EP1885823A2 - Produktion von biodiesel aus balanites aegyptiaca - Google Patents

Produktion von biodiesel aus balanites aegyptiaca

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Publication number
EP1885823A2
EP1885823A2 EP06756177A EP06756177A EP1885823A2 EP 1885823 A2 EP1885823 A2 EP 1885823A2 EP 06756177 A EP06756177 A EP 06756177A EP 06756177 A EP06756177 A EP 06756177A EP 1885823 A2 EP1885823 A2 EP 1885823A2
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EP
European Patent Office
Prior art keywords
oil
biodiesel
aegyptiaca
balanites aegyptiaca
balanites
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06756177A
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English (en)
French (fr)
Inventor
Sarina Grinberg
Mordechay Herskowitz
Zeev Wiesman
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Ben Gurion University of the Negev Research and Development Authority Ltd
Original Assignee
Ben Gurion University of the Negev Research and Development Authority Ltd
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Application filed by Ben Gurion University of the Negev Research and Development Authority Ltd filed Critical Ben Gurion University of the Negev Research and Development Authority Ltd
Publication of EP1885823A2 publication Critical patent/EP1885823A2/de
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/1802Organic compounds containing oxygen natural products, e.g. waxes, extracts, fatty oils
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/02Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/04Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11CFATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C1/00Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/08Refining
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11CFATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1011Biomass
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to the production of biodiesel fuel from Balanites aegyptiaca.
  • Biodiesel is a biofuel consisting of a mixture of methyl or ethyl esters of long chain fatty acids produced through transesterification of oils from a biological source such as plant oils, animal fats, waste vegetable oils, or microalgae oils. It is a renewable fuel that provides a viable alternative to the petroleum-based diesel fuel. Biodiesel has been produced from a variety of vegetable oils by well-established processes starting from seeds for extraction of the oil followed by transesterification with methanol or ethanol to produce methyl or ethyl ester mixtures. Pretreatment and purification steps have been applied depending on the type and quality of the oil and the quality of the biodiesel product.
  • biodiesel The following properties show the distinct potential of biodiesel: (i) the higher cetane number of biodiesel compared to petro-diesel indicates its potential for higher engine performance; tests have shown that biodiesel has similar or better fuel consumption, horsepower, and torque and haulage rates as conventional diesel; (ii) the superior lubricating properties of biodiesel increases functional engine efficiency; (iii) the higher flash point of biodiesel makes them safer to store; (iv) the biodiesel molecules are simple hydrocarbon chains, that contain no sulfur or aromatic substances associated with fossil fuels; (v) biodiesel contains higher amount (up to 10%) of oxygen that ensures more complete combustion of hydrocarbons; and (vi) biodiesel almost completely eliminates lifecycle carbon dioxide emissions.
  • the biodiesel When compared to petro-diesel, it reduces emission of particulate matter by 40%, unburned hydrocarbons by 68%, carbon monoxide by 44%, sulphates by 100%, polycyclic aromatic hydrocarbons (PAHs) by 80%, and the carcinogenic nitrated PAHs by 90% on an average.
  • the biodiesel can be blended with conventional diesel fuel or used as neat fuel (100% biodiesel).
  • biodiesel One of the disadvantages of the biodiesel is the fact that its use in cars requires some modification in the car, although many car brands are currently marketed ready for use of biodiesel.
  • Another disadvantage is the high CFPP (cold filter plugging point) values and hence solidification and clogging of the system at low temperatures, a problem that occurs in places where the temperature decreases to around O 0 C.
  • CFPP cold filter plugging point
  • the vegetable oil for preparation of biodiesel is obtained by extraction from seeds, usually conducted in developing countries by pressing methods. Prior to extraction, pre-treatment of the fruits is required. This procedure depends on the type of fruits yielding seeds to be fed to the crusher. The material from the crusher that contains the crushed hulls and the seeds is fed to the press extruder.
  • the by- product meal from the extruder contains 10-20% weight of the total oil, depending on the type of extruder.
  • Solvent extraction is applied in certain processes to improve the oil yield.
  • the oil is normally filtered to remove fines that may be detrimental to the downstream processes for the production of the biodiesel. Additional treatment of the oil prior to its transformation to biodiesel depends on the type of oil.
  • the vegetable oils are triglycerides of C 16 and C 18 straight-chain saturated and unsaturated carboxylic acids.
  • a pre-treatment of crude oil includes degumming (elimination of phospho- and glyco-lipids) with phosphoric acid and subsequent neutralization of acidity.
  • Methanol is mostly used in current processes and its concentration in the mixture varies from 12 to 16% weight.
  • KOH is the most efficient catalyst operating at 25-60 0 C at 0.5-1.5% weight. Since the process is reversible, separation of glycerol during the process drives the reaction to completion at a high yield. Therefore, multi-stage processes with intermittent glycerol separation have been developed, and continuous separation of glycerol has also been proposed.
  • WO 2004/035396 describes a very small container (a hand held device) to produce small amounts of biodiesel by a transesterification process.
  • WO 03/087279/US 20030229238 discloses a continuous transesterification process for converting at least one triglyceride feedstock to at least one fatty-acid methyl ester product, wherein converting is carried out in a continuous, plug-flow environment at a temperature of 80-180°C.
  • WO 2004/085579 describes a method and apparatus for producing biodiesel fuel wherein the transesterification catalyst is prepared by spraying alkyl alcohol under pressure through jets at metal hydroxide pellets until full reaction of the pellets with the alcohol.
  • WO 03/022961 describes a batch reaction process for esterifying waste oil.
  • WO 03/066567 discloses a continuous process for preparing an alkyl ester of fatty acids with high purity by reacting vegetable oil with a lower alcohol in the presence of alkali catalyst using a tubular reactor.
  • US 6,440,057 describes the reaction under dynamic turbulence in the reaction section and the transesterification is performed under pressure, wherein the pressure is reduced during transesterification.
  • the present invention relates to a process for producing biodiesel from Balanites aegyptiaca oil comprising reaction of the oil with a C 1 -C 4 alkanol at a molar ratio of oil:alkanol from 1 : 12 to 1 :3, preferably 1 :8: or 1 :6, at a temperature within the range of 25-100 0 C, preferably 25-8O 0 C, more preferably 25-6O 0 C, under intensive mixture conditions, in the presence of a transesterification catalyst, and allowing the transesterification to occur while removing the glycerol formed during the reaction.
  • the biodiesel product thus obtained comprising a mixture Of C 1 -C 4 alkyl esters of the fatty acids present in the Balanites aegyptiaca oil, that may contain Balanites aegyptiaca saponins, is washed with water to remove the catalyst, and the Balanites aegyptiaca biodiesel is recovered.
  • the present invention relates to a process for producing biodiesel from Balanites aegyptiaca crushed nuts, comprising the following steps: (i) homogenizing Balanites aegyptiaca crushed nuts with a C 1 -C 4 alkanol, at a temperature within the range of 25-100 0 C, preferably 25-8O 0 C, more preferably 25-6O 0 C; (ii) reacting the homogenate obtained in step (i) with a transesterification catalyst; (iii) filtering the reaction mixture product obtained in step (ii); (iv) extracting Balanites aegyptiaca biodiesel comprising a mixture of C 1 - C 4 alkyl esters of fatty acids and optionally Balanites aegyptiaca saponins from the filtrate obtained in step (iii); (v) neutralizing the mixture product obtained in step (iv) and removing C 1 -C 4 al
  • the C 1 -C 4 alkanol is methanol or ethanol.
  • the present invention also relates to a method for production of the B. aegyptiaca oil from B. aegyptiaca seeds and to the biodiesel obtained from B. aegyptiaca oil or crushed nuts.
  • biodiesel of the present invention can be used either alone or in blends with conventional diesel or other types of biodiesel.
  • FIGURES show images of the various fractions obtained from B.
  • FIG. 2 shows the gas chromatography profile of B. aegyptiaca biodiesel produced from crushed nuts, indicating the presence of linoleic acid (18:2), oleic acid (18:1), palmitic acid (16:0) and stearic acid (18:0).
  • the Balanites are plants of the Zygophyllaceae family, comprising 9 species and 11 intraspecific taxa.
  • the plants used in the present invention are the species Balanites aegyptiaca Del, also known as thorn tree, Egyptian balsam and Zachum oil tree, which is one of the most common species of the genus Balanites and widely grown desert tree with a multitude of potential uses. It is found throughout the Sudano-Sahelian region of Africa and in other arid and semi arid regions of Africa, the Middle East, India and Burma. It is one of the most drought-resistance tree species in these arid regions. In Israel, B.
  • aegyptiaca plants are found in various locations, mainly along the Jordan Valley and the Arava, where it is grown with industrial sewage water containing high salinity ( ⁇ 5 dS/m) and relatively high level of heavy metals contamination.
  • Plant tissues from B. aegyptiaca have been used in a variety of folk medicines in Africa and Asia. Extracts from several parts of this tree have been intensively used in Africa and India for various ethnobotanical purposes. For example, Balanites extracts were shown to exhibit antifeedant, antidiabetic, molluscicide, anthelmintic and contraceptive activities. Earlier studies have shown that B.
  • aegyptiaca contains saponins, which are amphiphilic molecules consisting of a hydrophobic sterolic aglycone linked to one or more hydrophilic glycoside chains, and most of these studies have reported that the presence of saponins is the main cause behind these activities. Besides its medicinal uses, Balanites trees are widely used as fodder, and for timber purposes.
  • B. aegyptiaca fruits contain a glycoside pulp (35% /fresh weight), nut (45% /fresh weight) and kernel (25% /fresh weight). The kernel contains about 45% oil.
  • B. aegyptiaca trees usually live and remain productive for dozen of years. Recent studies carried out in Israel, clearly showed that the productivity of low quality partially purified waste saline water irrigated B. aegyptiaca trees of various origins were significantly increased to about 15,000 kg per hectare (420 trees planted in one hectare).
  • B. aegyptiaca can be cultivated and be productive in marginal and contaminated environments. This approach may support large world desertification combating campaign and produce significant amounts of green raw material for low cost alternative biofuel. Furthermore, it would support a world initiative of reclamation of industrial contaminated soil and water resources.
  • the B. aegyptiaca oil for use in the present invention may be produced from B. aegyptiaca seeds.
  • the extraction process comprises the following steps: (i) washing the B. aegyptiaca fruits with water in a large rotating pan to dissolve and to remove the glycosides from the seed coats; (ii) overnight oven drying of the washed B. aegyptiaca seeds plus its heavy coat; (iii) crushing the seeds plus its heavy coats by a metal hammer crusher to a relatively homogenous powder; (iv) extruding the powder, draining the B.
  • aegyptiaca oil out of the mixture extraction of the oil may also be done using an organic solvent such as hexane or tetrachloroethane); and optionally (v) decantation of the oil for about least two weeks and/or centrifugation followed by vacuum filtering the B. aegyptiaca oil through a 0.4 micron membrane, if it is desired to remove the amph philic emulsifying particles.
  • the B. aegyptiaca oil extracted from fruits collected in the Ben-Gurion Balanites genetic material collection plot located in Arava rift valley has a composition of triglycerides of mainly C16:0 and Cl 8:0 saturated and unsaturated fatty acids, with a very high content of C 18:2 linoleic acid and of C 18: 1 oleic acid, similar to soybean, corn and cottonseed oils (see Table 1 hereinabove). Moreover, the very low free fatty acid ( ⁇ 0.04 meq/g) and water content (0.16-0.9%) are an excellent basis for the transesterification and no pre-treatment is needed.
  • the transesterification step in the processes of the present invention may be carried out in the presence of any transesterification catalyst known in the art.
  • the catalyst may be a homogeneous catalyst such as, but not limited to, potassium hydroxide or methoxide or sodium hydroxide or methoxide, or a heterogeneous solid basic catalyst such as zeolite ETS-10.
  • the transesterification catalyst is potassium hydroxide.
  • the alcohol used for the transesterification is a Ci-C 4 alkanol such as methanol, ethanol, propanol or butanol.
  • the alcohol is methanol.
  • the alcohol is ethanol.
  • the ethanol may be obtained from any suitable source.
  • one of said sources may be the ethanol produced by fermentation of free sugars obtained from the glycosides removed from the Balanites seed coats (mesocarp), after extraction of the oil.
  • the alcohol is used in excess, for example, at a molar ratio oil:alcohol from
  • the temperature of the reactions is in the range of about 25-100 0 C, preferably about 25-8O 0 C, and more preferably about 25-6O 0 C.
  • the transesterification reaction is carried out at room temperature (25 0 C). In another embodiment, it is carried out at about 60 0 C, for example, at 63 0 C.
  • Other important factors of the process in which biodiesel is produced from B. aegyptiaca oil are the mixing of the transesterification mixture and the separation of the formed glycerol.
  • the reaction can be carried out in a batch or tubular reactor, with proper mixing. A static mixer as known in the art may be suitable.
  • the process is conducted in two stages with interim separation of glycerol.
  • the biodiesel product namely, the mixture of alkyl esters, is washed with water to remove the esterification catalyst and any other non-desired residues.
  • the extraction of the B. aegyptiaca biodiesel from the filtrate and from the filter-cake obtained in step (iii) may be performed using any suitable organic solvent.
  • the extraction of the filtrate is performed using petroleum ether or ether, and the extraction of the filter-cake is performed using hexane, dichloromethane or tetrachloroethane.
  • Table 2 Fatty acid profile of B. aegyptiaca oil and biodiesel
  • the diesel characteristics which are important for potential applications are: (i) Cetane number (CN) 5 that rates the ignition quality of diesel fuels; (ii) Density, normally expressed as specific gravity, which defines the ratio of the mass of a volume of the fuel to the mass of the same volume of water; (iii) Viscosity, that measures the fluid resistance to flow; (iv) Heat of combustion (HC), which measures the available energy in the fuel; (v) Carbon residue, that correlates with the amount of carbonaceous deposits in the combustion chamber; (vi) Ash, which refers to extraneous solids that reside after combustion; (vii) Sulfur; (viii) Lubricity, that can be defined as "the property of a lubricant that causes a difference in friction under conditions of boundary lubrication when all the known factors except the lubricant itself are the same".
  • the biodiesel of the present invention was analyzed according to European biodiesel standard EN 14214 and the results are summarized in Table 3 below, showing that all its properties met corresponding standard specifications. Furthermore, as illustrated in Example 3 hereinafter, various blends of diesel fuel containing either 5, 10 or 25% biodiesel of the present invention as well as a pure sample of this biodiesel were tested for engine performance, namely, fuel consumption, moment yield and emission profile, and the results were compared with those obtained from a pure conventional diesel fuel. As illustrated in detail in Example 3, the biodiesel of the present invention keeps the same moment of the engine as conventional diesel and reduces toxic emission gases such as CO, CO 2 and hydrocarbons. In addition, fuel consumption was also slightly increased in comparison with conventional diesel, as also known for other biodiesel sources. Table 3: Properties of B. aegyptiaca biodiesel according to EN 14214 standard
  • saponins can reduce fuel drop size by increasing and improving atomization due to reduction of surface tension, thus improving the combustion of the fuel and maximizing the caloric value obtained.
  • B. aegyptiaca oil contains relatively high amount of saponins, which are expected to be found in the produced biodiesel.
  • aegyptiaca saponins were found to be assembled in nanovesicles shape and are able to encapsulate hydrophilic materials. These properties further enable B. aegyptiaca saponins to trap and encapsulate water residues available in the bottom of the fuel tank, acting as a detergent and reducing the rate of corrosion. Furthermore, since these saponins are able to encapsulate toxic metals highly available in conventional diesel, adding the biodiesel of the present invention to any other diesel and/or biodiesel source will add an additional adjuvant (surfactant) highly important to the fuel efficiency and to the engine, enabling a smoother operation and improving the engine performance. It should be noted that no other biodiesel source having a high saponin content has been reported yet.
  • the level of B. aegyptiaca saponins expected to be found in the biodiesel of the present invention is in the range of 0.01-0.05%, and might be sufficient to improve the fuel and contribute to the engine operation and maintainance. However, in some cases there may be a need to enrich this level up to 0.1%, for example, by supplementing saponins washed from the B. aegyptiaca pulp in the very beginning of the fruit processing, as described in detail in the US Provisional Applications No. 60/692,661 and No. 60/781,332 mentioned above. Since the content of saponins in B.
  • aegyptiaca crushed nuts, containing both kernel and fibers is relatively high, it is extepcted that supplement of saponins may be mainly required, if at all, in biodiesel produced from B. aegyptiaca oil.
  • higher level of saponins may be obtained also in the biodiesel produced from crushed nuts by less intensive fiber separation prior to the production process.
  • the oil of Balanites roxburghii another common species of the genus Balanites distributed in the semi- arid regions of northern and southern India, has been recently disclosed as suitable for the production of biodiesel (Current Science, Vol. 188, No.
  • the iodine number of the B. roxburghii oil is significantly lower compared to the B. aegyptiaca oil, indicating a higher degree of saturated fatty acids which is further supported by the higher viscosity of this oil.
  • the refractive index of the B. roxburghii oil is also somewhat lower, indicating a lower degree of glycosides, which may be correlated with a higher amount of free sterols.
  • the B. roxburghii oil contains significantly lower content of unsaponifiable matter such as saponins.
  • aegyptiaca oil is linoleic acid followed by oleic acid, the main fatty acid in the B. roxburghii oil is oleic acid followed by linoleic acid.
  • the relatively high level of saponins found in the B. aegyptiaca oil and expected to be found in the produced biodiesel as well seems to be of great importance, as will be explained hereinafter.
  • the present invention also provides a relatively fast and efficient process for the preparation of B. aegyptiaca crushed nuts, containing more than 89% of the overall oil potential, that can be used for oil extraction or directly for biodiesel production, as described in Examples 5-6 hereinafter.
  • Example 1 Transesterification reaction of B. aegyptiaca oil with ethanol at room temperature
  • a mixture of 233 g of Balanites aegyptiaca oil (0.27 mol), 99.4 g (2.16 mol) absolute ethanol and 2.3 g KOH (1 wt% with respect to the Balanites aegyptiaca oil) was mechanically stirred at room temperature (25 0 C) in a batch reactor for 3 h, and the two phases obtained were separated. The upper phase was washed with 50 ml of a saturated solution of NaCl and then dried over magnesium sulfate, filtered and evaporated to yield 215.8 g of the Balanites aegyptiaca biodiesel (ethyl esters) with a purity of 97%.
  • Example 2 Transesterification reaction of B. aegyptiaca oil with ethanol at a temperature of about 6O 0 C
  • a mixture of 153 g (0.176 mol) of the Balanites aegyptiaca oil, 50 g absolute ethanol (1.08 mol) and 1.5 g KOH (1 wt% with respect to the Balanites aegyptiaca oil) was stirred at 63 0 C for 40 min.
  • the reaction mixture was allowed to stand for about two days, but no phase separation could be detected. After the addition of 20 ml of water, a phase separation was observed.
  • the upper organic phase was separated and washed with 20 ml of a saturated solution of NaCl and then dried over magnesium sulfate, filtered and evaporated to yield the the Balanites aegyptiaca biodiesel (ethyl esters) in 82% with a purity of 93%.
  • the lower glycerol phase contained 33.2 g and gave, after ethanol evaporation and extraction with hexane, an additional amount of ethyl esters (7.2 g). Hence, the overall yield of the biodiesel was 86.7%.
  • the fatty acid profile of the B. aegyptiaca biodiesel obtained was analyzed by a GC/MS and compared to the fatty acid profiles of B. aegyptiaca oil and soy biodiesel.
  • four main fatty acids namely, palmitic, linoleic, oleic (9) and stearic acids account for 98.39%, 98.85% and 97.25% of the total fatty acids found in B. aegyptiaca oil, B. aegyptiaca biodiesel and soy biodiesel, respectively.
  • oleic acid (10) stands for 10-octadecenoic acid, usually present in minor quantities in almost all oils and not detected by less sensitive methods than the one used here.
  • B. aegyptiaca and B. roxburghii are the two most common species of the genus Balanites, which belongs to the family Zygpophyllaceae and consists of 9 species and 11 intraspecific taxa.
  • B. aegyptiaca is found mainly throughout the Sudano-Sahelian region of Africa and in other arid and semi-arid regions of Africa and the Middle-East
  • the B. roxburghii is distributed in the semi- arid regions of northern and southern India.
  • the purpose of this study was to compare morphological parameters of the fruits of these two species, the properties and profile of the oil obtained from the fruits of each of the species, and their saponin content and composition.
  • B. aegyptiaca fruits were collected from the Balanites plant grown in Kibutz Samar, Arava valley, Israel, and B. roxburghii fruits were collected from Jodhpur, Bengal State of India.
  • the results of this comparative study are summarized in Tables 8-14 hereinafter.
  • the fruits of B. roxburghii are much bigger and about 4-5 times heavier than the fruits of B. aegyptiaca, and the same for the kernels of each of the fruits, from which the majority of the oil may be obtained.
  • the oil content in the B. roxburghii kernel is about 8-10% higher than in the B. aegyptiaca kernel.
  • Table 10 shows that the physical properties of the oils obtained from the kernel of these two species are significantly different.
  • the iodine number of the B. roxburghii oil is significantly lower, indicating a lower degree of unsaturated fatty acids and a higher degree of saturated acids, and this finding is further supported by the higher oil viscosity.
  • the refractive index of the B. roxburghii oil is also somewhat lower, indicating a lower degree of glycosides.
  • An additional significant difference relates to the saponification value and unsaponifiable matter percent, indicating a significantly higher content of unsaponifiable matter, such as saponins, in the B. aegyptiaca oil.
  • Table 11 shows the considerably different fatty acid profile in each oil, indicating that although both species belong to the same genus, they are clearly genetically different.
  • the main fatty acid in B. aegyptiaca oil is linoleic acid (45.19%) followed by oleic acid (22.03%)
  • the main fatty acid in B. roxburghii oil is oleic acid (37.49%) followed by linoleic acid (29.37%).
  • the free sterol composition of these two oil is different and the overall amount of free sterol in B. aegyptiaca oil is about 25% less in comparison to B.
  • roxburghii oil (Table 12). Since sterols in nature are components highly conjugated with glycosides, the lower amount of free sterols in the B. aegyptiaca oil may be correlated with the higher degree of glycosides in this oil, as indicated by the refractive index.
  • the B. roxburghii pulp (mesocarp) contains more saponins than the B. aegyptiaca pulp. However, as shown in Tables 13-14, the saponin composition of the oil obtained from each of these species is significantly different and the overall saponin content in B. aegyptiaca kernel is about 50% higher than in B. roxburghii kernel.
  • Table 12 B. aegyptiaca and B. roxburghii oils sterols composition (mg/kg)
  • Sapogenin was calculated as steroid aglycone equivalent according to the method described by Baccou et al. (1977) and Uematsu et al. (2000), with some modification by Chapagain and Wiesman (2005).
  • Table 14 B. aegyptiaca and B. roxburghii oils major saponins composition
  • Example 5 Oil extraction from B. aegyptiaca crushed nuts
  • Balanites aegyptiaca fruits were processed for the extraction of oil using two different methods as described hereinbelow.
  • Known amounts of B. aegyptiaca fruit and water were loaded onto an electrical mixer and were allowed to mix for several hours.
  • mesocarp washing was completed, the liquid saponin-rich extract formed was unloaded and filtered to remove exocarp particles and nuts.
  • the nuts were washed off the saponin extract, left overnight for water drainage, and then dried for several days in a 7O 0 C oven.
  • Table 15 shows the amounts of dry stone obtained in each one of the experiments performed and the mean percentage of dry stone weight out of the whole fruit weight. As shown, after removal of the pulp, about 41.5% (mean) of the whole fruit weight remained as dry matter for the next stages of oil extraction. Table 15: 5. aegyptiaca fruit washing to remove the glycosidic pulp
  • the dry stone ( ⁇ 41.5%, mean weight) consists of the nut built of strong endocarp, which consists of sugar polymeric fibers and the kernel, highly enriched with oil.
  • the dry nuts were subsequently crushed using a roll-crusher to produce a crushed material with differences in particle size distribution between kernel and outer stone. This fact enabled use of different hole-size sieves in order to separate the oil-rich kernel from the outer stone. 4 mm- and 10 mm-mesh sieves were chosen, and crushed material was prepared to three degrees of purity: unsieved crushed material, 4 mm-mesh- sieved crushed material and 10 mm-mesh- sieved crushed material.
  • Oil was extracted from each one of the crushed materials utilizing either mechanical oil extraction or hexane solvent extraction using the Soxhlet system.
  • the Horiba oil content analyzer (OC 350) was used in order to set a reference value for oil content in the various samples investigated.
  • oil percentages of 10 mm-mesh-sieved crushed material were the highest in both methods, while oil percentages for 4 mm-mesh sieved crushed material and unsieved material were second high and lowest, respectively.
  • oil percentages obtained through the Soxhlet system were very close to the reference values of the Horiba oil content analyzer, while oil percentages obtained through the extrusion method tended to be significantly lower than the reference values, indicating that quiet a considerable amount of oil remains inside the press cake without being extracted.
  • Table 16 Oil percentage of various purity degree B. aegyptiaca crushed nuts
  • Kernel percentage of dry nuts used for this experiment was found to be approximately 21% (w/w), and the percentage of the various crushed fractions obtained is given in Table 17.
  • Figs. 1A-1D show images of the >10, >8, >6.3 and >4 mm-mesh-sieved fractions obtained from B. aegyptiaca nuts crushed using a disk mill at the fasted feed rate, respectively
  • Figs. 1E-1F show images of the ⁇ 4 mm-mesh-sieved fraction that was separated using an air-classifier into a heavy fraction (IE) and a light fraction (IF).
  • IE heavy fraction
  • IF light fraction

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