Indian Patents. 215092:"NOVEL PROCESS FOR CRACKENG OF OLEIC ACID AND HIGH OLEIC VEGETABLE OILS BY INVOLVING HYPERACIDIC CATALYSTS PREPARED BYIMPROVED PROCESS"

Title of Invention	"NOVEL PROCESS FOR CRACKENG OF OLEIC ACID AND HIGH OLEIC VEGETABLE OILS BY INVOLVING HYPERACIDIC CATALYSTS PREPARED BYIMPROVED PROCESS"
Abstract	A process for cracking oleic acid and high oleic vegetable oils by involving hyper acidic catalyst- surface supported sulfated zirconium silicates that offers quantitative yields and is reproducible.

Full Text	FORM 2 THE PATENTS ACT, 1970 (39 of 1970) COMPLETE SPECIFICATION [See section 10; rule 13] "A PROCESS FOR CRACKING OF OLEIC ACD3 AND fflGH OLEIC VEGETABLE OILS BY INVOLVING HYPERACIDIC CATALYSTS" (a) MALSHE VINOD CHINTAMANI (b) 1, Staff Quarters, UDCT Campus, Matunga Mumbai - 400 019. India (c) Indian National The following specification describes the nature of this invention and the manner in which it is to be performed: Related Application Related application for patent: Related application for "surface supported sulphated zirconium silicate catalyst" with application no. 1018/MUM/2003 is disclosed and reported herein. TECHNICAL FIELD This invention related to a process for cracking oleic acid and high oleic vegetable oils by involving hyper acidic catalyst which is surface supported sulfated zirconium silicates that offers quantitative and reproducible yield. BACKGROUND AND PRIOR ART Renewable raw materials are organic materials from vegetable or animal sources, which can be used in part or as whole as raw materials for industry or as energy carriers. Unlike fossil raw materials they are renewed annually. For many centuries various fats, oils and waxes have served as source of fuel, light, food, soap and other basic materials necessary for life. The availability of petroleum is gradually -decreasing, so to solve this problem renewable raw materials provide good alternatives. Vegetable oils are becoming very popular for a wide variety of technical and chemical uses (Battersby et al; Chemosphere; 24; 1989-2000 (1992), Mc Ketta Encyclopedia of Unit Processes Vol 6, 401-420), as they have facile chemical structure and inexpensive production methods. The major components of vegetable oil are triglycerides containing different aliphatic chains which may be saturated or unsaturated, and the degree of unsaturation varies providing excellent sites for reactions. Currently they are used for wide range of applications like production of 2 cosmetics, pharmaceutical products, leather care products, paints, varnishes, emulsifiers, plasticizers, surfactants, plastics, solvents and resins. Uses of vegetable oils have grown during the past years because they are inherently biodegradable, having low ecotoxicity and low toxicity towards humans, are derived from renewable resources and do not contribute volatile organic chemicals (VOC) and hence are essential components of green chemistry. The various uses of alkenes have grown over last few years. They are an essential feed stock for the manufacture of linear low-density poly ethylene (LLDPE), oxo alcohols, solvent soluble colours, lubricants, packaging materials for foods, textiles, adhesives, sealants, wire and cable insulators, manufacture of automotive parts and detergent alkylates as described in Ullman's Encyclopedia of Chemical Technologies Vol 5, p-704. All of these represent a significant volume business with sizable value addition. The demand cannot be completely fulfilled as they can be obtained only from the petroleum products i.e. alkanes. The conventional methods to synthesize alkenes completely depend on the availability of the raw materials which are non renewable and hence there is a need to look for alternatives as alkenes are widely used in chemical industries for various reasons. Olefin metathesis is an important catalytic reaction in organic synthesis, in which olefin are converted into new products via the rupture and reformation of carbon -carbon double bonds. Unsaturated fatty acid esters and oils are very promising renewable and cheap sources for metathesis which makes the metathesis reaction of interest to the chemical industry by offering novel routes to new and existing procedures. This reaction is a unique combination of part natural and part mineral product to produce alkenes of different molecular weight. Nylon 9 is prepared by a laborious route as described in Ullmann's Encyclopedia of Industrial Chemistry volume A 10, p- 567 to 655 starting from ozonide of oleic acid, which is first converted, in a linear Cg aldehyde with a terminal carboxylic acid group. The aldehyde is converted to an amino group by reductive amination using ammonia and a reducing catalyst. Even though a clean reaction, ozonolysis is an expensive 3 proposal for production of bulk chemicals and cheaper alternatives must be sought. The synthesis of Nylon 11 is based on a five-step process from castor oil to 11-amino undecanoic acid with very poor yield. Besides, the highly volatile price of castor oil has constantly discouraged new entrants in this business. The anti Morkonikov addition of hydrogen bromide on the terminal double bond of undecylenic acid is probably another complication, which is a closely guarded secret and is equally crucial •for the correct quality of Nylon 11 monomer. A 30-40% aqueous dispersion of the acid can be polycondensed in 3-steps and Nylon His formed. This polymer is too expensive for general use and its use is restricted to a few special applications in luggage, ropes, transmission belts, sports goods, gears, coatings for special applications and brush bristles. No technical report could be found on catalytic cracking of oleic acid and oleic acid rich vegetable oils in published or patent literature. We considered the possibility of a selective cleavage of oleic acid at the 9-10 double bond of oleic acid by acidic catalyst anticipating the following sequence of reactions. H3C (CH2)7 HC—CH (CH2)7 C00H Oleic acid f 1 H3C (CH2)T HC=— CH2 H3C (CH2)5 HC=CH2 + + H2C= HC (CH2) 5 C00H H2C=HC P2)7 C00H Due to the possibility of formation of the carbo cation on either side of the double bond with equal ease, four products were expected. Of these, the two olefins would be easily separated. Due to the difference in their carbon number and similarly the two terminally unsaturated carboxylic acids are amenable to separation and at least three 4 reactions (carbonylation, hydroformylation followed by animation or oxidation) and would be potential source of monomers for Nylon 9 and Nylon 11. These possibilities are in addition to the usual hydrogen bromide addition and amination to form amino acids. Properties of Nylon 9 and Nylon 11 are fairly similar and these could be considered as bulk plastics of the future. Only high cost separates them from their volume usage. Highly acidic catalysts are known to cleave carbon-carbon bond at high temperatures, silica alumina being the most well known to crack the hydrocarbons. Using silica alumina necessitates a high temperature 550° C at which the selectivity of the reaction would be very low since most of the products would be low molecular weight olefins. Use of sulphated zirconia as a catalyst has been reported by Yadav and Nair in "Microporous and Mesoporous materials" (1999) 33, 148. Sulfated zirconia has been described as the most promising and emerging catalyst for the times to come. In that paper the zirconia or zirconium oxide catalyst was prepared with modified anion such as sulfate ions form highly acidic catalyst depending upon the method of treatment. The characterization and various parameters affecting catalyst preparation were also studied. These prepared catalysts were examined for their reactivity and reusability for various model reactions such as hydrocarbon isomerisation, alkylation, acylation, esterification, etherification, condensation, nitration, cyclisation, cracking, and various other reactions where acidic catalysts are used. The results obtained from these catalysts were compared with conventional catalyst and comparative conclusions were derived confirming the better activity of sulfated zirconia catalysts. Until 1999 only sulfated zirconia was extensively studied. The concept of supported sulfated zirconia has emerged only in the new millennium. In the last three years, Sulfated zirconia was supported on various supports which were not reported earlier. Various methods of preparations were reported since then. In one of the methods alumina promoted sulfated zirconia was supported on mesoporous molecular sieves of pure silica MCM-41 and SB A -15. The catalyst was prepared by direct impregnation of metal oxide onto the silica surface, followed by solid state dispersion and thermal decomposition. Chen et al (Chen et al, Catalysis Letters (2002), 78 (1-4), 223-229) 5 reported the supported sulfated zirconia by direct exchange of metal containing precursor for the surfactants in the synthesized MCM-41 material. Wang S., Guin J.A. (Microporous and Mesoporous Meterials (2001), 50 (2-3), 201-208) reported the preparation of supported sulfated zirconia catalyst by precipitation of Zr (NO3) 2 with NH3 at pHIO and further calcination at 600°C. The reactivity was enhanced by 30 -50 % compared with acid resin Amberlyst 15 in etherification reaction (Chemical communication (2000), (24), 2499-2500). Lei, T; Xu et al. (Lei et al, Applied catalysis A (2000), 181-188) was prepared catalyst [(S04)2 - Zr02] (SZ) supported on A1203 or Si02 by impregnation method. This catalyst was used for isomerisation reaction of n -butane. Huan, yin- yan et al. (Haun, et al, Applied catalysis (1998), 173, (1), 27-35) reported silica or alumina supported sulfated zirconia prepared by dispersion followed by calcinations at 750° C. Another supported catalyst was modified by Grau , Javier Mario et al by the addition of Pt over various pure and heterogeneous supported sulfated zirconia like (i) pure (SO4 - Zr02 (ii) Mechanically mixed (SO4) - Zr02 with A12O3 or Si02 and (iii) (SC»4)2 - Zr02 supported over Al203 or Si02 and comparative studies of their reactivity was done where it was seen that (SO4)- Zr02 supported over AI2O3 or S1O2 and Pt/ Si02/ (SO4)2 - Zr02 was the most stable and reactive catalyst (Grau et al, Applied Catalysis, A (1998), 172(2), 311-326). In another study the supported sulfated zirconia catalyst had been prepared by Anderson et. al (Can. J. Phys. Chem. (1995), 99(3), 1444-1449) for the oxidation of S02 or by impregnation with sulfuric acid and its surface properties and acidity have been characterized by IR spectroscopy. Another ecofriendly catalyst having sulfated metal oxide and mesoporous zeolites was prepared by Yadav, G. D. et al in GB 2332155 (1999) who used it for producing oligomers from a- olefins, Fridel - craft's alkylation and acylation reaction. In another work by Yadav, G.D. et al. the reported in Green Chem (1999) Dec, (269-274) the catalyst was prepared by precipitating zirconia on calcined HMS and further treated with NH3 and was calcined at 550°C. This catalyst was used for alkylation of p-cresol with MTBE where major product was obtained with highest yield and conversion when compared to other conventional catalysts. The reactivity of this catalyst has been studied for isobutene alkylation by butane by Paukshtis, E. A. et al. in 2002, as reported in studies in surface science and catalysis (2002), 130c. It was seen that it has better catalytic activity and shape selectivity when 6 compared to conventional acidic catalyst like AICI3 and BF3. The performance of Pt catalyst supported on sulfated zirconia-silica with different stoichiometries was investigated by Salmones, J. in n-pentane hydromerization reaction with enhancement in catalytic activity (Catal. Lett.; (1996) 36(3,4), 135-138). In another study by Inada, K et al in Chem. Lett.; (1993), 10, 1795-1798, silica supported sulfated zirconia catalyst was used for reduction of aldehydes and ketones with 2- propanol, corresponding alcohols were obtained in high yields. In the catalyst silica supported sulfated zirconia the results obtained agreed with the models proposed by De Jong et al in Surface Interface Anal. (1992), 18(6), 412 - 416 for sulfated zirconia catalyst on porous silica supports. Sulfated zirconia is known for high surface acidity. In spite of these products being known for about 20 years and their extensive capability to substitute homogeneous acid catalyst, no commercial product seems to have emerged. In a lecture delivered at UDCT in 1999 on sulfated zirconia catalyst, Dr. Francis Figueres commented that the problem of reproducibility in preparation of sulfated zirconia is so great that every time one made a catalyst, it was a new catalyst. This comment led us to the thinking and the development of surface sulfated zirconium silicate catalyst being reported here. Most of the reported synthesis starts from zirconium oxychloride precipitation as hydroxide followed by calcinations, sulfation with sulfuric acid or ammonium sulfate, then calcination to fix the acid sites and surface area. The attempt to fix surface area and acid sites simultaneously causes problem of variation in surface area, pore volume and pore size distribution, which is a well-known phenomenon in hydrous oxides. Secondly if a bulk of zirconium oxide is used up in preparing the massive matrix, it cannot contribute to the activity of the catalyst. Wang et al in Chem. Commun, (2000), 2499-1500 have reported preparation of silica supported sulfated zirconia and studied the conversion of methanol and isobutylene to MTBE. They have studied loading from 15 to 50 % and found a loading of 50% to give best performance. The authors have not considered the atom efficiency of the 7 1019 MUM)2003) catalyst. (Zirconium is not a noble metal; it is still expensive compared to elementary acidic materials like silica and alumina). Silica supported surfated zirconia catalyst has following benefits; 1 It is possible to tailor physical properties such as surface area, pore volume, bulk density and particle size conveniently. 2 It is resistant to acids such as sulfuric acid, which are involved in next step of preparation. , .." 3 It forms covalent bond with group IV elements such as Ti, Zr, and Hf, hydroxides through the surface silanol groups that might be helpful in retaining the catalytic activity. 4 It is the most abundant element and is very inexpensive, has no disposal or toxicity problem. r-:" 5 In pure state, it is colorless. Not many other industrial supports such as activated carbon, activated alumina or activated clay could offer these benefits. We noticed that there is no published study on the use of supported sulfated zirconia for the cracking of vegetable oils. In this work we are reporting preliminary findings of the catalytic cleaving of oleic acid or vegetable oils rich in mono unsaturated acids. Soyabean oil is one of the cheapest vegetable oils in the tropical regions and would form a good feed stock for chemical products. SUMMARY OF INVENTION A process for cracking of oleic acid and high oleic vegetable oils by involving hyperacidic catalysts such as surface supported sulfated zirconium silicate catalysts to produce a-olefins and terminally unsaturated carboxylic acids wherein the said process comprising (i) introducing oleic acid or / and unsaturated fatty acids such as high oleic vegetable oils such as soybean oil into a reactor; (ii) adding 1% hyperacidic catalyst such: as surface supported sulfated zirconium silicate catalyst to the said reactant; (iii) heating the said reaction mixture to 280°C to 300°C till distillate comes out from the said reaction mixture; 8 (iv) adding sodium alkali metal alkoxide; preferably sodium methoxide to saponify the carboxylic acid in the said distillate; (v) adding organic solvent, hexane to the said saponified distillate to give two phase system; (vi) extracting product I, a-olefins in hexafie" by vigorously shaking the said two phase system; (vii) separating the organic layer, hexane from the said two phase system; (viii) collecting the said organic extracts ; (ix) distilling out hexane to isolate the product I (a-olefin) i.e.C8 and CIO a -Olefin; (x) acidifying aqueous phase of the said two phase system after extraction; (xi) adding the hexane to the said acidified aqueous phase to give two phase system, (xii) extracting product II, C8 and CIO terminally unsaturated carboxylic acid in organic phase containing hexane from the said two phase system; (xiii) distilling out the hexane from the said organic phase to isolate the product II (acid) ; and (xiv) the residue comprising terminally unsaturated carboxylic acid bonded to glycerin obtained in step iii is saponified with alcoholic potassium hydroxide, preferably in ethanol solvent, removing the alcohol by distillation and repeating the steps (x) to (xiii) described above to isolate the terminally unsaturated carboxylic acid. DETAILED DESCRIPTION OF THE INVENTION A process for cracking oleic acid and high oleic vegetable oils by involving hyper acidic catalyst that offers quantitative and reproducible yield is disclosed. More specifically catalyst used in this process of cracking of Oleic aciddand high oleic vegetable oils to produce a-olefines and terminally unsaturated carboxylic acid is surface supported Sulphated Zirconium Silicate catalyst. The process for the synthesis of the said catalyst is disclosed in our application number 1018/MUM/2003. 9 Methods for Analysis Employed Chemical Method 1) Acid value (ASTM 1639-70) About 0.5-1 gm of the sample was accurately weighed in the conical flask. 25 ml of neutral alcohol was added to dissolve the sample. 3-4 drops of 1% phenolphthalein solution (in ethanol) was added. The mixture in the conical flask was titrated against 0.1N alcoholic potassium hydroxide solution. Acid value was calculated as follows: A.JWI 56.1 X normality of KOH X ml of KOH Weight of the sample in grams Acid number is expressed as milligrams of KOH per gram of sample 2) Iodine number (method of American oil chemists society) About 1 gm of sample was weighed in a 250ml quick fit conical flask and was dissolved in carbon tetrachloride. 25 ml of Wij's solution was added to it with constant stirring. The solution was kept in dark for 30 mins. 10 ml of 10% KI was then added and the liberated iodine was titrated against Na2SC>3 using starch indicator. A blank reading was carried out simultaneously. The saponification number was calculated using following formula: 56.1 X normality of Na2S03X(B-S) Iodine Number = —-—- Weight of the sample in grams B = ml of Na2S03 of required for blank S= ml of Na2S03 required for sample Iodine number is expressed as grams of Iodine per 100 gram of sample 10 Instrumental Methods: 1. Gas Chromatography - Mass Spectroscopy All the products obtained were characterized by GC - MS analysis using GC- MS spectrophotometer (Q Mass 910 of Perkin Elmer make). Materials used: Soybean oil was obtained from M/s Jayant Oil Mills Ltd., Mumbai Other chemical used such as zirconium oxychloride, silica, sulphuric acid, oleic acid, sodium thiosulphate, chloroform, sodium methoxide, hexane, methanol, etc were obtained from S. D. Fine chem. Ltd. EXPERIMENTAL^ 1. Catalyst preparation: Silica gel with pore volume of 0.9 ml/g was prepared by potassium hydroxide leaching of the surface and used as a support for the catalyst preparation. The particle size of the silica gel was 2-5 mm. Dry silica gel was loaded with zirconium oxide as zirconium oxychloride with various loading levels from 1 to 4% from its aqueous solution. Calculated quantity of zirconium oxychloride on the basis of weight of silica was dissolved in water (volume of water equivalent to the pore volume of silica was taken). Weighed quantity of silica was soaked in zirconium oxychloride solution for 30 min. The loaded zirconium oxychloride was precipitated as zirconium hydroxide by exposing to ammonia vapours for 2-3 hrs. in a closed vessel, dried in an oven at 120°C for 12 hrs, sulfated by using IN sulfuric acid followed by calcining at 450 °C for 4hrs.This catalyst was then washed with water to remove traces of sulfuric acid and again calcined at 450°C for 2 hrs, cooled, crushed into powder of 40 mesh size and used for the experimental part. 11 Optimization of the catalyst: In most of the reported studies the loading of the sulfated zirconia on silica is in the higher range of 15-50 %. This high loading level could be advantageous in getting higher rate in simple ammoxidation, esterification, etherification, oxidation etc. In these cases the reaction proceeds in the surface layer as well as in the interiors i.e. bulk phase, of the solid acid catalysts. But as far as other reactions being carried out at higher temperatures, it is observed that the reactions catalyzed by solid acids proceed mainly on the surface, at least in the surface layers. Experimental Details 1:1 mole ratio of butanol to acetic acid was taken in a three-neck flask fitted with a thermometer pocket with thermometer, a Dean-stark apparatus filled with butanol, a water condenser. The amount of catalyst with 1% zirconia was 5% by weight of the reactant, added in the first batch. The whole assembly was kept in a heating mantel with controller. Temperature was maintained in the range of 100-120°C.The reaction was monitored by measuring the amount of water collected in the Dean-Stark apparatus. The same procedure was repeated for the remaining catalysts with different loading levels, care was taken in maintaining the amount of zirconia in each batch constant i.e. for 2% loading exactly half quantity of catalyst was added to the first batch, for 3% one-third of the catalyst in the first batch was added and for 4% one-fourth of catalyst in the first batch was added. Simple esterification of butanol and acetic acid was carried out using 1-4% loading of sulfated zirconia on silica. Concentration of zirconia was maintained constant in all the five batches. In the first batch, 5% catalyst was used by weight of the reactant and the percentage of zirconia was maintained constant for the remaining batches with varying loading levels of zirconia in the catalyst. The results are shown In Table 1. Product butyl acetate was used as an entrainer for the co product water. The reaction was monitored by measurement of product water, which is the direct evidence of extent of reaction. This method of analysis was followed to avoid the disturbance in the reaction while sampling if analyses were to be carried out by determining acid value. On the basis of this data, the loading level of 1% was selected for the cracking reaction since atom efficiency was unaffected up to this level. 12 The present invention is further illustrated by the following examples Example 1 Cracking of oleic acid and unsaturated fatty acids 100 g of Oleic acid was heated at 280 - 300° C and any distillation activity was observed. No cracking activity was observed without a catalyst. Example 2 Cracking of oleic acid and unsaturated fatty acids Known amount (100 gms) of Oleic acid was taken in a three-neck flask fitted with a thermometer pocket with thermometer and the distillation unit. The amount of catalyst surface supported sulfated zirconia silicate catalyst was 1% by weight of the reactant with 1% zirconia loading. The whole assembly was kept in a heating mantle with controller, temperature was maintained in the range of 280-300°C. As the cracking reaction progressed, the reaction was continued till distillate was coming out from the reaction mixture. The amount of distillate coming out was measured at 30 minutes interval. Separation of products in oleic acid cracking In oleic acid cracking the complete reaction mass was distilled out and was further subjected to fractional distillation to separate both the products and these were further characterized. It was noticed that a small part of the fatty acid was always present in the olefin. This was separated by passing the product mixture on a bed of basic alumina adsorbent till the emerging product had no acid value. After the bed was saturated with carboxylic acid, the acid was recovered by passing alcoholic hydrochloride over the bed and then regenerating the bed with alcoholic caustic solution and was made available for reuse. The regenerated acid was mixed with the carboxylic after separation of alcohol. 13 Example 3 Separation of products in soybean oil cracking In the case of soyabean oil, only the olefin was removable by distillation since the fatty acid was bonded to glycerin from the other end. The distillate which also contained a small portion of fatty acids was isolated as follows: At the end of reaction that is when no further distillate came out, sodium methoxide was added to distillate to neutralize acid groups present. The solution obtained was then extracted with hexane (3 X 100 ml), the organic fractions were collected and solvent was distilled to obtain Product 1 (C8 and CIO Olefin). The aqueous extract was acidified, then again extracted with hexane (2 X 100 ml) and all the extracts were collected and solvent was distilled to obtain Product 2 (C8 and CIO acid). The acid could also be separated by treatment with alumina bed as explained earlier in cracking of oleic acid. Example 4 Alkaline hydrolysis of the product obtained in soybean oil cracking The residual product obtained in the soybean oil cracking was the acid moiety bonded with the glyceride thus making it difficult to distill out and part of it might have polymerized due to the high reaction temperature. This residue was saponified using ethanol and alcoholic potassium hydroxide for 3h. At the end of reaction, the mixture was neutralized with hydrochloric acid, diluted sufficiently with water to cause separation of fatty acids and the fatty acid layer was separated by a separating funnel. The first criterion studied was cracking reaction with and without catalyst. Here it was observed that no cracking occurred without catalyst. Some amount of distillate that came out was not olefin or acid which was expected in the cracking reaction whereas with catalyst the expected olefins and acids distilled out in relatively good yields. 14 Example 5 The second step of the study was to optimize the catalyst composition for the best performance and then establish its reusability. Various loading levels of zirconia in catalyst were studied for butanol and acetic acid esterification for optimization of the catalytic activity. Table 1 : Various loading levels of Zirconia in catalyst to study butanol and acetic acid esterification. Catalyst 1% 2% 3% 4% Loading Time (Hr.) Catalyst Catalyst Catalyst Catalyst Quantity Quantity Quantity Quantity 6.7 g 3.35 g 2.23 g 1.17g % Conversion 0.5 2.22 3.88 4.44 5.55 1 18.88 23.88 17.22 25 1.5 30.5 41.66 34.44 37.22 2 33.88 51.11 47.77 43.88 2.5 37.22 57.77 56.66 47.22 3 39.44 61.11 60.55 49.55 Various loading levels of Zirconia in catalyst to study butanol and acetic acid esterification are described in FIG 1 From the results it was seen that even departure from 2 to 3 % zirconium oxide loading on silica resulted in partial reduction of activity. This level was therefore used for studying the stability of the catalyst. 15 Reusability study: Example 6 After optimization of the catalyst the reusability of the catalyst was checked with esterification of butanol-acetic acid using a 2% Zirconia loaded catalyst. After the reaction was completed, the catalyst was separated by filtration. The catalyst was recycled to the next batch without further treatment. Additional fresh raw materials were added and further reactions were continued. The results of this reaction are given in Table No. 2. From the Table No. 2 and graphical representation of this data in Fig 2 it is observed that, there is no much difference in the results obtained, which implies the catalyst activity is consistent throughout the 5 batches, thus proving the reusability of the catalyst. TABLE 2: Catalyst reusability study in esterification of butanol Time % Conversion (hr) BATCH BATCH BATCH BATCH I II III rv 0.5 3.88 3.33 3.33 3.33 1.5 23.88 22.22 22.77 21.66 2.5 41.66 40 39.44 38.88 3.5 51.11 50.55 49.44 47.77 4.5 57.77 56.11 55.55 53.88 5.0 61.11 60.55 58.88 56.66 Results of Reusability study of the catalyst for butanol esterification is shown in FIG.2 16 Example 7 TABLE 3 : Reusability study of the catalyst for cracking of oleic acid Time AMOUNT OF DISTILLATE COLLECTED (mins) (gms) Batch Batch Batch Batch Batch I II ffl rv V 30 13.69 11.31 9.63 7.41 5.39 60 27.51 24.39 22.61 20.43 17.61 90 47.56 43.69 41.31 39.61 37.59 120 68.42 65.34 63.21 60.96 58.14 150 80.61 77.85 74.69 72.34 69.98 180 95.93 93.13 91.11 89.91 87.03 The residue after reaction was not separated from the catalyst and fresh oleic acid was added to start the next batch. Results of reusability study of the catalyst for cracking of oleic acid is indicated in FIG.3 As can be seen, there is a small loss in catalytic activity after cracking about 500 g oleic acid / g catalyst. Example 8 TABLE 4: Amount of distillate collected in reaction in 30 mins interval with soyabean oil and oleic acid. (lOOg oil or oleic acid) Time Amount of distillate collected (mins) (gms) Soybean oil Oleic acid 30 5.69 13.69 60 11.25 27.51 90 21.55 47.56 17 120 33.80 68.42 150 43.97 80.61 180 - 95.93 Further distillate was subjected to vacuum distillation where 2 fractions were obtained. 1st in the range of 125-140° C (Weight of 1st distillate; 26.79 gms) which represents 60.92 %. The 2nd distillate was in the range of 155-165° C (Weight of 2nd distillate: 15.69 gms) which represented 35.68 %. Total yield of liquid products was 96.6%. Example 9 TABLE 5: Acid value of distillate collected in reaction in 30 mins interval with soyabean oil and oleic acid. (lOOg oil or oleic acid) Time (mins) Acid value of distillate collected Soybean oil Oleic acid 30 21.85 62.49 60 44.51 100.13 90 67.15 141.84 120 85.21 158.52 150 100.62 182.62 180 - 189.25 The another criterion studied was effect of agitation. It was observed that without agitation the distillation was faster but incomplete. Some part of the reaction mass polymerizes due to high temperature applied for the reaction. Whereas when agitation was applied the rate of distillation was slower but all the reaction mass distills out completely without any polymerization. 18 Example 10 TABLE 6: Amount of distillate collected in reaction in 30 mins interval with oleic acid.(lOOg) Time (mins) amount of distillate collected Without agitation With agitation 30 13.69 7.15 60 27.51 16.57 90 47.56 27.87 120 68.42 39.91 150 80.61 58.43 180 95.93 71.41 210 - 84.21 240 _ 95.02 Material Balance for Oleic Acid Cracking Weight of starting material: 100 gms Weight of distillate : 48.93 gms Weight of residue: 47.00gms Total yield of liquid products = 95.93 % Characterization of Products GC - MS analysis was done for all the products obtained and it was found that the product obtained were 1-octene, 1-decene, 9-decenoic acid, 7-octenoic acid. The data generated by the GCMS indicates that oleic acid contained in the soyabean oil is cleanly cracked in two pieces leading to the formation of an olefin and a terminally unsaturated carboxylic acid. This can be shown by the following reaction as anticipated. 19 H3C (CH2)7 HC—CH (CH2)7 COOH Oleic acid 280 - 300°c 1%SSZ2Ctalyst H3C (CH2)T HC=CH2 H2C= HC P2) 5 COOH H3C-CH2)5—HC=CH2 + CH2=CH—(CH2)7—COOH 20 Mechanism of cracking and role of H+: Here the hydride ion generated from the acidic catalyst is added across the double bond forming a carbo cation, which on simultaneous hydride transfers and fission yields the products. The position of the carbon on which the cation is formed decides the products of cracking. The proposed mechanism agrees with the results obtained. DESCRIPTION OF ACCOMPANYING DRAWINGS Various loading levels of Zirconia in catalyst to study butanol and acetic acid esterification are described in FIG 1. X axis (1) denotes time in hours and Y axis denotes conversion. Graphs 3, 4, 5 and 6 denote % conversion of the esterification reaction using 1,2, 3 and 4 % catalyst respectively. Results of reusability study of the catalyst for butanol esterification are shown in FIG. 2. X-axis (number 7) denotes time in hours and Y axis (number 8) denotes % conversion in esterification. Graphs 9, 10, 11 and 12 denote % conversion of esterification obtained by recycling catalyst in 4 batches. Results of reusability study of the catalyst for cracking of oleic acid are indicated in FIG. 3. X-axis (13) denotes time in hours and Y- axis (14) denote amount of product distillate and collected. Graphs 15, 16, 17, 18 and 19 denote amount of distillate collected with respect to time by recycling the catalyst in four batches. While the present invention is described above in connection with preferred or illustrative embodiments, these embodiments are not intended to be exhaustive or limiting of the invention. Rather, the invention is intended to cover all alternatives, modifications and equivalents included within its spirit and scope, as defined by appended claims. 21 Claim, 1. A process for cracking of oleic acid and high oleic vegetable oils by involving hyperacidic catalysts such as surface supported sulfated zirconium silicate catalysts to produce a-olefms and terminally unsaturated carboxylic acids wherein the said process comprising (i) introducing oleic acid or / and unsaturated fatty acids such as high oleic vegetable oils such as soybean oil into a reactor; (ii) adding 1% hyperacidic catalyst such as surface supported sulfated zirconium silicate catalyst to the said reactant; (iii) heating the said reaction mixture to 280°C to 300°C till distillate comes out from the said reaction mixture; (iv) adding sodium alkali metal oxide to saponify the carboxylic acid in the said distillate; (v) adding organic solvent, hexane to the said saponified distillate to give two phase system; (vi) extracting product I, a-olefms in hexane by vigorously shaking the said two phase system; (vii) separating the organic layer, hexane from the said two phase system; (viii) collecting the said organic extracts ; (ix) distilling out hexane to isolate the product I (a-olefin); (x) acidifying aqueous phase of the said two phase system after extraction; (xi) adding the hexane to the said acidified aqueous phase to give two phase system, (xii) extracting product II, terminally unsaturated carboxylic acid in organic phase containing hexane from the said two phase system; (xiii) distilling out the hexane from the said organic phase to isolate the product II (acid); and 22 (xiv) the residue comprising terminally unsaturated carboxylic acid bonded to glycerin obtained in step iii is saponified with alcoholic potassium hydroxide, preferably in ethanol solvent, removing the alcohol by distillation and repeating the steps (x) to (xiii) described above to isolate the terminally unsaturated carboxylic acid. 2. A process for cracking of oleic acid and high oleic vegetable oils by involving hyperacidic catalysts such as surface supported sulfated zirconium silicate catalysts to produce a-olefins and terminally unsaturated carboxylic acids as substantially described herein with reference to foregoing examples 1 to 10. Dated this the 26th day of September 2003 Dr. Gopakumar G. Nair Agent for the Applicant 25 the residue comprising terminally unsaturated carboxylic acid bonded to glycerin obtained in step iii is saponified with alcoholic potassium hydroxide, preferably in ethanol solvent, removing the alcohol by distillation and repeating the steps (x) to (xiii) described above to isolate the terminally unsaturated carboxylic acid. 2. A process for cracking of oleic acid and high oleic vegetable oils by involving hyperacidic catalysts such as surface supported sulfated zirconium silicate catalysts to produce a-olefins and terminally unsaturated carboxylic acids as substantially described herein with reference to foregoing examples 1 to 10. rth Dated this the 26tn day of September 2003 25 Dr. Gopakumar G. Nair Agent for the Applicant catalyst. (Zirconium is not a noble metal; it is still expensive compared to elementary acidic materials like silica and alumina). Silica supported surfated zirconia catalyst has following benefits; 1 It is possible to tailor physical properties such as surface area, pore volume, bulk density and particle size conveniently. 2 It is resistant to acids such as sulfuric acid, which are involved in next step of preparation. 3 It forms covalent bond with group IV elements such as Ti, Zr, and Hf, hydroxides through the surface silanol groups that might be helpful in retaining the catalytic activity. 4 It is the most abundant element and is very inexpensive, has no disposal or toxicity problem. 5 In pure state, it is colorless. Not many other industrial supports such as activated carbon, activated alumina or activated clay could offer these benefits. We noticed that there is no published study on the use of supported sulfated zirconia for the cracking of vegetable oils. In this work we are reporting preliminary findings of the catalytic cleaving of oleic acid or vegetable oils rich in mono unsaturated acids. Soyabean oil is one of the cheapest vegetable oils in the tropical regions and would form a good feed stock for chemical products. SUMMARY OF INVENTION A process for cracking of oleic acid and high oleic vegetable oils by involving hyperacidic catalysts such as surface supported sulfated zirconium silicate catalysts to produce a-olefins and terminally unsaturated carboxylic acids wherein the said process comprising (i) introducing oleic acid or / and unsaturated fatty acids such as high oleic vegetable oils such as soybean oil into a reactor; (ii) adding 1% hyperacidic catalyst such as surface supported sulfated zirconium silicate catalyst to the said reactant; (iii) heating the said reaction mixture to 280HC to 300°C till distillate comes out from the said reaction mixture; 8 (iv) adding sodium alkali metal alkoxide; preferably sodium methoxide to saponify the carboxylic acid in the said distillate; (v) adding organic solvent, hexane to the said saponified distillate to give two phase system; (vi) extracting product I, a-olefins in hexane by vigorously shaking the said two phase system; (vii) separating the organic layer, hexane from the said two phase system; (viii) collecting the said organic extracts ; (ix) distilling out hexane to isolate the product I (a-olefin) i.e.C8 and CIO a -Olefin; (x) acidifying aqueous phase of the said two phase system after extraction; (xi) adding the hexane to the said acidified aqueous phase to give two phase system, (xii) extracting product II, C8 and CIO terminally unsaturated carboxylic acid in organic phase containing hexane from the said two phase system; (xiii) distilling out the hexane from the said organic phase to isolate the product II (acid) ; and (xiv) the residue comprising terminally unsaturated carboxylic acid bonded to glycerin obtained in step iii is saponified with alcoholic potassium hydroxide, preferably in ethanol solvent, removing the alcohol by distillation and repeating the steps (x) to (xiii) described above to isolate the terminally unsaturated carboxylic acid. DETAILED DESCRIPTION OF THE INVENTION A process for cracking oleic acid and high oleic vegetable oils by involving hyper acidic catalyst that offers quantitative and reproducible yield is disclosed. More specifically catalyst used in this process of cracking of Oleic acid and high oleic vegetable oils to produce a-olefines and terminally unsaturated carboxylic acid is surface supported Sulphated Zirconium Silicate catalyst. The process for the synthesis of the said catalyst is disclosed in our application number 1018/MUM/2003. 9 catalyst. (Zirconium is not a noble metal; it is still expensive compared to elementary acidic materials like silica and alumina). Silica supported surfated zirconia catalyst has following benefits; 1 It is possible to tailor physical properties such as surface area, pore volume, bulk density and particle size conveniently. 2 It is resistant to acids such as sulfuric acid, which are involved in next step of preparation, 3 It forms covalent bond with group IV elements such as Ti, Zr, and Hf, hydroxides through the surface silanol groups that might be helpful in retaining the catalytic activity. 4 It is the most abundant element and is very inexpensive, has no disposal or toxicity problem. 5 In pure state, it is colorless. Not many other industrial supports such as activated carbon, activated alumina or activated clay could offer these benefits. We noticed that there is no published study on the use of supported sulfated zirconia for the cracking of vegetable oils. In this work we are reporting preliminary findings of the catalytic cleaving of oleic acid or vegetable oils rich in mono unsaturated acids. Soyabean oil is one of the cheapest vegetable oils in the tropical regions and would form a good feed stock for chemical products. SUMMARY OF INVENTION A process for cracking oleic acid and high oleic vegetable oils by involving hyper acidic catalyst that offers quantitative and reproducible yield is disclosed in this invention. 8 More specifically a process of cracking of Oleic acid and high oleic vegetable oils to produce a-olefines and terminally unsaturated carboxylic acid by use of surface supported Sulphated Zirconium Silicate catalyst is dislcosed. DETAILED DESCRIPTION OF THE INVENTION A process for cracking oleic acid and high oleic vegetable oils by involving hyper acidic catalyst that offers quantitative and reproducible yield is disclosed. More specifically catalyst used in this process of cracking of Oleic acid and high oleic vegetable oils to produce a-olefines' and terminally unsaturated carboxylic acid is surface supported Sulphated Zirconium Silicate catalyst. The process for the synthesis of the said catalyst is disclosed in our application number 1018/MXJM/2003. Methods for Analysis Employed Chemical Method 1) Acid value (ASTM 1639-70) About 0.5-1 gm of the sample was accurately weighed in the conical flask. 25 ml of neutral alcohol was added to dissolve the sample. 3-4 drops of 1% phenolphthalein solution (in ethanol) was added. The mixture in the conical flask was titrated against 0.1N alcoholic potassium hydroxide solution. Acid value was calculated as follows: Acid Value 56.1 X normality of KOH X ml of KOH Weight of the sample in grams Acid number is expressed as milligrams of KOH per gram of sample 9 2) Iodine number (method of American oil chemists society) About 1 gm of sample was weighed in a 250ml quick fit conical flask and was dissolved in carbon tetrachloride. 25 ml of Wij's solution was added to it with constant stirring. The solution was kept in dark for 30 mins. 10 ml of 10% KI was then added and the liberated iodine was titrated against Na2SO3 using starch indicator. A blank reading was carried out simultaneously. The saponification number was calculated using following formula: 56.1 X normality of Na2SO3X(B-S) Iodine Number =- Weight of the sample in grams B = ml of Na2S03 of required for blank S= ml of Na2SC3 required for sample Iodine number is expressed as grams of Iodine per 100 gram of sample Instrumental Methods: 1. Gas Chromatography - Mass Spectroscopy All the products obtained were characterized by GC - MS analysis using GC- MS spectrophotometer (Q Mass 910 of Perkin Elmer make). Materials used: Soybean oil was obtained from M/s Jayant Oil Mills Ltd., Mumbai Other chemical used such as zirconium oxychloride, silica, sulphuric acid, oleic acid, sodium thiosulphate, chloroform, sodium methoxide, hexane, methanol, etc were obtained from S. D. Fine chem. Ltd. 10 EXPERIMENTALS 1. Catalyst preparation: Silica gel with pore volume of 0.9 ml/g was prepared by potassium hydroxide leaching of the surface and used as a support for the catalyst preparation. The particle size of the silica gel was 2-5 mm- Dry silica gel was loaded with zirconium oxide as zirconium oxychloride with various loading levels from 1 to 4% from its aqueous solution. Calculated quantity of zirconium oxychloride on the basis of weight of silica was. disssoled in water (volume of water equivalennt to the pore volume OF sillcat was taken). Weighed quantity of silica was soaked in zirconium oxychloride solution for 30 min. The loaded zirconium oxychloride was precipitated as zirconium hydroxide by exposing to ammonia vapours for 2-3 hrs. in a closed vessel, dried in an oven at 120°C for 12 hrs, sulfated by using IN sulfuric acid followed by calcining at 450 °C for 4hrs.This catalyst was then washed with water to remove traces of sulfuric acid and again calcined at 450°C for 1 hrs, cooled, crushed into powder of 40 mesh size and used for the experimental part. Optimization of the catalyst: In most of the reported studies the loading of the sulfated zirconia on silica is in the higher range of 15-50 %. This high loading level could be advantageous in getting higher rate in simple ammoxidation, esterification, etherification, oxidation etc. In these cases the reaction proceeds in the surface layer as well as in the interiors i.e. bulk phase, of the solid acid catalysts. But as far as other reactions being carried out at higher temperatures, it is observed that the reactions catalyzed by solid acids proceed mainly on the surface, at least in the surface layers. Experimental Details 1:1 mole ratio of butanol to acetic acid was taken in a three-neck flask fitted with a thermometer pocket with thermometer, a Dean-stark apparatus filled with butanol, a water condenser. The amount of catalyst with 1% zirconia was 5% by weight of the reactant, added in the first batch. The whole assembly was kept in a heating mantel with controller. Temperature was maintained in the range of 100-120 C.The reaction was monitored by measuring the amount of water collected in the Dean-Stark 11 apparatus. The same procedure was repeated for the remaining catalysts with different loading levels, care was taken in maintaining the amount of zirconia in each batch constant i.e. for 2% loading exactly half quantity of catalyst was added to the first batch, for 3% one-third of the catalyst in the first batch was added and for 4% one-fourth of catalyst in the first batch was added. Simple esterification of butanol and acetic acid was carried out using 1-4% loading of sulfated zirconia on silica. Concentration of zirconia was maintained constant in all the five batches. In the first batch, 5% catalyst was used by weight of the reactant and the percentage of zirconia was maintained constant for the remaining batches with varying loading levels of zirconia in the catalyst. The results are shown In Table 1. Product butyl acetate was used as an entrainer for the co product water. The reaction was monitored by measurement of product water, which is the direct evidence of extent of reaction. This method of analysis was followed to avoid the disturbance in the reaction while sampling if analyses were to be carried out by determining acid value. On the basis of this data, the loading level of 1% was selected for the cracking reaction since atom efficiency was unaffected up to this level. The present invention is further illustrated by the following examples Example 1 Cracking of oleic acid and unsaturated fatty acids 100 g of Oleic acid was heated at 280 - 300° C and any distillation activity was observed. No cracking activity was observed without a catalyst. Example 2 Cracking of oleic acid and unsaturated fatty acids Known amount (100 gms) of Oleic acid was taken in a three-neck flask fitted with a thermometer pocket with thermometer and the distillation unit. The amount of catalyst surface supported sulfated zirconia silicate catalyst was 1% by weight of the reactant with 1% zirconia loading. The whole assembly was kept in a heating mantle with 12 controller, temperature was maintained in the range of 280-300°C. As the cracking reaction progressed, the reaction was continued till distillate was coming out from the reaction mixture. The amount of distillate coming out was measured at 30 minutes interval. Separation of products in oleic acid cracking In oleic acid cracking the complete reaction mass was distilled out and was further subjected to fractional distillation to separate both the products and these were further characterized. It was noticed that a small part of the fatty acid was always present in the olefin. This was separated by passing the product mixture on a bed of basic alumina adsorbent till the emerging product had no acid value. After the bed was saturated with carboxylic acid, the acid was recovered by passing alcoholic hydrochloride over the bed and then regenerating the bed with alcoholic caustic solution and was made available for reuse. The regenerated acid was mixed with the carboxylic after separation of alcohol. Example 3 Separation of products in soybean oil cracking In the case of soyabean oil, only the olefin was removable by distillation since the fatty acid was bonded to glycerin from the other end. The distillate which also contained a small portion of fatty acids was isolated as follows: At the end of reaction that is when no further distillate came out, sodium methoxide was added, to distillate to neutralize acid groups present. The solution obtained was then extracted with hexane (3 X 100 ml), the organic fractions were collected and solvent was distilled to obtain Product 1 (C8 and CIO Olefin). The aqueous extract was acidified, then again extracted with hexane (2 X 100 ml) and all the extracts were collected and solvent was distilled to obtain Product 2 (C8 and C10 acid). The acid could also be separated by treatment with alumina bed as explained earlier in cracking of oleic acid. 13 Example 4 Alkaline hydrolysis of the product obtained in soybean oil cracking The residual product obtained in the soybean oil cracking was the acid moiety bonded with the glyceride thus making it difficult to distill out and part of it might have polymerized due to the high reaction temperature. This residue was saponified using ethanol and alcoholic potassium hydroxide for 3h At the end of reaction, the mixture was neutralized with hydrochloric acid, diluted sufficiently with water to cause separation of fatty acids and the fatty acid layer was separated by a separating funnel. The first criterion studied was cracking reaction with and without catalyst. Here it was observed that no cracking occurred without catalyst. Some amount of distillate that came out was not olefin or acid which was expected in the cracking reaction whereas with catalyst the expected olefins and acids distilled out in relatively good yields. Example 5 The second step of the study was to optimize the catalyst composition for the best performance and then establish its reusability. Various loading levels of zirconia in catalyst were studied for butanol and acetic acid esterification for optimization of the catalytic activity. Table 1 : Various loading levels of Zirconia in catalyst to study butanol and acetic acid esterification. Catalyst 1% 2% 3% 4% Loading Time (Hr.) Catalyst Catalyst Catalyst Catalyst Quantity Quantity Quantity Quantity 6.7 g 3.35 g 2.23 g l-17g % Conversion 0.5 2.22 3.88 4.44 5.55 1 18.88 23.88 17.22 25 1.5 30.5 41.66 34.44 37.22 2 33.88 51.11 47.77 43.88 2.5 37.22 57.77 56.66 47.22 3 39.44 61.11 60.55 49.55 14 Various loading levels of Zirconia in catalyst to study butanol and acetic acid esterification are described in FIG 1 From the results it was seen that even departure from 2 to 3 % zirconium oxide loading on silica resulted in partial reduction of activity. This level was therefore used for studying the stability of the catalyst. Reusability study: Example 6 After optimization of the catalyst the reusability of the catalyst was checked with esterification of butanol-acetic acid using a 2% Zirconia loaded catalyst. After the reaction was completed, the catalyst was separated by filtration. The catalyst was recycled to the next batch without further treatment. Additional fresh raw materials were added and further reactions were continued. The results of this reaction are given in Table No. 2. From the Table No. 2 and graphical representation of this data in Fig 2 it is observed that, there is no much difference in the results obtained, which implies the catalyst activity is consistent throughout the 5 batches, thus proving the reusability of the catalyst. TABLE 2: Catalyst reusability study in esterification of butanol Time % Conversion (hr) BATCH BATCH BATCH BATCH I II HI rv 0.5 3.88 3.33 3.33 3.33 1.5 23.88 22.22 22.77 21.66 2.5 41.66 40 39.44 38.88 3.5 sun 50.55 49.44 47.77 4.5 57.77 56.11 55.55 53.88 5.0 61.11 60.55 58.88 56.66 15 Results of Reusability study of the catalyst for butanol esterification is shown in FIG.2 Example 7 TABLE 3 : Reusability study of the catalyst for cracking of oleic acid Time AMOUNT OF DISTILLATE COLLECTED (mins) (gms) Batch Batch Batch Batch Batch I II III IV V 30 13.69 11.31 9.63 7.41 5.39 60 27.51 24.39 22.61 20.43 17.61 90 47.56 43.69 41.31 39.61 37.59 120 68.42 65.34 63.21 60.96 58.14 150 80.61 77.85 74.69 72.34 69.98 180 95.93 93.13 91.11 89.91 87.03 The residue after reaction was not separated from the catalyst and fresh oleic acid was added to start the next batch. Results of reusability study of the catalyst for cracking of oleic acid is indicated in FIG.3 As can be seen, there is a small loss in catalytic activity after cracking about 500 g oleic acid / g catalyst. Example S TABLE 4: Amount of distillate collected in reaction in 30 mins interval with soyabean oil and oleic acid. (lOOg oil or oleic acid) Time Amount of distillate collected (mins) (gms) Soybean oil Oleic acid 30 5.69 13.69 16 60 11.25 27.51 90 21.55 47.56 120 33.80 68.42 150 43.97 80.61 180 - 95.93 Further distillate was subjected to vacuum distillation where 2 fractions were obtained. 1st in the range of 125-140° C (Weight of 1st distillate: 26.79 gms) which represents 60.92 %. The 2nd distillate was in the range of 155-165° C (Weight of 2nd distillate: 15.69 gms) which represented 35.68 %. Total yield of liquid products was 96.6%. Example 9 TABLE 5: Acid value of distillate collected in reaction in 30 mins interval with soyabean oil and oleic acid. (lOOg oil or oleic acid) Time (mins) Acid value of distillate collected Soybean oil Oleic acid 30 21.85 62.49 60 44.51 100.13 90 67.15 141.84 120 85.21 158.52 150 100.62 182.62 180 - 189.25 The another criterion studied was effect of agitation. It was observed that without agitation the distillation was faster but incomplete. Some part of the reaction mass polymerizes due to high temperature applied for the reaction. Whereas when agitation was applied the rate of distillation was slower but all the reaction mass distills out completely without any polymerization. 17 Example 10 TABLE 6: Amount of distillate collected in reaction in 30 mins interval with oleic acid. (lOOg) Time (mins) amount of distillate collected Without agitation With agitation 30 13.69 7.15 60 27.51 16.57 90 47.56 27.87 120 68.42 39.91 150 80.61 58.43 180 95.93 71.41 210 - 84.21 240 - 95.02 Material Balance for Oleic Acid Cracking Weight of starting material: 100 gms Weight of distillate : 48.93 gms Weight of residue: 47.00gms Total yield of liquid products = 95.93% Characterization of Products GC - MS analysis was done for all the products obtained and it was found that the product obtained were 1-octene, 1-decene, 9-decenoic acid, 7-octenoic acid. The data generated by the GCMS indicates that oleic acid contained in the soyabean oil is cleanly cracked in two pieces leading to the formation of an olefin and a terminally unsaturated carboxylic acid. This can be shown by the following reaction as anticipated. 18 Oleic acid 280 - 300°c 1%SSZ2 Ctalyst Y ' Mechanism of cracking and role of H: 19 Here the hydride ion generated from the acidic catalyst is added across the double bond forming a carbo cation, which on simultaneous hydride transfers and fission yields the products. The position of the carbon on which the cation is formed decides the products of cracking. The proposed mechanism agrees with the results obtained. DESCRIPTION OF ACCOMPANYING Various loading levels of Zirconia in catalyst to study butanol and acetic acid esterification are described in FIG 1. X axis (1) denotes time in hours and Y axis denotes conversion. Graphs 3, 4, 5 and 6 denote % conversion of the esterification reaction using 1, 2, 3 and 4 % catalyst respectively. Results of reusability study of the catalyst for butanol esterification are shown in FIG. 2. X-axis (number 7) denotes time in hours and Y axis (number 8) denotes % conversion in esterification. Graphs 9, 10, 11 and 12 denote % conversion of esterification obtained by recycling catalyst in 4 batches. Results of reusability study of the catalyst for cracking of oleic acid are indicated in FIG. 3. X-axis (13) denotes time in hours and Y- axis (14) denote amount of product distillate and collected. Graphs 15, 16, 17, 18 and 19 denote amount of distillate collected with respect to time by recycling the catalyst in four batches. While the present invention is described above in connection with preferred or illustrative embodiments, these embodiments are not intended to be exhaustive or limiting of the invention. Rather, the invention is intended to cover all alternatives, modifications and equivalents included within its spirit and scope, as defined by appended claims. 20 Claim, 1. A process for cracking of oleic acid and high oleic vegetable oils by involving hyperacidic catalysts such as surface supported sulfated zirconium silicate catalysts to produce a-olefins and terminally unsaturated carboxylic acids wherein the said process comprising of (i) introducing oleic acid or / and unsaturated fatty acids such as high oleic vegetable oils such as soybean oil into a reactor; (ii) adding 1% hyperacidic catalyst such as surface supported sulfated zirconium silicate catalyst to the said reactant; (iii) heating the said reaction mixture to 280"C to 300°C till f$ distillate ——.,^,x.„, comes out from the said reaction mixture; ' (iv) adding sodium alkali metal oxide to saponify the carboxylic acid in the said distillate; (v) adding organic solvent, hexane to the said saponified distillate to give two phase system; (vi) extracting product I, a-olefins in hexane by vigorously shaking the said two phase system; (vii) separating the organic layer, hexane from the said two phase system; (viii) collecting the said organic extracts ; (ix) distilling out hexane to isolate the product I (a-olefin) ; (x) acidifying aqueous phase of the said two phase system after extraction; (xi) adding the hexane to the said acidified aqueous phase to give two phase system, (xii) extracting product II, terminally unsaturated carboxylic acid in organic phase containing hexane from the said two phase system; (xiii) distilling out the hexane from the said organic phase to isolate the product II (acid); and (xiv) the residue comprising terminally unsaturated carboxylic acid bonded to glycerin obtained in step iii is saponified with sodium hydroxide, preferably in alcohol solvent, removing the alcohol by distillation and g 21 repeating the steps (x) to (xiii) described above to isolate the terminally unsaturated carboxylic acid. 2) A process for cracking of oleic acid and high oleic vegetable oils by involving hyperacidic catalysts such as surface supported sulfated zirconium silicate catalysts to produce a-olefins and terminally unsaturated carboxylic acids as claimed in claim 1 wherein alkali metal oxide used in saponification is not acid, diluted sufficiently with water to cause separation of fatty acids and the fatty acid layer, separated by a separating funnel. 22 hyperacidic catalysts such as surface supported sulfated zirconium silicate catalysts to produce a-olefins and terminally unsaturated carboxylic acids as substantially described herein with reference to the foregoing example 1 to 10. Dated this the 26th day of Sept 2003 44 To The Controller of Patents The Patent Office, At Mumbai. 23 Dr. Gopakumar G. Nair Agent for the Applicant Gopakumar Nair Associates Nair Baug, Akurli Road, Kandivli (East), Mumbai - 400 101

Full Text

FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
COMPLETE SPECIFICATION
[See section 10; rule 13]
"A PROCESS FOR CRACKING OF OLEIC ACD3 AND fflGH OLEIC VEGETABLE OILS BY INVOLVING HYPERACIDIC CATALYSTS"
(a) MALSHE VINOD CHINTAMANI
(b) 1, Staff Quarters, UDCT Campus, Matunga Mumbai - 400 019. India
(c) Indian National
The following specification describes the nature of this invention and the manner in which it is to be performed:

Related Application
Related application for patent: Related application for "surface supported sulphated zirconium silicate catalyst" with application no. 1018/MUM/2003 is disclosed and reported herein.
TECHNICAL FIELD
This invention related to a process for cracking oleic acid and high oleic vegetable oils by involving hyper acidic catalyst which is surface supported sulfated zirconium silicates that offers quantitative and reproducible yield.
BACKGROUND AND PRIOR ART
Renewable raw materials are organic materials from vegetable or animal sources, which can be used in part or as whole as raw materials for industry or as energy carriers. Unlike fossil raw materials they are renewed annually. For many centuries various fats, oils and waxes have served as source of fuel, light, food, soap and other basic materials necessary for life. The availability of petroleum is gradually -decreasing, so to solve this problem renewable raw materials provide good alternatives.
Vegetable oils are becoming very popular for a wide variety of technical and chemical uses (Battersby et al; Chemosphere; 24; 1989-2000 (1992), Mc Ketta Encyclopedia of Unit Processes Vol 6, 401-420), as they have facile chemical structure and inexpensive production methods. The major components of vegetable oil are triglycerides containing different aliphatic chains which may be saturated or unsaturated, and the degree of unsaturation varies providing excellent sites for reactions. Currently they are used for wide range of applications like production of
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cosmetics, pharmaceutical products, leather care products, paints, varnishes, emulsifiers, plasticizers, surfactants, plastics, solvents and resins.
Uses of vegetable oils have grown during the past years because they are inherently biodegradable, having low ecotoxicity and low toxicity towards humans, are derived from renewable resources and do not contribute volatile organic chemicals (VOC) and hence are essential components of green chemistry.
The various uses of alkenes have grown over last few years. They are an essential feed stock for the manufacture of linear low-density poly ethylene (LLDPE), oxo alcohols, solvent soluble colours, lubricants, packaging materials for foods, textiles, adhesives, sealants, wire and cable insulators, manufacture of automotive parts and detergent alkylates as described in Ullman's Encyclopedia of Chemical Technologies Vol 5, p-704. All of these represent a significant volume business with sizable value addition. The demand cannot be completely fulfilled as they can be obtained only from the petroleum products i.e. alkanes. The conventional methods to synthesize alkenes completely depend on the availability of the raw materials which are non renewable and hence there is a need to look for alternatives as alkenes are widely used in chemical industries for various reasons.
Olefin metathesis is an important catalytic reaction in organic synthesis, in which olefin are converted into new products via the rupture and reformation of carbon -carbon double bonds. Unsaturated fatty acid esters and oils are very promising renewable and cheap sources for metathesis which makes the metathesis reaction of interest to the chemical industry by offering novel routes to new and existing procedures. This reaction is a unique combination of part natural and part mineral product to produce alkenes of different molecular weight.
Nylon 9 is prepared by a laborious route as described in Ullmann's Encyclopedia of Industrial Chemistry volume A 10, p- 567 to 655 starting from ozonide of oleic acid, which is first converted, in a linear Cg aldehyde with a terminal carboxylic acid group. The aldehyde is converted to an amino group by reductive amination using ammonia and a reducing catalyst. Even though a clean reaction, ozonolysis is an expensive
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proposal for production of bulk chemicals and cheaper alternatives must be sought. The synthesis of Nylon 11 is based on a five-step process from castor oil to 11-amino undecanoic acid with very poor yield. Besides, the highly volatile price of castor oil has constantly discouraged new entrants in this business. The anti Morkonikov addition of hydrogen bromide on the terminal double bond of undecylenic acid is probably another complication, which is a closely guarded secret and is equally crucial •for the correct quality of Nylon 11 monomer. A 30-40% aqueous dispersion of the acid can be polycondensed in 3-steps and Nylon His formed. This polymer is too expensive for general use and its use is restricted to a few special applications in luggage, ropes, transmission belts, sports goods, gears, coatings for special applications and brush bristles.
No technical report could be found on catalytic cracking of oleic acid and oleic acid rich vegetable oils in published or patent literature. We considered the possibility of a selective cleavage of oleic acid at the 9-10 double bond of oleic acid by acidic catalyst anticipating the following sequence of reactions.
H3C (CH2)7 HC—CH (CH2)7 C00H
Oleic acid

f 1
H3C (CH2)T HC=— CH2 H3C (CH2)5 HC=CH2
+ +
H2C= HC (CH2) 5 C00H H2C=HC P2)7 C00H
Due to the possibility of formation of the carbo cation on either side of the double bond with equal ease, four products were expected. Of these, the two olefins would be easily separated. Due to the difference in their carbon number and similarly the two terminally unsaturated carboxylic acids are amenable to separation and at least three
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reactions (carbonylation, hydroformylation followed by animation or oxidation) and would be potential source of monomers for Nylon 9 and Nylon 11. These possibilities are in addition to the usual hydrogen bromide addition and amination to form amino acids. Properties of Nylon 9 and Nylon 11 are fairly similar and these could be considered as bulk plastics of the future. Only high cost separates them from their volume usage.
Highly acidic catalysts are known to cleave carbon-carbon bond at high temperatures, silica alumina being the most well known to crack the hydrocarbons. Using silica alumina necessitates a high temperature 550° C at which the selectivity of the reaction would be very low since most of the products would be low molecular weight olefins.
Use of sulphated zirconia as a catalyst has been reported by Yadav and Nair in "Microporous and Mesoporous materials" (1999) 33, 148. Sulfated zirconia has been described as the most promising and emerging catalyst for the times to come. In that paper the zirconia or zirconium oxide catalyst was prepared with modified anion such as sulfate ions form highly acidic catalyst depending upon the method of treatment. The characterization and various parameters affecting catalyst preparation were also studied. These prepared catalysts were examined for their reactivity and reusability for various model reactions such as hydrocarbon isomerisation, alkylation, acylation, esterification, etherification, condensation, nitration, cyclisation, cracking, and various other reactions where acidic catalysts are used. The results obtained from these catalysts were compared with conventional catalyst and comparative conclusions were derived confirming the better activity of sulfated zirconia catalysts.
Until 1999 only sulfated zirconia was extensively studied. The concept of supported sulfated zirconia has emerged only in the new millennium. In the last three years, Sulfated zirconia was supported on various supports which were not reported earlier. Various methods of preparations were reported since then. In one of the methods alumina promoted sulfated zirconia was supported on mesoporous molecular sieves of pure silica MCM-41 and SB A -15. The catalyst was prepared by direct impregnation of metal oxide onto the silica surface, followed by solid state dispersion and thermal decomposition. Chen et al (Chen et al, Catalysis Letters (2002), 78 (1-4), 223-229)
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reported the supported sulfated zirconia by direct exchange of metal containing precursor for the surfactants in the synthesized MCM-41 material. Wang S., Guin J.A. (Microporous and Mesoporous Meterials (2001), 50 (2-3), 201-208) reported the preparation of supported sulfated zirconia catalyst by precipitation of Zr (NO3) 2 with NH3 at pHIO and further calcination at 600°C. The reactivity was enhanced by 30 -50 % compared with acid resin Amberlyst 15 in etherification reaction (Chemical communication (2000), (24), 2499-2500). Lei, T; Xu et al. (Lei et al, Applied catalysis A (2000), 181-188) was prepared catalyst [(S04)2 - Zr02] (SZ) supported on A1203 or Si02 by impregnation method. This catalyst was used for isomerisation reaction of n -butane. Huan, yin- yan et al. (Haun, et al, Applied catalysis (1998), 173, (1), 27-35) reported silica or alumina supported sulfated zirconia prepared by dispersion followed by calcinations at 750° C. Another supported catalyst was modified by Grau , Javier Mario et al by the addition of Pt over various pure and heterogeneous supported sulfated zirconia like (i) pure (SO4 - Zr02 (ii) Mechanically mixed (SO4) - Zr02 with A12O3 or Si02 and (iii) (SC»4)2 - Zr02 supported over Al203 or Si02 and comparative studies of their reactivity was done where it was seen that (SO4)- Zr02 supported over AI2O3 or S1O2 and Pt/ Si02/ (SO4)2 - Zr02 was the most stable and reactive catalyst (Grau et al, Applied Catalysis, A (1998), 172(2), 311-326). In another study the supported sulfated zirconia catalyst had been prepared by Anderson et. al (Can. J. Phys. Chem. (1995), 99(3), 1444-1449) for the oxidation of S02 or by impregnation with sulfuric acid and its surface properties and acidity have been characterized by IR spectroscopy. Another ecofriendly catalyst having sulfated metal oxide and mesoporous zeolites was prepared by Yadav, G. D. et al in GB 2332155 (1999) who used it for producing oligomers from a- olefins, Fridel - craft's alkylation and acylation reaction. In another work by Yadav, G.D. et al. the reported in Green Chem (1999) Dec, (269-274) the catalyst was prepared by precipitating zirconia on calcined HMS and further treated with NH3 and was calcined at 550°C. This catalyst was used for alkylation of p-cresol with MTBE where major product was obtained with highest yield and conversion when compared to other conventional catalysts.
The reactivity of this catalyst has been studied for isobutene alkylation by butane by Paukshtis, E. A. et al. in 2002, as reported in studies in surface science and catalysis (2002), 130c. It was seen that it has better catalytic activity and shape selectivity when
6

compared to conventional acidic catalyst like AICI3 and BF3. The performance of Pt catalyst supported on sulfated zirconia-silica with different stoichiometries was investigated by Salmones, J. in n-pentane hydromerization reaction with enhancement in catalytic activity (Catal. Lett.; (1996) 36(3,4), 135-138). In another study by Inada, K et al in Chem. Lett.; (1993), 10, 1795-1798, silica supported sulfated zirconia catalyst was used for reduction of aldehydes and ketones with 2- propanol, corresponding alcohols were obtained in high yields. In the catalyst silica supported sulfated zirconia the results obtained agreed with the models proposed by De Jong et al in Surface Interface Anal. (1992), 18(6), 412 - 416 for sulfated zirconia catalyst on porous silica supports.
Sulfated zirconia is known for high surface acidity. In spite of these products being known for about 20 years and their extensive capability to substitute homogeneous acid catalyst, no commercial product seems to have emerged. In a lecture delivered at UDCT in 1999 on sulfated zirconia catalyst, Dr. Francis Figueres commented that the problem of reproducibility in preparation of sulfated zirconia is so great that every time one made a catalyst, it was a new catalyst. This comment led us to the thinking and the development of surface sulfated zirconium silicate catalyst being reported here.
Most of the reported synthesis starts from zirconium oxychloride precipitation as hydroxide followed by calcinations, sulfation with sulfuric acid or ammonium sulfate, then calcination to fix the acid sites and surface area. The attempt to fix surface area and acid sites simultaneously causes problem of variation in surface area, pore volume and pore size distribution, which is a well-known phenomenon in hydrous oxides. Secondly if a bulk of zirconium oxide is used up in preparing the massive matrix, it cannot contribute to the activity of the catalyst.
Wang et al in Chem. Commun, (2000), 2499-1500 have reported preparation of silica supported sulfated zirconia and studied the conversion of methanol and isobutylene to MTBE. They have studied loading from 15 to 50 % and found a loading of 50% to give best performance. The authors have not considered the atom efficiency of the
7

1019 MUM)2003)
catalyst. (Zirconium is not a noble metal; it is still expensive compared to elementary acidic materials like silica and alumina). Silica supported surfated zirconia catalyst has following benefits;
1 It is possible to tailor physical properties such as surface area, pore volume, bulk density and particle size conveniently.
2 It is resistant to acids such as sulfuric acid, which are involved in next step of preparation. , .."
3 It forms covalent bond with group IV elements such as Ti, Zr, and Hf, hydroxides through the surface silanol groups that might be helpful in retaining the catalytic activity.
4 It is the most abundant element and is very inexpensive, has no disposal or toxicity problem. r-:"
5 In pure state, it is colorless.
Not many other industrial supports such as activated carbon, activated alumina or activated clay could offer these benefits. We noticed that there is no published study on the use of supported sulfated zirconia for the cracking of vegetable oils. In this work we are reporting preliminary findings of the catalytic cleaving of oleic acid or vegetable oils rich in mono unsaturated acids. Soyabean oil is one of the cheapest vegetable oils in the tropical regions and would form a good feed stock for chemical products.
SUMMARY OF INVENTION
A process for cracking of oleic acid and high oleic vegetable oils by involving hyperacidic catalysts such as surface supported sulfated zirconium silicate catalysts to produce a-olefins and terminally unsaturated carboxylic acids wherein the said process comprising
(i) introducing oleic acid or / and unsaturated fatty acids such as high oleic
vegetable oils such as soybean oil into a reactor; (ii) adding 1% hyperacidic catalyst such: as surface supported sulfated
zirconium silicate catalyst to the said reactant; (iii) heating the said reaction mixture to 280°C to 300°C till distillate comes out from the said reaction mixture;
8

(iv) adding sodium alkali metal alkoxide; preferably sodium methoxide to saponify the carboxylic acid in the said distillate;
(v) adding organic solvent, hexane to the said saponified distillate to give two phase system;
(vi) extracting product I, a-olefins in hexafie" by vigorously shaking the said two phase system;
(vii) separating the organic layer, hexane from the said two phase system;
(viii) collecting the said organic extracts ;
(ix) distilling out hexane to isolate the product I (a-olefin) i.e.C8 and CIO a -Olefin;
(x) acidifying aqueous phase of the said two phase system after extraction;
(xi) adding the hexane to the said acidified aqueous phase to give two phase system,
(xii) extracting product II, C8 and CIO terminally unsaturated carboxylic acid in organic phase containing hexane from the said two phase system;
(xiii) distilling out the hexane from the said organic phase to isolate the product II (acid) ; and (xiv) the residue comprising terminally unsaturated carboxylic acid bonded to glycerin obtained in step iii is saponified with alcoholic potassium hydroxide, preferably in ethanol solvent, removing the alcohol by distillation and repeating the steps (x) to (xiii) described above to isolate the terminally unsaturated carboxylic acid.
DETAILED DESCRIPTION OF THE INVENTION
A process for cracking oleic acid and high oleic vegetable oils by involving hyper acidic catalyst that offers quantitative and reproducible yield is disclosed. More specifically catalyst used in this process of cracking of Oleic aciddand high oleic vegetable oils to produce a-olefines and terminally unsaturated carboxylic acid is surface supported Sulphated Zirconium Silicate catalyst.
The process for the synthesis of the said catalyst is disclosed in our application number 1018/MUM/2003.
9

Methods for Analysis Employed
Chemical Method
1) Acid value (ASTM 1639-70)
About 0.5-1 gm of the sample was accurately weighed in the conical flask. 25 ml of neutral alcohol was added to dissolve the sample. 3-4 drops of 1% phenolphthalein solution (in ethanol) was added. The mixture in the conical flask was titrated against 0.1N alcoholic potassium hydroxide solution. Acid value was calculated as follows:
A.JWI 56.1 X normality of KOH X ml of KOH
Weight of the sample in grams
Acid number is expressed as milligrams of KOH per gram of sample
2) Iodine number (method of American oil chemists society)
About 1 gm of sample was weighed in a 250ml quick fit conical flask and was dissolved in carbon tetrachloride. 25 ml of Wij's solution was added to it with constant stirring. The solution was kept in dark for 30 mins. 10 ml of 10% KI was then added and the liberated iodine was titrated against Na2SC>3 using starch indicator. A blank reading was carried out simultaneously. The saponification number was calculated using following formula:
56.1 X normality of Na2S03X(B-S)
Iodine Number = —-—-
Weight of the sample in grams
B = ml of Na2S03 of required for blank S= ml of Na2S03 required for sample
Iodine number is expressed as grams of Iodine per 100 gram of sample
10

Instrumental Methods:
1. Gas Chromatography - Mass Spectroscopy
All the products obtained were characterized by GC - MS analysis using GC- MS spectrophotometer (Q Mass 910 of Perkin Elmer make).
Materials used:
Soybean oil was obtained from M/s Jayant Oil Mills Ltd., Mumbai Other chemical used such as zirconium oxychloride, silica, sulphuric acid, oleic acid, sodium thiosulphate, chloroform, sodium methoxide, hexane, methanol, etc were obtained from S. D. Fine chem. Ltd.
EXPERIMENTAL^
1. Catalyst preparation:
Silica gel with pore volume of 0.9 ml/g was prepared by potassium hydroxide leaching of the surface and used as a support for the catalyst preparation. The particle size of the silica gel was 2-5 mm. Dry silica gel was loaded with zirconium oxide as zirconium oxychloride with various loading levels from 1 to 4% from its aqueous solution. Calculated quantity of zirconium oxychloride on the basis of weight of silica was dissolved in water (volume of water equivalent to the pore volume of silica was taken). Weighed quantity of silica was soaked in zirconium oxychloride solution for 30 min. The loaded zirconium oxychloride was precipitated as zirconium hydroxide by exposing to ammonia vapours for 2-3 hrs. in a closed vessel, dried in an oven at 120°C for 12 hrs, sulfated by using IN sulfuric acid followed by calcining at 450 °C for 4hrs.This catalyst was then washed with water to remove traces of sulfuric acid and again calcined at 450°C for 2 hrs, cooled, crushed into powder of 40 mesh size and used for the experimental part.
11

Optimization of the catalyst:
In most of the reported studies the loading of the sulfated zirconia on silica is in the higher range of 15-50 %. This high loading level could be advantageous in getting higher rate in simple ammoxidation, esterification, etherification, oxidation etc. In these cases the reaction proceeds in the surface layer as well as in the interiors i.e. bulk phase, of the solid acid catalysts. But as far as other reactions being carried out at higher temperatures, it is observed that the reactions catalyzed by solid acids proceed mainly on the surface, at least in the surface layers.
Experimental Details
1:1 mole ratio of butanol to acetic acid was taken in a three-neck flask fitted with a thermometer pocket with thermometer, a Dean-stark apparatus filled with butanol, a water condenser. The amount of catalyst with 1% zirconia was 5% by weight of the reactant, added in the first batch. The whole assembly was kept in a heating mantel with controller. Temperature was maintained in the range of 100-120°C.The reaction was monitored by measuring the amount of water collected in the Dean-Stark apparatus. The same procedure was repeated for the remaining catalysts with different loading levels, care was taken in maintaining the amount of zirconia in each batch constant i.e. for 2% loading exactly half quantity of catalyst was added to the first batch, for 3% one-third of the catalyst in the first batch was added and for 4% one-fourth of catalyst in the first batch was added.
Simple esterification of butanol and acetic acid was carried out using 1-4% loading of sulfated zirconia on silica. Concentration of zirconia was maintained constant in all the five batches. In the first batch, 5% catalyst was used by weight of the reactant and the percentage of zirconia was maintained constant for the remaining batches with varying loading levels of zirconia in the catalyst. The results are shown In Table 1. Product butyl acetate was used as an entrainer for the co product water. The reaction was monitored by measurement of product water, which is the direct evidence of extent of reaction. This method of analysis was followed to avoid the disturbance in the reaction while sampling if analyses were to be carried out by determining acid value. On the basis of this data, the loading level of 1% was selected for the cracking reaction since atom efficiency was unaffected up to this level.
12

The present invention is further illustrated by the following examples Example 1
Cracking of oleic acid and unsaturated fatty acids
100 g of Oleic acid was heated at 280 - 300° C and any distillation activity was observed. No cracking activity was observed without a catalyst.
Example 2
Cracking of oleic acid and unsaturated fatty acids
Known amount (100 gms) of Oleic acid was taken in a three-neck flask fitted with a thermometer pocket with thermometer and the distillation unit. The amount of catalyst surface supported sulfated zirconia silicate catalyst was 1% by weight of the reactant with 1% zirconia loading. The whole assembly was kept in a heating mantle with controller, temperature was maintained in the range of 280-300°C. As the cracking reaction progressed, the reaction was continued till distillate was coming out from the reaction mixture. The amount of distillate coming out was measured at 30 minutes interval.
Separation of products in oleic acid cracking
In oleic acid cracking the complete reaction mass was distilled out and was further subjected to fractional distillation to separate both the products and these were further characterized.
It was noticed that a small part of the fatty acid was always present in the olefin. This was separated by passing the product mixture on a bed of basic alumina adsorbent till the emerging product had no acid value. After the bed was saturated with carboxylic acid, the acid was recovered by passing alcoholic hydrochloride over the bed and then regenerating the bed with alcoholic caustic solution and was made available for reuse. The regenerated acid was mixed with the carboxylic after separation of alcohol.
13

Example 3
Separation of products in soybean oil cracking
In the case of soyabean oil, only the olefin was removable by distillation since the fatty acid was bonded to glycerin from the other end. The distillate which also contained a small portion of fatty acids was isolated as follows:
At the end of reaction that is when no further distillate came out, sodium methoxide was added to distillate to neutralize acid groups present. The solution obtained was then extracted with hexane (3 X 100 ml), the organic fractions were collected and solvent was distilled to obtain Product 1 (C8 and CIO Olefin). The aqueous extract was acidified, then again extracted with hexane (2 X 100 ml) and all the extracts were collected and solvent was distilled to obtain Product 2 (C8 and CIO acid).
The acid could also be separated by treatment with alumina bed as explained earlier in cracking of oleic acid.
Example 4
Alkaline hydrolysis of the product obtained in soybean oil cracking
The residual product obtained in the soybean oil cracking was the acid moiety bonded with the glyceride thus making it difficult to distill out and part of it might have polymerized due to the high reaction temperature. This residue was saponified using ethanol and alcoholic potassium hydroxide for 3h. At the end of reaction, the mixture was neutralized with hydrochloric acid, diluted sufficiently with water to cause separation of fatty acids and the fatty acid layer was separated by a separating funnel. The first criterion studied was cracking reaction with and without catalyst. Here it was observed that no cracking occurred without catalyst. Some amount of distillate that came out was not olefin or acid which was expected in the cracking reaction whereas with catalyst the expected olefins and acids distilled out in relatively good yields.
14

Example 5
The second step of the study was to optimize the catalyst composition for the best performance and then establish its reusability. Various loading levels of zirconia in catalyst were studied for butanol and acetic acid esterification for optimization of the catalytic activity.
Table 1 : Various loading levels of Zirconia in catalyst to study butanol and acetic acid esterification.

Catalyst 1% 2% 3% 4%
Loading
Time (Hr.) Catalyst Catalyst Catalyst Catalyst
Quantity Quantity Quantity Quantity
6.7 g 3.35 g 2.23 g 1.17g
% Conversion
0.5 2.22 3.88 4.44 5.55
1 18.88 23.88 17.22 25
1.5 30.5 41.66 34.44 37.22
2 33.88 51.11 47.77 43.88
2.5 37.22 57.77 56.66 47.22
3 39.44 61.11 60.55 49.55
Various loading levels of Zirconia in catalyst to study butanol and acetic acid esterification are described in FIG 1
From the results it was seen that even departure from 2 to 3 % zirconium oxide loading on silica resulted in partial reduction of activity. This level was therefore used for studying the stability of the catalyst.
15

Reusability study:
Example 6
After optimization of the catalyst the reusability of the catalyst was checked with esterification of butanol-acetic acid using a 2% Zirconia loaded catalyst. After the reaction was completed, the catalyst was separated by filtration. The catalyst was recycled to the next batch without further treatment. Additional fresh raw materials were added and further reactions were continued. The results of this reaction are given in Table No. 2. From the Table No. 2 and graphical representation of this data in Fig 2 it is observed that, there is no much difference in the results obtained, which implies the catalyst activity is consistent throughout the 5 batches, thus proving the reusability of the catalyst. TABLE 2: Catalyst reusability study in esterification of butanol

Time % Conversion
(hr)
BATCH BATCH BATCH BATCH
I II III rv
0.5 3.88 3.33 3.33 3.33
1.5 23.88 22.22 22.77 21.66
2.5 41.66 40 39.44 38.88
3.5 51.11 50.55 49.44 47.77
4.5 57.77 56.11 55.55 53.88
5.0 61.11 60.55 58.88 56.66
Results of Reusability study of the catalyst for butanol esterification is shown in FIG.2
16

Example 7
TABLE 3 : Reusability study of the catalyst for cracking of oleic acid

Time AMOUNT OF DISTILLATE COLLECTED
(mins) (gms)
Batch Batch Batch Batch Batch
I II ffl rv V
30 13.69 11.31 9.63 7.41 5.39
60 27.51 24.39 22.61 20.43 17.61
90 47.56 43.69 41.31 39.61 37.59
120 68.42 65.34 63.21 60.96 58.14
150 80.61 77.85 74.69 72.34 69.98
180 95.93 93.13 91.11 89.91 87.03
The residue after reaction was not separated from the catalyst and fresh oleic acid was
added to start the next batch.
Results of reusability study of the catalyst for cracking of oleic acid is indicated in
FIG.3
As can be seen, there is a small loss in catalytic activity after cracking about 500 g
oleic acid / g catalyst.
Example 8
TABLE 4: Amount of distillate collected in reaction in 30 mins interval with soyabean oil and oleic acid. (lOOg oil or oleic acid)

Time Amount of distillate collected
(mins) (gms)
Soybean oil Oleic acid
30 5.69 13.69
60 11.25 27.51
90 21.55 47.56
17

120 33.80 68.42
150 43.97 80.61
180 - 95.93
Further distillate was subjected to vacuum distillation where 2 fractions were obtained. 1st in the range of 125-140° C (Weight of 1st distillate; 26.79 gms) which represents 60.92 %. The 2nd distillate was in the range of 155-165° C (Weight of 2nd distillate: 15.69 gms) which represented 35.68 %. Total yield of liquid products was 96.6%.
Example 9
TABLE 5: Acid value of distillate collected in reaction in 30 mins interval with soyabean oil and oleic acid. (lOOg oil or oleic acid)

Time (mins) Acid value of distillate collected
Soybean oil Oleic acid
30 21.85 62.49
60 44.51 100.13
90 67.15 141.84
120 85.21 158.52
150 100.62 182.62
180 - 189.25
The another criterion studied was effect of agitation. It was observed that without agitation the distillation was faster but incomplete. Some part of the reaction mass polymerizes due to high temperature applied for the reaction. Whereas when agitation was applied the rate of distillation was slower but all the reaction mass distills out completely without any polymerization.
18

Example 10
TABLE 6: Amount of distillate collected in reaction in 30 mins interval with oleic
acid.(lOOg)
Time (mins) amount of distillate collected
Without agitation With agitation

30 13.69 7.15
60 27.51 16.57
90 47.56 27.87
120 68.42 39.91
150 80.61 58.43
180 95.93 71.41
210 - 84.21
240 _ 95.02
Material Balance for Oleic Acid Cracking
Weight of starting material: 100 gms Weight of distillate : 48.93 gms Weight of residue: 47.00gms Total yield of liquid products = 95.93 %
Characterization of Products
GC - MS analysis was done for all the products obtained and it was found that the product obtained were 1-octene, 1-decene, 9-decenoic acid, 7-octenoic acid.
The data generated by the GCMS indicates that oleic acid contained in the soyabean oil is cleanly cracked in two pieces leading to the formation of an olefin and a terminally unsaturated carboxylic acid. This can be shown by the following reaction as anticipated.
19

H3C (CH2)7 HC—CH (CH2)7 COOH
Oleic acid
280 - 300°c 1%SSZ2Ctalyst
H3C (CH2)T HC=CH2 H2C= HC P2) 5 COOH
H3C-CH2)5—HC=CH2 + CH2=CH—(CH2)7—COOH

20
Mechanism of cracking and role of H+:

Here the hydride ion generated from the acidic catalyst is added across the double bond forming a carbo cation, which on simultaneous hydride transfers and fission yields the products. The position of the carbon on which the cation is formed decides the products of cracking. The proposed mechanism agrees with the results obtained.
DESCRIPTION OF ACCOMPANYING DRAWINGS
Various loading levels of Zirconia in catalyst to study butanol and acetic acid esterification are described in FIG 1. X axis (1) denotes time in hours and Y axis denotes conversion. Graphs 3, 4, 5 and 6 denote % conversion of the esterification reaction using 1,2, 3 and 4 % catalyst respectively.
Results of reusability study of the catalyst for butanol esterification are shown in FIG. 2. X-axis (number 7) denotes time in hours and Y axis (number 8) denotes % conversion in esterification. Graphs 9, 10, 11 and 12 denote % conversion of esterification obtained by recycling catalyst in 4 batches.
Results of reusability study of the catalyst for cracking of oleic acid are indicated in FIG. 3. X-axis (13) denotes time in hours and Y- axis (14) denote amount of product distillate and collected. Graphs 15, 16, 17, 18 and 19 denote amount of distillate collected with respect to time by recycling the catalyst in four batches.
While the present invention is described above in connection with preferred or illustrative embodiments, these embodiments are not intended to be exhaustive or limiting of the invention. Rather, the invention is intended to cover all alternatives, modifications and equivalents included within its spirit and scope, as defined by appended claims.
21

Claim,
1. A process for cracking of oleic acid and high oleic vegetable oils by involving hyperacidic catalysts such as surface supported sulfated zirconium silicate catalysts to produce a-olefms and terminally unsaturated carboxylic acids wherein
the said process comprising
(i) introducing oleic acid or / and unsaturated fatty acids such as high oleic
vegetable oils such as soybean oil into a reactor; (ii) adding 1% hyperacidic catalyst such as surface supported sulfated
zirconium silicate catalyst to the said reactant; (iii) heating the said reaction mixture to 280°C to 300°C till distillate comes
out from the said reaction mixture; (iv) adding sodium alkali metal oxide to saponify the carboxylic acid in the
said distillate; (v) adding organic solvent, hexane to the said saponified distillate to give
two phase system; (vi) extracting product I, a-olefms in hexane by vigorously shaking the said
two phase system; (vii) separating the organic layer, hexane from the said two phase system; (viii) collecting the said organic extracts ; (ix) distilling out hexane to isolate the product I (a-olefin); (x) acidifying aqueous phase of the said two phase system after extraction; (xi) adding the hexane to the said acidified aqueous phase to give two
phase system, (xii) extracting product II, terminally unsaturated carboxylic acid in organic
phase containing hexane from the said two phase system; (xiii) distilling out the hexane from the said organic phase to isolate the
product II (acid); and
22

(xiv) the residue comprising terminally unsaturated carboxylic acid bonded to glycerin obtained in step iii is saponified with alcoholic potassium hydroxide, preferably in ethanol solvent, removing the alcohol by distillation and repeating the steps (x) to (xiii) described above to isolate the terminally unsaturated carboxylic acid.
2. A process for cracking of oleic acid and high oleic vegetable oils by involving hyperacidic catalysts such as surface supported sulfated zirconium silicate catalysts to produce a-olefins and terminally unsaturated carboxylic acids as substantially described herein with reference to foregoing examples 1 to 10.
Dated this the 26th day of September 2003
Dr. Gopakumar G. Nair Agent for the Applicant
25

the residue comprising terminally unsaturated carboxylic acid bonded to glycerin obtained in step iii is saponified with alcoholic potassium hydroxide, preferably in ethanol solvent, removing the alcohol by distillation and repeating the steps (x) to (xiii) described above to isolate the terminally unsaturated carboxylic acid.

2. A process for cracking of oleic acid and high oleic vegetable oils by involving hyperacidic catalysts such as surface supported sulfated zirconium silicate catalysts to produce a-olefins and terminally unsaturated carboxylic acids as substantially described herein with reference to foregoing examples 1 to 10.

rth
Dated this the 26tn day of September 2003

25

Dr. Gopakumar G. Nair Agent for the Applicant

catalyst. (Zirconium is not a noble metal; it is still expensive compared to elementary acidic materials like silica and alumina). Silica supported surfated zirconia catalyst has following benefits;
1 It is possible to tailor physical properties such as surface area, pore volume, bulk density and particle size conveniently.
2 It is resistant to acids such as sulfuric acid, which are involved in next step of preparation.
3 It forms covalent bond with group IV elements such as Ti, Zr, and Hf, hydroxides through the surface silanol groups that might be helpful in retaining the catalytic activity.
4 It is the most abundant element and is very inexpensive, has no disposal or toxicity problem.
5 In pure state, it is colorless.
Not many other industrial supports such as activated carbon, activated alumina or activated clay could offer these benefits. We noticed that there is no published study on the use of supported sulfated zirconia for the cracking of vegetable oils. In this work we are reporting preliminary findings of the catalytic cleaving of oleic acid or vegetable oils rich in mono unsaturated acids. Soyabean oil is one of the cheapest vegetable oils in the tropical regions and would form a good feed stock for chemical products.
SUMMARY OF INVENTION
A process for cracking of oleic acid and high oleic vegetable oils by involving hyperacidic catalysts such as surface supported sulfated zirconium silicate catalysts to produce a-olefins and terminally unsaturated carboxylic acids wherein the said process comprising
(i) introducing oleic acid or / and unsaturated fatty acids such as high oleic
vegetable oils such as soybean oil into a reactor; (ii) adding 1% hyperacidic catalyst such as surface supported sulfated
zirconium silicate catalyst to the said reactant; (iii) heating the said reaction mixture to 280HC to 300°C till distillate comes out from the said reaction mixture;
8

(iv) adding sodium alkali metal alkoxide; preferably sodium methoxide to saponify the carboxylic acid in the said distillate;
(v) adding organic solvent, hexane to the said saponified distillate to give two phase system;
(vi) extracting product I, a-olefins in hexane by vigorously shaking the said two phase system;
(vii) separating the organic layer, hexane from the said two phase system;
(viii) collecting the said organic extracts ;
(ix) distilling out hexane to isolate the product I (a-olefin) i.e.C8 and CIO a -Olefin;
(x) acidifying aqueous phase of the said two phase system after extraction;
(xi) adding the hexane to the said acidified aqueous phase to give two phase system,
(xii) extracting product II, C8 and CIO terminally unsaturated carboxylic acid in organic phase containing hexane from the said two phase system;
(xiii) distilling out the hexane from the said organic phase to isolate the product II (acid) ; and (xiv) the residue comprising terminally unsaturated carboxylic acid bonded to glycerin obtained in step iii is saponified with alcoholic potassium hydroxide, preferably in ethanol solvent, removing the alcohol by distillation and repeating the steps (x) to (xiii) described above to isolate the terminally unsaturated carboxylic acid.
DETAILED DESCRIPTION OF THE INVENTION
A process for cracking oleic acid and high oleic vegetable oils by involving hyper acidic catalyst that offers quantitative and reproducible yield is disclosed. More specifically catalyst used in this process of cracking of Oleic acid and high oleic vegetable oils to produce a-olefines and terminally unsaturated carboxylic acid is surface supported Sulphated Zirconium Silicate catalyst.
The process for the synthesis of the said catalyst is disclosed in our application number 1018/MUM/2003.
9

catalyst. (Zirconium is not a noble metal; it is still expensive compared to elementary acidic materials like silica and alumina).
Silica supported surfated zirconia catalyst has following benefits;
1 It is possible to tailor physical properties such as surface area, pore volume, bulk density and particle size conveniently.
2 It is resistant to acids such as sulfuric acid, which are involved in next step of preparation,
3 It forms covalent bond with group IV elements such as Ti, Zr, and Hf, hydroxides through the surface silanol groups that might be helpful in retaining the catalytic activity.
4 It is the most abundant element and is very inexpensive, has no disposal or toxicity problem.
5 In pure state, it is colorless.
Not many other industrial supports such as activated carbon, activated alumina or activated clay could offer these benefits.
We noticed that there is no published study on the use of supported sulfated zirconia for the cracking of vegetable oils. In this work we are reporting preliminary findings of the catalytic cleaving of oleic acid or vegetable oils rich in mono unsaturated acids. Soyabean oil is one of the cheapest vegetable oils in the tropical regions and would form a good feed stock for chemical products.
SUMMARY OF INVENTION
A process for cracking oleic acid and high oleic vegetable oils by involving hyper acidic catalyst that offers quantitative and reproducible yield is disclosed in this invention.
8

More specifically a process of cracking of Oleic acid and high oleic vegetable oils to produce a-olefines and terminally unsaturated carboxylic acid by use of surface supported Sulphated Zirconium Silicate catalyst is dislcosed.
DETAILED DESCRIPTION OF THE INVENTION
A process for cracking oleic acid and high oleic vegetable oils by involving hyper acidic catalyst that offers quantitative and reproducible yield is disclosed.
More specifically catalyst used in this process of cracking of Oleic acid and high oleic vegetable oils to produce a-olefines' and terminally unsaturated carboxylic acid is surface supported Sulphated Zirconium Silicate catalyst.
The process for the synthesis of the said catalyst is disclosed in our application number 1018/MXJM/2003.
Methods for Analysis Employed
Chemical Method
1) Acid value (ASTM 1639-70)
About 0.5-1 gm of the sample was accurately weighed in the conical flask. 25 ml of neutral alcohol was added to dissolve the sample. 3-4 drops of 1% phenolphthalein solution (in ethanol) was added. The mixture in the conical flask was titrated against 0.1N alcoholic potassium hydroxide solution. Acid value was calculated as follows:
Acid Value 56.1 X normality of KOH X ml of KOH
Weight of the sample in grams
Acid number is expressed as milligrams of KOH per gram of sample
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2) Iodine number (method of American oil chemists society)
About 1 gm of sample was weighed in a 250ml quick fit conical flask and was dissolved in carbon tetrachloride. 25 ml of Wij's solution was added to it with constant stirring. The solution was kept in dark for 30 mins. 10 ml of 10% KI was then added and the liberated iodine was titrated against Na2SO3 using starch indicator. A blank reading was carried out simultaneously. The saponification number was calculated using following formula:
56.1 X normality of Na2SO3X(B-S)
Iodine Number =-
Weight of the sample in grams
B = ml of Na2S03 of required for blank S= ml of Na2SC3 required for sample
Iodine number is expressed as grams of Iodine per 100 gram of sample
Instrumental Methods:
1. Gas Chromatography - Mass Spectroscopy
All the products obtained were characterized by GC - MS analysis using GC- MS spectrophotometer (Q Mass 910 of Perkin Elmer make).
Materials used:
Soybean oil was obtained from M/s Jayant Oil Mills Ltd., Mumbai Other chemical used such as zirconium oxychloride, silica, sulphuric acid, oleic acid, sodium thiosulphate, chloroform, sodium methoxide, hexane, methanol, etc were obtained from S. D. Fine chem. Ltd.
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EXPERIMENTALS
1. Catalyst preparation:
Silica gel with pore volume of 0.9 ml/g was prepared by potassium hydroxide leaching of the surface and used as a support for the catalyst preparation. The particle size of the silica gel was 2-5 mm- Dry silica gel was loaded with zirconium oxide as zirconium oxychloride with various loading levels from 1 to 4% from its aqueous solution. Calculated quantity of zirconium oxychloride on the basis of weight of silica was. disssoled in water (volume of water equivalennt to the pore volume OF sillcat was taken). Weighed quantity of silica was soaked in zirconium oxychloride solution for 30 min. The loaded zirconium oxychloride was precipitated as zirconium hydroxide by exposing to ammonia vapours for 2-3 hrs. in a closed vessel, dried in an oven at 120°C for 12 hrs, sulfated by using IN sulfuric acid followed by calcining at 450 °C for 4hrs.This catalyst was then washed with water to remove traces of sulfuric acid and again calcined at 450°C for 1 hrs, cooled, crushed into powder of 40 mesh size and used for the experimental part.
Optimization of the catalyst:
In most of the reported studies the loading of the sulfated zirconia on silica is in the higher range of 15-50 %. This high loading level could be advantageous in getting higher rate in simple ammoxidation, esterification, etherification, oxidation etc. In these cases the reaction proceeds in the surface layer as well as in the interiors i.e. bulk phase, of the solid acid catalysts. But as far as other reactions being carried out at higher temperatures, it is observed that the reactions catalyzed by solid acids proceed mainly on the surface, at least in the surface layers.
Experimental Details
1:1 mole ratio of butanol to acetic acid was taken in a three-neck flask fitted with a thermometer pocket with thermometer, a Dean-stark apparatus filled with butanol, a water condenser. The amount of catalyst with 1% zirconia was 5% by weight of the reactant, added in the first batch. The whole assembly was kept in a heating mantel with controller. Temperature was maintained in the range of 100-120 C.The reaction was monitored by measuring the amount of water collected in the Dean-Stark
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apparatus. The same procedure was repeated for the remaining catalysts with different loading levels, care was taken in maintaining the amount of zirconia in each batch constant i.e. for 2% loading exactly half quantity of catalyst was added to the first batch, for 3% one-third of the catalyst in the first batch was added and for 4% one-fourth of catalyst in the first batch was added.
Simple esterification of butanol and acetic acid was carried out using 1-4% loading of sulfated zirconia on silica. Concentration of zirconia was maintained constant in all the five batches. In the first batch, 5% catalyst was used by weight of the reactant and the percentage of zirconia was maintained constant for the remaining batches with varying loading levels of zirconia in the catalyst. The results are shown In Table 1. Product butyl acetate was used as an entrainer for the co product water. The reaction was monitored by measurement of product water, which is the direct evidence of extent of reaction. This method of analysis was followed to avoid the disturbance in the reaction while sampling if analyses were to be carried out by determining acid value. On the basis of this data, the loading level of 1% was selected for the cracking reaction since atom efficiency was unaffected up to this level.
The present invention is further illustrated by the following examples
Example 1
Cracking of oleic acid and unsaturated fatty acids
100 g of Oleic acid was heated at 280 - 300° C and any distillation activity was observed. No cracking activity was observed without a catalyst.
Example 2
Cracking of oleic acid and unsaturated fatty acids
Known amount (100 gms) of Oleic acid was taken in a three-neck flask fitted with a thermometer pocket with thermometer and the distillation unit. The amount of catalyst surface supported sulfated zirconia silicate catalyst was 1% by weight of the reactant with 1% zirconia loading. The whole assembly was kept in a heating mantle with
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controller, temperature was maintained in the range of 280-300°C. As the cracking
reaction progressed, the reaction was continued till distillate was coming out from the
reaction mixture. The amount of distillate coming out was measured at 30 minutes
interval.
Separation of products in oleic acid cracking
In oleic acid cracking the complete reaction mass was distilled out and was further
subjected to fractional distillation to separate both the products and these were further
characterized.
It was noticed that a small part of the fatty acid was always present in the olefin. This was separated by passing the product mixture on a bed of basic alumina adsorbent till the emerging product had no acid value. After the bed was saturated with carboxylic acid, the acid was recovered by passing alcoholic hydrochloride over the bed and then regenerating the bed with alcoholic caustic solution and was made available for reuse. The regenerated acid was mixed with the carboxylic after separation of alcohol.

Example 3
Separation of products in soybean oil cracking
In the case of soyabean oil, only the olefin was removable by distillation since the fatty acid was bonded to glycerin from the other end. The distillate which also contained a small portion of fatty acids was isolated as follows:

At the end of reaction that is when no further distillate came out, sodium methoxide
was added, to distillate to neutralize acid groups present. The solution obtained was
then extracted with hexane (3 X 100 ml), the organic fractions were collected and
solvent was distilled to obtain Product 1 (C8 and CIO Olefin). The aqueous extract
was acidified, then again extracted with hexane (2 X 100 ml) and all the extracts were
collected and solvent was distilled to obtain Product 2 (C8 and C10 acid).
The acid could also be separated by treatment with alumina bed as explained earlier in cracking of oleic acid.
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Example 4
Alkaline hydrolysis of the product obtained in soybean oil cracking
The residual product obtained in the soybean oil cracking was the acid moiety bonded
with the glyceride thus making it difficult to distill out and part of it might have
polymerized due to the high reaction temperature. This residue was saponified using
ethanol and alcoholic potassium hydroxide for 3h At the end of reaction, the mixture
was neutralized with hydrochloric acid, diluted sufficiently with water to cause
separation of fatty acids and the fatty acid layer was separated by a separating funnel. The first criterion studied was cracking reaction with and without catalyst. Here it was observed that no cracking occurred without catalyst. Some amount of distillate that came out was not olefin or acid which was expected in the cracking reaction whereas with catalyst the expected olefins and acids distilled out in relatively good yields.
Example 5
The second step of the study was to optimize the catalyst composition for the best
performance and then establish its reusability. Various loading levels of zirconia in
catalyst were studied for butanol and acetic acid esterification for optimization of the
catalytic activity.
Table 1 : Various loading levels of Zirconia in catalyst to study butanol and acetic
acid esterification.

Catalyst 1% 2% 3% 4%
Loading
Time (Hr.) Catalyst Catalyst Catalyst Catalyst
Quantity Quantity Quantity Quantity
6.7 g 3.35 g 2.23 g l-17g
% Conversion
0.5 2.22 3.88 4.44 5.55
1 18.88 23.88 17.22 25
1.5 30.5 41.66 34.44 37.22
2 33.88 51.11 47.77 43.88
2.5 37.22 57.77 56.66 47.22
3 39.44 61.11 60.55 49.55
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Various loading levels of Zirconia in catalyst to study butanol and acetic acid esterification are described in FIG 1
From the results it was seen that even departure from 2 to 3 % zirconium oxide loading on silica resulted in partial reduction of activity. This level was therefore used for studying the stability of the catalyst.
Reusability study:
Example 6
After optimization of the catalyst the reusability of the catalyst was checked with esterification of butanol-acetic acid using a 2% Zirconia loaded catalyst. After the reaction was completed, the catalyst was separated by filtration. The catalyst was recycled to the next batch without further treatment. Additional fresh raw materials were added and further reactions were continued. The results of this reaction are given in Table No. 2. From the Table No. 2 and graphical representation of this data in Fig 2 it is observed that, there is no much difference in the results obtained, which implies the catalyst activity is consistent throughout the 5 batches, thus proving the reusability of the catalyst. TABLE 2: Catalyst reusability study in esterification of butanol

Time % Conversion
(hr)
BATCH BATCH BATCH BATCH
I II HI rv
0.5 3.88 3.33 3.33 3.33
1.5 23.88 22.22 22.77 21.66
2.5 41.66 40 39.44 38.88
3.5 sun 50.55 49.44 47.77
4.5 57.77 56.11 55.55 53.88
5.0 61.11 60.55 58.88 56.66
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Results of Reusability study of the catalyst for butanol esterification is shown in FIG.2
Example 7
TABLE 3 : Reusability study of the catalyst for cracking of oleic acid

Time AMOUNT OF DISTILLATE COLLECTED
(mins) (gms)
Batch Batch Batch Batch Batch
I II III IV V
30 13.69 11.31 9.63 7.41 5.39
60 27.51 24.39 22.61 20.43 17.61
90 47.56 43.69 41.31 39.61 37.59
120 68.42 65.34 63.21 60.96 58.14
150 80.61 77.85 74.69 72.34 69.98
180 95.93 93.13 91.11 89.91 87.03
The residue after reaction was not separated from the catalyst and fresh oleic acid was
added to start the next batch.
Results of reusability study of the catalyst for cracking of oleic acid is indicated in
FIG.3
As can be seen, there is a small loss in catalytic activity after cracking about 500 g
oleic acid / g catalyst.
Example S
TABLE 4: Amount of distillate collected in reaction in 30 mins interval with soyabean oil and oleic acid. (lOOg oil or oleic acid)

Time Amount of distillate collected
(mins) (gms)
Soybean oil Oleic acid
30 5.69 13.69
16

60 11.25 27.51
90 21.55 47.56
120 33.80 68.42
150 43.97 80.61
180 - 95.93
Further distillate was subjected to vacuum distillation where 2 fractions were obtained. 1st in the range of 125-140° C (Weight of 1st distillate: 26.79 gms) which represents 60.92 %. The 2nd distillate was in the range of 155-165° C (Weight of 2nd distillate: 15.69 gms) which represented 35.68 %. Total yield of liquid products was 96.6%.
Example 9
TABLE 5: Acid value of distillate collected in reaction in 30 mins interval with soyabean oil and oleic acid. (lOOg oil or oleic acid)

Time (mins) Acid value of distillate collected
Soybean oil Oleic acid
30 21.85 62.49
60 44.51 100.13
90 67.15 141.84
120 85.21 158.52
150 100.62 182.62
180 - 189.25
The another criterion studied was effect of agitation. It was observed that without agitation the distillation was faster but incomplete. Some part of the reaction mass polymerizes due to high temperature applied for the reaction. Whereas when agitation was applied the rate of distillation was slower but all the reaction mass distills out completely without any polymerization.
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Example 10
TABLE 6: Amount of distillate collected in reaction in 30 mins interval with oleic acid. (lOOg)

Time (mins) amount of distillate collected
Without agitation With agitation
30 13.69 7.15
60 27.51 16.57
90 47.56 27.87
120 68.42 39.91
150 80.61 58.43
180 95.93 71.41
210 - 84.21
240 - 95.02
Material Balance for Oleic Acid Cracking
Weight of starting material: 100 gms Weight of distillate : 48.93 gms Weight of residue: 47.00gms Total yield of liquid products = 95.93%
Characterization of Products
GC - MS analysis was done for all the products obtained and it was found that the product obtained were 1-octene, 1-decene, 9-decenoic acid, 7-octenoic acid.
The data generated by the GCMS indicates that oleic acid contained in the soyabean oil is cleanly cracked in two pieces leading to the formation of an olefin and a terminally unsaturated carboxylic acid. This can be shown by the following reaction as anticipated.
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Oleic acid
280 - 300°c 1%SSZ2 Ctalyst
Y '

Mechanism of cracking and role of H:

19

Here the hydride ion generated from the acidic catalyst is added across the double bond forming a carbo cation, which on simultaneous hydride transfers and fission yields the products. The position of the carbon on which the cation is formed decides the products of cracking. The proposed mechanism agrees with the results obtained.
DESCRIPTION OF ACCOMPANYING
Various loading levels of Zirconia in catalyst to study butanol and acetic acid esterification are described in FIG 1. X axis (1) denotes time in hours and Y axis denotes conversion. Graphs 3, 4, 5 and 6 denote % conversion of the esterification reaction using 1, 2, 3 and 4 % catalyst respectively.
Results of reusability study of the catalyst for butanol esterification are shown in FIG. 2. X-axis (number 7) denotes time in hours and Y axis (number 8) denotes % conversion in esterification. Graphs 9, 10, 11 and 12 denote % conversion of esterification obtained by recycling catalyst in 4 batches.
Results of reusability study of the catalyst for cracking of oleic acid are indicated in FIG. 3. X-axis (13) denotes time in hours and Y- axis (14) denote amount of product distillate and collected. Graphs 15, 16, 17, 18 and 19 denote amount of distillate collected with respect to time by recycling the catalyst in four batches.
While the present invention is described above in connection with preferred or illustrative embodiments, these embodiments are not intended to be exhaustive or limiting of the invention. Rather, the invention is intended to cover all alternatives, modifications and equivalents included within its spirit and scope, as defined by appended claims.
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Claim,
1. A process for cracking of oleic acid and high oleic vegetable oils by involving hyperacidic catalysts such as surface supported sulfated zirconium silicate catalysts to produce a-olefins and terminally unsaturated carboxylic acids wherein the said process comprising of
(i) introducing oleic acid or / and unsaturated fatty acids such as high oleic
vegetable oils such as soybean oil into a reactor; (ii) adding 1% hyperacidic catalyst such as surface supported sulfated
zirconium silicate catalyst to the said reactant;
(iii) heating the said reaction mixture to 280"C to 300°C till f$ distillate
——.,^,x.„,
comes out from the said reaction mixture; '
(iv) adding sodium alkali metal oxide to saponify the carboxylic acid in the
said distillate; (v) adding organic solvent, hexane to the said saponified distillate to give
two phase system; (vi) extracting product I, a-olefins in hexane by vigorously shaking the said
two phase system; (vii) separating the organic layer, hexane from the said two phase system; (viii) collecting the said organic extracts ; (ix) distilling out hexane to isolate the product I (a-olefin) ; (x) acidifying aqueous phase of the said two phase system after extraction; (xi) adding the hexane to the said acidified aqueous phase to give two
phase system, (xii) extracting product II, terminally unsaturated carboxylic acid in organic
phase containing hexane from the said two phase system; (xiii) distilling out the hexane from the said organic phase to isolate the
product II (acid); and (xiv) the residue comprising terminally unsaturated carboxylic acid bonded
to glycerin obtained in step iii is saponified with sodium hydroxide,
preferably in alcohol solvent, removing the alcohol by distillation and
g 21

repeating the steps (x) to (xiii) described above to isolate the terminally unsaturated carboxylic acid.
2) A process for cracking of oleic acid and high oleic vegetable oils by involving hyperacidic catalysts such as surface supported sulfated zirconium silicate catalysts to produce a-olefins and terminally unsaturated carboxylic acids as claimed in claim 1 wherein alkali metal oxide used in saponification is not
acid, diluted sufficiently with water to cause separation of fatty acids and the fatty acid layer, separated by a separating funnel.
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hyperacidic catalysts such as surface supported sulfated zirconium silicate catalysts to produce a-olefins and terminally unsaturated carboxylic acids as substantially described herein with reference to the foregoing example 1 to 10.
Dated this the 26th day of Sept 2003

44

To
The Controller of Patents
The Patent Office,
At Mumbai.

23

Dr. Gopakumar G. Nair
Agent for the Applicant Gopakumar Nair Associates
Nair Baug, Akurli Road, Kandivli (East), Mumbai - 400 101

Documents:

1019-mum-2003-abstract(30-12-2004).pdf

1019-mum-2003-cancelled pages(30-10-2003).pdf

1019-mum-2003-claim(granted)-(30-12-2004).pdf

1019-mum-2003-corrospondence(30-12-2004).pdf

1019-mum-2003-corrospondence(ipo)-(09-09-2004).pdf

1019-mum-2003-drawing(30-12-2004).pdf

1019-mum-2003-form 1(30-10-2003).pdf

1019-mum-2003-form 19(30-10-2003).pdf

1019-mum-2003-form 2(granted)-(30-12-2004).pdf

1019-mum-2003-form 26(08-05-2003).pdf

1019-mum-2003-form 3(26-09-2003).pdf

1019-mum-2003-form 3(30-12-2004).pdf

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Patent Number

215092

Indian Patent Application Number

1019/MUM/2003

PG Journal Number

13/2008

Publication Date

31-Mar-2008

Grant Date

21-Feb-2008

Date of Filing

29-Sep-2003

Name of Patentee

MALSHE VINOD CHINTAMANI

Applicant Address

1, STAFF QUARTERS, UDCT CAMPUS, MATUNGA MUMBAI

Inventors:

#	Inventor's Name	Inventor's Address
1	MALSHE, VINOD CHINTAMANI	1, STAFF QUARTERS, UDCT CAMPUS, MATUNGA MUMBAI - 400 019.
2	MAHESHWARI, KOMAL DIAMOND	PPV SECTION, UICT, MATUNGA, MUMBAI —400 019.

PCT International Classification Number

C10 G 11/00

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA