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Title:
DEGUMMED AND TRANSESTERIFIED OIL OF OLAX SCANDENS AS BIO- ADDITIVE
Document Type and Number:
WIPO Patent Application WO/2011/145106
Kind Code:
A2
Abstract:
The present invention discloses the oil of Olax Scandens for use as bio-additive to petroleum diesel and to the process for extraction, modification and characterization of Olax scandens oil.

Inventors:
DAS, Premananda (B-221, Kalpataru TowersKapatru Tower,Akurli Road, Kandivali, IN)
Application Number:
IN2011/000310
Publication Date:
November 24, 2011
Filing Date:
May 03, 2011
Export Citation:
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Assignee:
DAS, Premananda (B-221, Kalpataru TowersKapatru Tower,Akurli Road, Kandivali, IN)
International Classes:
C10L1/02
Domestic Patent References:
2009-12-10
Foreign References:
EP1990398A12008-11-12
Other References:
None
Attorney, Agent or Firm:
NAIR, Gopakumar, G. (GOPAKUMAR NAIR ASSOCIATES, 3rd Floor "Shivmangal", Near Big Bazaar,Akurli Road,Kandivali, Mumbai 1 Maharashtra, 400 10, IN)
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Claims:
I claim,

1. Degummed and Transesterified oil obtained from seeds of Olax scandens, as bio- additive to petroleum diesel.

2. The degummed oil obtained from seeds of Olax scandens, as claimed in claim 1, wherein the said degummed oil is characterized by GC-MS of Figure 1.

3. The degummed oil obtained from seeds of Olax scandens, as claimed in claim 1, wherein, said degummed oil comprises the compounds as described in Table 1.

4. The transesterified oil obtained from seeds of Olax scandens, as claimed in claim 1, wherein the said transesterified oil is characterized by GC-MS of Figure 2.

5. The transesterified oil obtained from seeds of Olax scandens, as claimed in claim 1, wherein, said transesterified oil comprises the compounds as described in Table 2.

6. A process for preparation of degummed and transesterified oil obtained from the seeds of Olax scandens, comprising;

i. boiling the seeds of Olax scandens in a aliphatic solvent for about 4 hours and extracting the crude oil of Olax scandens;

ii. adding C1-C7 alcohol to the crude oil obtained in step (i) (oil to alcohol ratio is 2:1 v/v), centrifuging, and heating to obtain degummed Olax oil;

iii. esterifying the degummed Olax oil of step (ii) with a lower alcohol and in presence of a mineral acid (Oil: alcohol: mineral acid=50: 1:0.1, v/v/v), neutralized with alcoholic base and drying the esterified oil; followed by transesterification with lower alcohol in presence of a base as a catalyst to obtain bio-additive, and iv. separating the bio-additive so obtained from unreacted oil by partitioning with water, followed by centrifuging and recovering.

7. The process for preparation of degummed oil as claimed in claim 6, comprising;

i. boiling the seeds of Olax scandens in a aliphatic solvent for about 4 hours and extracting the crude oil of Olax scandens;

ii. adding C1-C7 alcohol to the crude oil (oil to solvent ratio is 2:1 v/v), centrifuging, heating to obtain degummed Olax oil along with recovery of the solvent.

8. The process for preparation of transesterified oil as claimed in claim 6, comprising; i. esterifying the degummed Olax oil with a C1-C7 alcohol in presence of a mineral acid (Oil: alcohol: mineral acid=50: 1:0.1, v/v/v) to obtain FAMEs; ii. neutralizing FAMEs of step (i) with alcoholic base and transesterifying with lower alcohol in presence of a base as a catalyst.

9. The process for preparation of degummed and transesterified oil obtained from the seeds of Olax scandens as claimed in claim 6 to 8; wherein, said solvent is selected from aliphatic solvents, C1-C7 alcohols.

10. The process for preparation of degummed and transesterified oil obtained from the seeds of Olax scandens as claimed in claim 6 to 8; wherein the catalytic base is selected from alkali and alkaline earth metal hydroxide.

11. A bio-additive as claimed in claim 1-10, wherein the said bio-additive is used to enhance the performance of diesel engines.

Description:
DEGUMMED AND TRANSESTERIFIED OIL OF OLAXSCANDENS AS

BIO-ADDITIVE"

TECHNICAL FILED OF THE INVENTION:

The present invention relates to the oil of Olax scandens for use as bio-additive to petroleum diesel. The present invention also relates to the process for extraction, modification and characterization of the Olax scandens oil.

BACKGROUND OF THE INVENTION:

With the exponential increase in population, soaring prices of food and edible oils have assumed a global crisis proportion. The only other crisis which has markedly attracted attention over food and edible oil prices is the energy crises. Depleting crude and diesel oil reserves due to industrial revolution, depleting petroleum resources have impacted crude oil prices. Further, increasing uncertainty about natural resources and global energy production and its supply as well as the requirement of the crude oil based biofuel has led to research for viable and economic alternatives.

It is therefore prudent and urgent to look for alternate economic resources from nature with high yield and affordable prices. In this perspective, considerable attention has been drawn towards the production of bio-diesel as diesel substitute. Due to the fact that plants, vegetable oils and animal fats are renewable biomass sources and due to its environmental benefits, bio-diesel has become universally attractive.

Biodiesel refers to a vegetable oil or animal fat-based diesel fuel consisting of long-chain alkyl (methyl, propyl or ethyl) esters. Biodiesel is typically made by chemically reacting lipids [e.g., vegetable oil, animal fat (tallow)] with an alcohol. Biodiesel is meant to be used in standard diesel engines and is thus distinct from the vegetable and waste oils used to fuel converted diesel engines. Biodiesel can be used alone, or blended with petrodiesel.

Extensive research has been carried out for extraction of biodiesel from various herbs, plants etc. however, commercialization of bio-diesel at high price is a major commonly faced problem. Further, considering the increasing global demand and improvement in quality of life style in countries like India and China, there is urgent and pressing need for additional viable economic source for edible oil.

l Among the known sources of biodiesel, Palm oil has been widely accepted and used conventionally. However, being edible oil the diversion for commercial use is unacceptable. In recent times, Jatropha curcas and Pongamia pinnata have emerged as potential candidates for biodiesel production. Since the seeds of these plants are primarily the source for biodiesel, the gestation period is high, often from 5-7 years.

The abovementioned Jatropha curcas oil and Pongamia pinnata oil have certain disadvantages such as high volatility, high viscosity and cause injection problems in engines.

Olax scandens which is a perennial plant belongs to genus Olax and family Olacaceae. The plant is available primarily in Sri Lanka and is commonly called as " adalaagnchi". It exists as a scandent shrub in open forests. It is described in "The wealth of India: a dictionary of Indian raw materials and industrial products." Raw materials. Delhi. (Wealth India RM), 1948-1976 by Council of Scientific and Industrial Research (CSIR), India. However, the available information on Olax scandens is very scanty and limited.

Olax scandens which is a widely distributed scandent shrub spread all over Asian region, have been used for various medicinal properties in countries like Thailand, Malaysia and other. While the parts of the herb have been reported to be used for medicinal purposes such as hexane extract of Olax scandens is used to inhibit Klebsiella pneumonia, no mention or reports of the oil extracted from Olax scandens for use as a bio-additive to petroleum diesel is reported / documented anywhere in the literature.

Therefore, it is the object of the current invention to provide extract of Olax scandens as potential source of oil for use as a bio-additive to petroleum diesel.

SUMMARY OF THE INVENTION

In an aspect, the present invention provides the crude oil extracted from Olax scandens seeds, which is further processed to obtain the oil for use as bio-additive to petroleum diesel. In another aspect, the present invention provides a process for extraction, modification and characterization of crude oil from the seeds of Olax scandens to obtain degummed and transesterified oil as bio-additive.

DETAILED DESCRIPTION OF DRAWINGS

Figure 1 depicts GC-MS Chromatogram of Degummed Olax oil

Figure 2 depicts GC-MS Chromatogram of Transesterified Olax oil

DETADLED DESCRIPTION OF THE INVENTION

The invention will now be described in detail in connection with certain preferred and optional embodiments, so that various aspects thereof may be more fully understood and appreciated. The embodiments as described are not limiting or restricting the scope of the invention.

For the purpose of this invention, "FAMEs" refers to fatty acid methyl esters, "FFAs" refers to free fatty acids, "TEO" refers to Transesterified oil, "DGO" refers to Degummed oil and "PD" refers to Petroleum Diesel.

The inventor of the present invention has for the first time ever, come up with the process of extraction of crude Olax scandens oil for use as a bio-additive in a liquid fuel to enhance its efficacy by cost effective, industrially viable method.

The extraction of Olax scandens oil, its economic benefits along with favorable emission and pollution parameters is evaluated by the present inventor. The bio-additive so obtained is with high efficiency, and better biodegradability. Olax scandens oil is highly economic, eco-friendly and an efficient bio-additive which is economically accessible without any seasonal restriction. By undertaking cultivation on large scale, the availability can be assured with short gestation period and all-round the year.

The plant material used in the present invention i.e. Olax scandens seeds are collected from Botanical Garden and Research Center, Bhubaneswar, Odisha, wherein the plants of Olax scandens have been cultivated and grown by the inventor in his own medicinal garden and research center. The present invention discloses a degummed and transesterified oil of Olax scandens, which has been characterized by GC-MS (Gas Chromatography-Mass Spectroscopy). The modified and processed oil is useful as bio-additive to petroleum diesel.

In an embodiment, the present invention discloses a process of extraction, modification as well as characterization of the degummed and transesterified oil of Olax scandens.

In the process, the crude oil extracted from Olax scandens seeds, is modified through several steps to reduce the free fatty acid profiles, viscosity and to improve physical and chemical properties of the crude Olax oil.

In another aspect of the invention, a process for preparation of degummed and transesterified oil obtained from the oil of Olax scandens, which is extracted from seeds of Olax scandens is described herein as follows: i. boiling the seeds of Olax scandens in a aliphatic solvent for about 4 hours and extracting the crude oil of Olax scandens;

ii. adding C1-C7 alcohol to the crude oil obtained in step (i) (oil to solvent ratio is 2:1 v/v), centrifuging, and heating to obtain degummed Olax oil;

iii. esterifying the degummed Olax oil of step (ii) with a lower alcohol and in presence of a mineral acid (Oil: alcohol: mineral acid=50: 1:0.1, v/v/v), neutralized with alcoholic base and drying the esterified oil; followed by transesterification with lower alcohol in presence of a base as a catalyst to obtain bio-additive, and iv. separating the bio-additive so obtained from unreacted oil by partitioning with water, followed by centrifuging and recovering.

According to the process, Oil from Olax seed is extracted by boiling the crushed seed with aliphatic solvent such as n-butane, n-pentane, n-hexane etc. (seed:n-solvent =l:3;w/v) . for about 4 hrs. To the crude oil is further added C1-C7 alcohol (Oil: alcohol =2:1, v/v), stirred mechanically for 30 sec and allowed to stand for 10 mins where coloured compound which is only soluble in diethylethers, are separated by decanting the oil solution. Solvent from the oil is recovered by heating on a heating mantle and then warm oil is kept under vacuum in a dessicator overnight. The resultant oil is stored as degummed Olax oil. The degummed oil obtained as above is esterified with a lower alcohol and in presence of a mineral acid such as sulphuric acid (Oil: alcohol: mineral acid=50: 1 :0.1, v/v/v), followed by transesterification with lower alcohol in presence of a base as a catalyst to obtain bio-additive. The lower alcohols are selected from methanol, ethanol, isopropanol, butanol etc. and the base is an inorganic base such alkali or alkaline metal hydroxides, preferably sodium hydroxide. During the said transesterification process, free fatty acids (FFA) present in the oil are converted to fatty acid methyl esters (FAMEs). The resultant transesterified oil is separated from unreacted oil and reagents, by-products and stored in an air-tight bottle. The transesterified oil so obtained is used as bio-additive to petroleum diesel.

Both degummed and transesterified Olax scandens oil is further analyzed and characterized by GC-MS (Gas Chromatography-Mass Spectroscopy). Results suggest that transesterification increased the peak height of FAMEs and decreased that of FFAs. Concentration of unsaturated fatty acids is also found to be comparatively higher in Transesterified oil (TEO) than that of Degummed oil (DGO). FAMEs of different saturated (example iso-myristate, hexadecenoate, palmitate, stearate and eicosenoate) and unsaturated (example hexadecatrienoic acid, linoleic acid, oleic acid, elaidic acid, linolelaidic acid, 9E octadecenoic acid, arachidonic acid) fatty acids are found in both DGO and TEO of Olax (modified) oil. In addition to these FAMEs and TEO Olax scandens oil also contains methyl esters of azelaic acid, sebacic acid, erucic acid, behenic acid. The said compounds are referred in Table 1 and Table 2 below.

The laboratory process described herein can be scaled up to industrial requirements by conventional methods of extraction, modification and in-process characterizing in commercial scale.

The density of crude Olax oil (0.941 g/cc.) decreases to 0.893g/cc for degummed oil and to 0.868g cc for TEO. Viscosity of olax oil (42.07) is also reduced due to modification, wherein, the viscosities of DGO and TEO are 8.39 and 5.13 respectively. Density and Viscosity of neat PD are 0.794 g/cc. and 4.74 respectively. The degummed and transesterified oil so obtained from the above process increases the efficiency of diesel engine.

Engine testing is performed with Petroleum Diesel (PD) that is mixed with 10% and 20% DGO and TEO respectively and the data are compared against that of neat PD. Results suggest that 10% addition of modified Olax scandens oil is more economical than 20% biofuel additive. Due to 10% addition of DGO with 33% PD, engine testing revealed that addition of biofuel with PD not only increased the run time but also reduced the temperature of the emitted gas from 274 ° C to 237 ° C and 219 C for DGO and TEO respectively. Pollution parameters of emitted smoke are also restricted due to addition of bio-additive in PD. 10% addition of DGO and TEO in PD decreased smoke and emission of CO, C0 2 , NO in smoke as compared to neat PD treatments.

The bio-additive of the present invention shows enhanced performance and hence significant engine efficiency at different given loads. Favorable trend in the fuel consumption pattern of the current bio-additive along with a drastic reduction in smoke, particulate matters and obnoxious polluting and carcinogenic gas emissions, highlights the salient features of the present invention.

The bio-additive of the present invention reduces fuel consumption, improves diesel engine efficacy and reduce pollution level as compared to neat petroleum diesel. Moreover, bio-additive of the present invention could find use in construction industry such as paints, emulsifiers, in pharmaceuticals, cosmetics etc.

The following examples, which include preferred embodiments, will serve to illustrate the practice of this invention, it being understood that the particulars shown are by way of example, for purpose of illustrative discussion of preferred embodiments of the invention, and are not limiting the scope of the invention.

EXAMPLES

EXAMPLE 1: DEGUMMING OF OIL

Oil from Olax seed was extracted by boiling the crushed seed with n-hexane (seed:n- hexane=l:3;w/v) for 4 hrs. The pure ' crude oil is light yellow coloured. To the crude oil was added isopropanol (Oil: IPA=2:1, v/v), stirred mechanically for 30 sec and allowed to stand for 10 mins, where coloured compounds which were only soluble in diethylethers, were separated by decanting the oil. Solvent from the oil was recovered by heating on a heating mantle and then warm oil was kept under vacuum in a dessicator over night. The resultant oil was stored as degummed Olax oil.

EXAMPLE 2: TRANSESTRIFICATION OF DEGUMMED OIL

The degummed oil was then esterified with methanolic H 2 S0 4 solution. Oil was mixed with methanol and H 2 S0 4 mixture (Oil: MeOH: H 2 SO 4 =50: 1 :0.1, v/v/v), and stirred constantly at 60 ° C for 3 hours. During this process, FFAs, present in the oil were converted to their FAMEs. The oil was then neutralized with methonolic NaOH solution and reaction by-products and unreacted reagents were recovered by shaking the oil with water. The oil was dried by passing the warm oil through anhydrous Na 2 S0 3 . The esterified oil was further transesterified with methanol in presence of NaOH as catalyst. The oil was constantly stirred mechanically at 200-250 rpm for 4 hours at 50 C. After completion of the reaction, bio-additive (transesterified oil) form a separate layer above unreacted oil and was separated using a separating funnel. Glycerol (main byproduct of the reaction), unreacted methanol and NaOH were removed from the oil by partitioning with water. The transesterified oil was then centrifuged to separate adsorbed moisture from oil. The oil were then kept in a dessicator under vacuum overnight and stored as transesterified oil.

EXAMPLE 3: GC-MS OF DEGUMMED AND TRANSESTERIFIED OIL

Both degummed and transesterified oil was analyzed by Gas Chromatography-Mass Spectrometry (GC-MS) using following conditions:-

Sample 01 : Degummed seed oil

Sample 02 : Trans-Esterified seed Oil

Gas Chromatography Conditions:

Column: VF 5-MS (30m x 0.25mm ID x 0.25um df)

Temperature oven: 45 °C, 1 min hold to 55°C @ 1 °C/min to 290 °C @ 15 °C/min, 5 min hold. Total Run Time: 31 min.

Flow: 1 ml/min He.

Injection: 1 μΐ split on 100 ml

Liner: Gooseneck Fritted liner 3.4mm, 1079 Injector @ 270 °C. Mass Spectrometer Conditions:

Instrument configuration: External El

Method segment: Ionization

Total Run Time: 31 min.

Mass range: 35m/z-550m/z

The GC-MS chromatogram of DGO and TEO are represented in Figure 1 and Figure 2 respectively.

The GC chromatograms of modified Olax oils showed that the bio-fuel additives predominantly contain the methyl esters of C s to C 20 fatty acids.

Results suggested that transesterification increased the peak height of FAMEs and decreased that of FFAs. Concentration of unsaturated fatty acids was also comparatively higher in Transesterified oil (TEO) than that of Degummed oil (DGO). These two factors are probably responsible for lower viscosity and better flow character of TEO as compared to DGO.

TABLE 1: COMPOUNDS FOUND IN DEGUMMED OLAX OIL (OGO)

TABLE 2: COMPOUNDS FOUND IN TRANSESTERIFIED OLAX OIL ΠΈΟ)

Heptadecanoic acid, methyl C18H3602 23.815 Methyl margarate 284 ester

9,12-Octadecadienoic acid C19H3402 24.322 Methyl !inoleate 294 (Z,Z)-, methyl ester

9-Octadecenoic acid, methyl C19H3602 24.423 Methyl elaidate 296 ester, (E)-

Octadecanoic acid, methyl C19H3802 24.494 Stearic acid, methyl 298 ester ester

9-Octadecynoic acid, methyl C19H3402 24.564 Methyl stearolate 294 ester

8,11-Octadecadienoic acid, C19H3402 24.625 Methyl (8E,11E)-8,11- 294 methyl ester octadecadienoate

9-Octadecenoic acid (Z)- C18H3402 24.746 Oleic acid 282

7,10-Octadecadienoic acid, C19H3402 24.868 Methyl (7E,10E)-7,10- 294 methyl ester octadecadienoate

9, 12, 15-Octadecatrienoic C20H34O2 25.272 Linolenic acid, ethyl 306 acid, ethyl ester, (Ζ,Ζ,Ζ)- ester

Methy 1 ( 11 E)- 11 -icosenoate C21H40O2 25.515 11-Eicosenoic acid, 324 methyl ester

Methyl arachisate C21H4202 25.657 Eicosanoic acid, methyl 326 ester

Methyl (6E,9E,12E,15E)- C23H3802 25.849 6,9,12,15- 346 6,9, 12, 15-docosatetraenoate Docosatetraenoic acid,

methyl ester

Octadecanoic acid, 9,10- C19H3804 26.133 Methyl 9,10- 330 dihydroxy-, methyl ester dihydroxystearate

Methyl (7E,10E,13E)- C21H3602 26.488 7, 10, 13-Eicosatrienoic 320 7, 10, 13-icosatrienoate acid, methyl ester

13-Docosenoic acid, (Z)- C22H4202 26.589 Erucic acid 338 Methyl (7E,10E,13E)- C21H3602 26.640 7, 10, 13-Eicosatrienoic 320 7, 10, 13-icosatrienoate acid, methyl ester n-Docosanoic acid methyl C23H4602 26.721 Methyl behenate 354 ester

Methyl (Z)-5,l l, 14,17- C21H3402 27.176 Methyl 318 eicosatetraenoate (5Z,11Z, 14Z,17Z)-

5,1 1,14,17- icosatetraenoate

Tetracosanoic acid, methyl C25H50O2 27.919 Methyl lignocerate 382 ester

(5Z,8Z,11Z,14Z)-5,8,11,14- C20H32O2 28.784 Arachidonic acid 304 Icosatetraenoic acid

The degummed and transesterified oil obtained from the crude oil extracted from the seeds of Olax scandens, is used as bio-additive to petroleum diesel. The degummed and transesterified oil of Olax scandens, is obtained from oil of Olax scandens by the aforementioned process, wherein, the so obtained degummed oil (DGO) and transesterified oil (TEO) are characterized by GC-MS and are shown in Fig. 1 and Fig. 2 respectively. The compounds in the degummed oil and transesterified oil are described in Table 1 and Table 2 respectively. Advantageously, the degummed and transesterified oil obtained in the present invention is found to enhance the performance of diesel engine and hence is effectively used as a bio-additive to petroleum diesel.