel plant, large quantity of ethanol is required for transesterfication and detoxification process.
The demand could get fulfilled by the bioethanoll which made this study as an integrated process.
The process is optimized by reducing the dilution as 1:1 along with vacuum distillation. Ethanol so obtained is of
84% purity in the first step itself.
FLOW SHEET
Pressing Extraction in Biodiesel plant
Castor cake
Drying
Milling
Saccrification of
starch with chemical
& enzyme treatment
Oil
Fermentation
Ethanol
Transesterification
Vacuum Distillation
Biodiesel
2
Materials and Methods
2.1 Materials
Samples of castor bean cake(CBC) are taken from the biodiesel plant “Gujrat Ambuja Exports Ltd.” and dried at
50.c for 24 hours.The unprocessed oil from cake is extracted on soxclet extractor to deoil it.
The first step is to analyze the cake for its content.
Sr.no.
1
2.
Castor
DOC
Proximate Analysis
Moisture(%)
Ash(%)
Volatile Matter(%)
Fixed carbon(%)
Gross calorific value (kcal/kg)
9.70
5.80
61.10
23.40
4285
2.2 Methods
2.2.1 Estimation of total solids
After calculating intial moisture content, remaining amount of deoiled cake was considered as total solids.
2.2.2 Estimation of reducing sugar
The reducing sugar was analysed by DNSA method with 1:1 dilution. The initial sugar content measured was 10.5g/lit.
2
Authors /American Journal of Oil and Chemical Technologies 5 (2014) 45-47
2.2.3 Saccrification of Starch with Chemical & Enzymatic Treatments
The non edible deoiled castor seed cake is treated with 1.5% (on wt. of cake) with chemical reagent. The chemical
reacts with the moisture content of cake to form gas and lime. The gas formed in-situ chemically partially degrades
the cake contents. The mixture of microbes containing amylase, cellulase, pullunase are added up to 5% and
allowed to react in an air tight steel vessel for 24 hrs. Water maximum up to 10% of mass is added and the properly
mixed massed is kept for 24 hrs. The same chemical reagent is added up to 1.5% and kept for 6 hrs. The compost is
tested for its C : H ration and volatiles are collected under vacuum by heating maximum up to 55 ’ C.It was diluted as
1:1 for further fermentation.
2.2.4 Compost Fermentation
The above composed cake was fermented with Saccharomyces cerevisiae ,at 28 .c for 72 hours with PH range 5to6.
The media was then autoclaved for 5 minutes at 15 psi.Harvesting was done by centrifuge at 10,000 rpm at 4 .c for
10 minutes.Sugar conversion (DNSA) and alcohol produced (Potassium Dichromate) with respect to time was
analyzed. The fermented compost cake was vacuum distilled upto 55C and 75 mm Hg. The 100 gm of CBC gives
25ml of ethanol.
3 Results and Discussion
3.1 Analysis of reducing sugar and ethanol with chemical and enzymatic hydrolysis
Intial reducing sugar content inCBC analyzed by DNSA was 10.5g.This sugar content was increased upto 63.5g by
the saccrification of starch with combined chemical and enzyme treatment with dilution 1:1. Fermentation was done
by using saccromucess cervese at 300c and PH maintained was 6, reaction time given is 72hr. Ethanol was extracted
by vacuum distillation which gives 25ml of ethanl from 100 gm of CBC.Hence on large scale calculation, 250 L 0f
Ethanol can be obtained per ton of CBC. The sample analyzed on gas chromatography has shown 84% purity.
According to this mass balance ,270L of ethanol per ton of processed CBC can be obtained.
The waste residue of hydrolysis and fermentation process was analyzed. It indicates the absence of starch in the
solid residue and has the composition as lipids,proteins,fibre,phosphorous,magnesium,magnesium and sodium.
Considering the increasing generation of waste associated with production of oil from castor bean seeds, the
utilization of CBC for co-generation of ethanol could be integrated to the transesterification process,reducing
cost,and giving solution to destination to CBCresidue.
Time Interval (Hr)
PH
Sugar Percentage(%S)
Alcohol
Production
3
0
6.5
63.5g
0
12
6.5
50.8g
15.5ml
24
6
34.5g
21.5ml
36
5.5
19.5g
48
6
8.5g
30ml
60
5.5
8.5g
30ml
27ml
Authors /American Journal of Oil and Chemical Technologies 5 (2014) 45-47
CBC Fermentation with Chemical and
Enzymatic Hydrolysis
70
60
Axis Title
50
40
ETHANOL
30
Reducing sugar
20
PH
10
0
40
47
54
61
68
75
82
89
96
Figure (I) Graphical representations for Ethanol fermentation with enzymatic hydrolysis
3.2 Fermentation Kinetics
The kinetic study of substrate fermented with respect to time was studied to estimate the order of reacrion.
Basis- 100 gm of castor seed cake substrate(s)
S
0.09
0.04
0.005
ds/dT
0.4
0.22
0.06
Sr.no.
Time(hr)
Substrate(%S)
ds/dT
1/s
1/( ds/dT)
1
0
73.5
--
---
---
2
12
60.8
0.225
0.12048
4.4444
3
24
54.5g
0.45833
0.357143
2.1818
4
36
39.0
0.0658
2.325581
15.1898
5
48
13.5
--
---
---
6
72
13.5
--
---
--
Conclusion
Nonedible deoiled castor been cake can be used as best resource for the production of bioethanol by fermentation .The
saccrification by combined chemical and enzyme treatment is found to give a better yield .The ethanol produced was
analyzed by gas chromatography equipped with ionic exchange column,distilled water is used as mobile phase . the
optimum operating conditions are found tobe 35 0c and optimum PH 5.5.The kinetics of the fermentation procees is found to
be first order with respect to substrate.
According to the saccrification and fermentation results, it is possible to produce 250L per ton of nonedible deoiled cake.
This value is 2 fold higher than the demanded ethanol volume in transesterification of extracted oil from 2 ton of cake
which makes the process intensified. The obtimization and the scale up are the main objectives of the new process
4
Authors /American Journal of Oil and Chemical Technologies 5 (2014) 45-47
development in this area according to recent work.
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