Ferrierite zeolite, its template free preparation and applications thereof

Abstract

The present disclosure relates to a template free modified ferrierite zeolite has a Si / Al ratio in the range of 12 to 13. Further, the present disclosure also provides a method of preparation of a modified ferrierite zeolite. The present disclosure also provides a process of conversion of oleic acid to iso-stearic acid by using the modified ferrierite zeolite. The commercial grade oleic acid conversion is about 85% and isostearic acid selectivity is about 86%.

Description

[0001] FERRIERITE ZEOLITE, ITS TEMPLATE FREE PREPARATION AND APPLICATIONS THEREOF

[0002] FIELD OF THE INVENTION

[0003] The present disclosure relates to a field of modified zeolite material. Particularly, the present disclosure provides a template free ferrierite zeolite. Further, the present disclosure also provides a method of preparation of a template free ferrierite zeolite. Furthermore, the present disclosure also provides a process of conversion of oleic acid to iso-stearic acid.

[0004] BACKGROUND OF THE INVENTION

[0005] Itabashi et al. [J. Am. Chem. Soc., 2012, 134, 11542-11549] discloses a seed-assisted, organic structure-directing agent (OSDA)-free synthesis was successfully achieved on ZSM-5, ZSM-11, and ZSM-12. Furthermore, the other successful route to the OSDA-free synthesis of ZSM-12 with the aid of beta seeds was reasonably explained by considering the combination of composite building units (mtw + cas) in the beta seeds (mtw) and the gel-yielding ZSM-5 (cas) when no seeds were added. The requirements for a successful seed-assisted, OSDA-free synthesis of zeolites are proposed on the basis of the synthesis results. Although the validity of the proposed hypothesis is supported by some Na-aluminosilicate zeolites and K-aluminosilicate ECR-18 described here.

[0006] Kim et al. [Catalysis today, 2023, 411-412, 113822] discloses a nanosized seed-derived FER zeolites (SFER, Si / Al molar ratio of ~11) with different FER seed concentration revealed a higher catalytic activity and stability for a gas-phase carbonylation of dimethyl ether (DME) to methyl acetate (MA). At optimal nanosized FER seed contents in the range of 7-15 wt% at much shorter synthesis duration less than 4 days, the larger amounts of stronger Brpnsted acid sites originated from the highly crystalline FER structures on the SFER (5) and SFER (7) even without using any organic structure directing agent (OSDA) were responsible for a higher DME conversion above 60 % and MA selectivity above 99.5 % with their slower deactivation. The positive observations were mainly attributed to the preferential formations of more active Brpnsted acid sites on the highly crystalline FER structures, which were also synthesized at much shorter hydrothermal synthesis duration less than 4 days with the help of the previously synthesized nanosized FER seed.

[0007] Rakoczy et al. [Chem. Eng. Technol., 2002, 25, 273-275] discloses organic templates in the hydrothermal synthesis of zeolites broadens the range of accessible nSi / nAl ratios in the products, enhances their crystallinity, and / or helps to control the nucleation rate during the synthesis Nevertheless, whenever it comes to the commercial- scale production of zeolites, there is a high incentive for template-free syntheses, both for ecological and economical reasons.

[0008] US 10087132 B2 discloses a process for converting an unsaturated fatty acid into a saturated branched-chain fatty acid through a zeolite-catalyzed process and methods of economically regenerating and reusing the zeolite catalyst. The processes include subjecting the unsaturated fatty acid to an isomerization reaction to result in a selective conversion of the unsaturated fatty acid into the saturated branched-chain fatty acid. The reaction occurs in the presence of (i) an activated zeolite catalyst, (ii) an effective amount of water, and (iii) optionally an oligomerization reducing agent. The spent zeolite catalyst may be regenerated by heating to create a regenerated zeolite catalyst that is functional for use as the activated zeolite catalyst.

[0009] Oleic acid (Cl 8 unsaturated linear fatty acid) can be isomerized to iso-stearic acid (Cl 8 saturated branch fatty acid) having application in Cosmetics Industry. Prior arts discloses use of commercial grade ferrierite zeolite for the pharma / AR grade oleic acid (purity >90% mostly supplied by Aldrich) isomerization to isostearic acid with oleic acid conversion of 94% and isostearic acid selectivity of 75%. This approach is not feasible from commercial point of view as commercial grade oleic acid is having purity of 72% and rest includes linoleic acid, linolenic acid palmitic acid etc. Thus, there is no prior art available where commercial grade oleic acid (72% purity) is used. No prior art is available on use of template free ferrierite zeolite for commercial or AR / Pharma grade oleic acid isomerization to isostearic acid. Prior art discloses use of commercial ferrierite zeolite (Si / Al=9) for conversion of Pharma / AR grade oleic acid (purity >90%) to isostearic acid.

[0010] There is a need to develop a cost-effective novel modified ferrierite zeolite by using economic starting materials. The modified ferrierite zeolite can be used in the conversion of oleic acid to iso-stearic acid.

[0011] OBJECTIVES OF THE INVENTION

[0012] The primary object of the present invention is to provide a ferrierite zeolite.

[0013] Another object of the present invention is to provide a method of template free preparation of said ferrierite zeolite. Still another object of the present invention is to provide a process of conversion of oleic acid to iso-stearic acid using said ferrierite zeolite.

[0014] SUMMARY OF THE INVENTION

[0015] This summary is provided to introduce in a simplified form of selection of concepts that are further described below in Detailed Description section. This summary is not intended to identify key features or essential features of the subject matter, nor is it intended to be used as an aid in determine the subject matter’s scope.

[0016] An aspect of the present disclosure is to provide a template free ferrierite zeolite for the conversion of oleic acid into iso-stearic acid having Si / Al ratio in the range of 12-13, particle size in the range of 0.5 to 2 micrometer, external surface are in the range of 250 m2 / g to 350 m2 / g, pore volume in the range of 0.15 cc / g to 0.25 cc / g and sheet or platelets size morphology.

[0017] Another aspect of the present disclosure is to provide a method of preparation of a template free ferrierite zeolite comprising: dissolving 0.93 to 0.18 kg of aluminum sulphate in 1 to 2.5 L of water with stirring to obtain a solution A; dissolving 3 kg of sodium silicate in 1 to 2 L of water with stirring to form a solution B; adding the solution B into the solution A under vigorous stirring for a period in the range of 30 min to 90 min to form a first mixture; dissolving 0 to 0.13 kg of sodium hydroxide in 1 to 2.5 L of water to form a solution C; adding the solution C in the first mixture to form a second mixture; adding 5 to 15 % wt. of FER seed in the second mixture with stirring for a period in the range of 1 to 3 hrs to obtain a homogeneity of the reaction mixture followed by transferring into 20 L SS autoclave and subjected to hydrothermal crystallization at a temperature in the range of 130 to 170 °C for a period in the range of 16 hrs to 75 hrs to obtain a slurry; filtering the slurry to obtain to a solid particles followed by washing with water until the filtrate’s pH fell below 10 to obtain and dried at a temperature in the range of 80 °C to 120 °C for a period in the range of 10 hr to 14 hr to obtain a modified ferrierite zeolite.

[0018] Another aspect of the present disclosure is to provide a process of conversion of oleic acid to iso-stearic acid comprising: contacting 10 to 50 g of oleic acid as a feed with 5 to 12.5 wt % of template free ferrierite zeolite with respect to feed, 4 to 12 wt % of water with respect to feed, 5 to 10 wt % of Triphenyl Phosphine with respect to modified ferrierite zeolite in a reactor at a temperature in the range of 250 to 300 °C for a period in the range of 10 to 24 hrs with stirring at a speed in the range of 100 to 200 rpm and nitrogen gas at a pressure in the range of 5 to 15 bar to obtain a resultant reaction mass have Unsaturated Branched Fatty acids (BUFA desired Product) and other products were predominant trans isomers; separating the water from the reaction mass and the catalyst was removed using centrifugation to obtain a reaction mass; subjecting the reaction mass to hydrogenation using 5 to 15 wt % Pd / C w.r. to reaction mass feed at a temperature in the range of 160 to 200 °C for a period in the range of 2 to 4 hrs to obtain a hydrogenated mass and Pd / C catalyst is separated by centrifugation; contacting the hydrogenated mass with methanol and sulphuric acid at a temperature in the range of 80 to 90 °C for a period in the range of 30 min to 90 min to obtain a methyl ester of hydrogenated mass; extracting the methyl ester of hydrogenated mass with dichloromethane to obtain iso-stearic acid.

[0019] Other aspects of the invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learnt by the practice of the invention.

[0020] ACRONYMS USED TO DESCRIBE THE INVENTION:

[0021] FER: Ferrierite Zeolite

[0022] BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 illustrates powder X-Ray diffraction of template free ferrierite zeolite.

[0024] Figure 2 illustrates FESEM Images of template free ferrierite zeolite.

[0025] Figure 3 illustrates GC-MS chromatogram of reaction mass after skeletal isomerization of commercial oleic feed catalyzed by indigenous Ferrite catalyst. The details of relevant peaks and compounds are:

[0026] DETAILED DESCRIPTION OF THE INVENTION

[0027] The following is a detailed description of embodiments of the disclosure. The embodiments are to clearly communicate the disclosure. However, the of detail offered is not intended to limit the anticipated variations of embodiments; to cover all modifications, equivalents, and alternatives fall within the spirit and scope of the present disclosure.

[0028] All publications herein are incorporated by reference to the same extent as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference. Where a definition or use of a term in an incorporated reference is inconsistent or contrary to the definition of that term provided herein, the definition of that term provided herein applies and the definition of that term in the reference does not apply.

[0029] A reference throughout this specification to “one embodiment” or “an embodiment” means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrases “in one embodiment” or “in an embodiment” in various places throughout this specification do not necessarily all refer to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.

[0030] As used in the description herein that follow, the meaning of “a,” “an,” and “the” includes plural reference unless the context clearly dictates otherwise. Also, as used in the description herein, the meaning of “in” includes “in” and “on” unless the context clearly dictates otherwise.

[0031] Unless the context requires otherwise, throughout the specification which follow, the word “comprise” and variations thereof, such as, “comprises” and “comprising” are to be construed in an open, inclusive sense that is as “including, but not limited to.”

[0032] The recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e. g. “such as”) provided with respect to certain embodiments herein is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention.

[0033] Groupings of alternative elements or embodiments of the invention disclosed herein are not to be construed as limitations. Each group member can be referred to individually or in any combination with other members of the group or other elements found herein. One or more members of a group can be included in, or deleted from, a group for reasons of convenience and / or patentability. When any such inclusion or deletion occurs, the specification is herein deemed to contain the group as modified.

[0034] The description that follows, and the embodiments described therein, is provided by way of illustration of an example, or examples, of particular embodiments of the principles and aspects of the present disclosure. These examples are provided for the purposes of explanation, and not of limitation, of those principles and of the disclosure.

[0035] It should also be appreciated that the present disclosure can be implemented in numerous ways, including as a system, a method or a device. In this specification, these implementations, or any other form that the invention may take, may be referred to as processes. In general, the order of the steps of the disclosed processes may be altered within the scope of the invention.

[0036] The headings and abstract of the invention provided herein are for convenience only and do not interpret the scope or meaning of the embodiments.

[0037] The following discussion provides many example embodiments of the inventive subject matter. Although each embodiment represents a single combination of inventive elements, the inventive subject matter is considered to include all possible combinations of the disclosed elements. Thus, if one embodiment comprises elements A, B, and C, and a second embodiment comprises elements B and D, then the inventive subject matter is also considered to include other remaining combinations of A, B, C, or D, even if not explicitly disclosed.

[0038] The terms “template free ferrierite zeolite” and “ferrierite zeolite” are used herein throughout the specification with the same or relatively same meaning. The present disclosure provides an efficient quasi-solid state zinc metal batteries, the present disclosure provides stuning the cathode-electrolyte interface to improve the performance of quasi-solid state zinc metal batteries. The combination of gel polymer electrolyte and modified cathode using the gel polymer electrolyte offers improved interface stability, increased ion transport, Zn dendrite not forming, extended cycle life, and corrosion mitigation etc.

[0039] An embodiment of the present disclosure provides a template free ferrierite zeolite for the conversion of oleic acid into iso-stearic acid having Si / Al ratio in the range of 12-13, particle size in the range of 0.5 to 2 micrometer, external surface are in the range of 250 m2 / g to 350 m2 / g, pore volume in the range of 0.15 cc / g to 0.25 cc / g and sheet or platelletes size morphology.

[0040] In a preferred embodiment, the template free ferrierite zeolite has a Si / Al ratio of 12.5, particle size in 1.5.to 2pm. micrometer, external surface are of 300 m2 / g and pore volume of 0.21 cc / g.

[0041] Another embodiment of the present disclosure provides a method of preparation of a template free ferrierite zeolite comprising: a) dissolving 0.93 to 0.18 kg of aluminum source in 1 to 2.5 L of water with stirring to obtain a solution A; b) dissolving 3 kg of silica source in 1 to 2 L of water with stirring to form a solution B; c) adding the solution B obtained at step b) into the solution A obtained at step a) under vigorous stirring for a period in the range of 30 min to 90 min to form a first mixture; d) dissolving 0 to 0.13 kg of sodium hydroxide in 1 to 2.5 L of water to form a solution C; e) adding the solution C obtained at step d) in the first mixture obtained at step c) to form a second mixture; f) adding 5 to 15 % wt. of FER seed in the second mixture obtained at step e) with stirring for a period in the range of 1 to 3 h to obtain a homogeneity of the reaction mixture; g) transferring the reaction mixture obtained at step f) into 20 L SS autoclave and subjected to hydrothermal crystallization at a temperature in the range of 130 to 170 °C for a period in the range of 16 h to 74 h to obtain a slurry; h) filtering the slurry obtained at step g) to obtain a solid particles followed by washing with water until the filtrate’s pH fell below 10; and i) drying at a temperature in the range of 80 to 120 °C for a period in the range of 10 to 14 h to obtain a template free ferrierite zeolite.

[0042] In another embodiment, fumed silica or sodium silicate is used as a silica source and aluminium sulphate or sodium aluminate is used as a source of aluminium.

[0043] In a preferred embodiment, sodium silicate and aluminium sulphate are used as silica and aluminium sources, respectively.

[0044] In a preferred embodiment, solution B obtained by dissolving 3 kg of sodium silicate in 1 L water is added to solution A of 0.37 kg of aluminum sulphate octadecahydrate into 1 L water under vigorous stirring for a period of 60 min.

[0045] In a preferred embodiment, 10% the FER seed with respect to the silica source is added in the second mixture with stirring for a period of 2 hrs to obtain a homogeneity of the reaction mixture followed by transferring into 20 L SS autoclave and subjected to hydrothermal crystallization at a temperature of 150 °C for a period in the range of 24 hrs to obtain a slurry.

[0046] In a preferred embodiment, the slurry is filtered to obtain a solid particles followed by washing with water until the filtrate’s pH fell in the range of 8 to 10 to and to dried at a temperature of 100 °C for a period in the range of 12 hrs to obtain a template free ferrierite zeolite.

[0047] In an embodiment, the dried sample thus obtained was further subjected for repetitive ion exchange using 1 M ammonium chloride solution (in the proportion 10 ml per gram of solid) for 3 times at a temperature in the range of 80 to 90 °C preferably 85 °C, for a period in the range of 2 to 4 h, preferably of 3 h. Excess salt was washed by deionized water until there was no detectable chloride ions and the solid was dried at a temperature in the range of 80 to 120 °C, preferably at 100 °C. These samples were further subjected to calcination at a temperature in the range of 400 to 600 °C preferably at 500 °C for a period in the range of 4 to 6 h preferably for 5 h under flowing air to convert them into corresponding protonic forms.

[0048] In an embodiment, the present invention provides a process of conversion of unsaturated linear acid into saturated linear or branched acid, wherein said process comprises the steps of: a) contacting unsaturated linear acid as a feed with 3 to 12.5 wt % of template free ferrierite zeolite as claimed in claim 1 with respect to feed, 4 to 12 wt % of water with respect to feed, and 5 to 10 wt. % of triphenyl phosphine with respect to ferrierite zeolite in a reactor at a temperature in the range of 250 to 300 °C for a period in the range of 10 to 24 h under stirring at a speed in the range of 100 to 200 rpm and a nitrogen gas at a pressure in the range of 5 to 15 bar to obtain a reaction mass having unsaturated branched fatty acids as a product and trans isomer products as other products; b) separating the water from the reaction mass obtained at step a) and removing the catalyst using centrifugation to obtain a reaction mass; c) subjecting the reaction mass obtained at step b) to hydrogenation using 4 to 15 wt. % Pd / C with respect to reaction mass feed at a temperature in the range of 120 to 200 °C for a period in the range of 2 to 24 h to obtain a hydrogenated mass and Pd / C catalyst is separated by centrifugation; d) contacting the hydrogenated mass obtained at step c) with methanol and sulfuric acid at a temperature in the range of 40 to 90 °C for a period in the range of 30 min to 120 min to obtain a methyl ester of hydrogenated mass; and e) extracting the methyl ester of hydrogenated mass obtained at step d) with dichloromethane to obtain rated linear or branched acid.

[0049] In an embodiment, the unsaturated linear acid is selected from C15 to C20 containing unsaturated linear acid.

[0050] In an embodiment, the saturated linear or branched acid is selected from C15 to C20 containing saturated linear or branched acid. Another embodiment of the present disclosure provides a process of conversion of oleic acid to iso-stearic acid comprising: a) contacting oleic acid as a feed with 3 to 12.5 wt % of template free ferrierite zeolite as claimed in claim 1 with respect to feed, 4 to 12 wt % of water with respect to feed, and 5 to 10 wt % of Triphenyl Phosphine with respect to modified ferrierite zeolite in a reactor at a temperature in the range of 250 to 300 °C for a period in the range of 10 to 24 hrs with stirring at a speed in the range of 100 to 200 rpm and under nitrogen gas at a pressure in the range of 5 to 15 bar to obtain a resultant reaction mass have Unsaturated Branched Fatty acids (BUFA desired Product) and other products were predominant trans isomers; b) separating the water from the reaction mass obtained at step a) and removing the catalyst using centrifugation to obtain a reaction mass; c) subjecting the reaction mass obtained at step b) to hydrogenation using 4 to 15 wt % Pd / C with respect to reaction mass feed at a temperature in the range of 120 to 200 °C for a period in the range of 2 to 24 hrs to obtain a hydrogenated mass and Pd / C catalyst is separated by centrifugation; d) contacting the hydrogenated mass obtained at step c) with methanol and sulphuric acid at a temperature in the range of 40 to 90 °C for a period in the range of 30 min to 120 min to obtain a methyl ester of hydrogenated mass; and e) extracting the methyl ester of hydrogenated mass obtained at step d) with dichloromethane to obtain iso-stearic acid.

[0051] In a preferred embodiment, 25 g of oleic acid as a feed with 10 wt. % of template free ferrierite zeolite w.r. to feed, 8 wt % of water w.r. to feed, 10 wt % of Triphenyl Phosphine w.r. to modified ferrierite zeolite in a reactor at a temperature in the range of 250 to 300 °C for a period in the range of 15 hrs with stirring at a speed in the range of 100 to 200 rpm and nitrogen gas at a pressure 10 bar to obtain a resultant reaction mass have

[0052] In a preferred embodiment, the reaction mass is subjected to hydrogenation using 4 wt % of 10%Pd / C with respect to reaction mass feed at a temperature of 180 °C for a period in the range of 3 hrs to obtain a hydrogenated mass and Pd / C catalyst is separated by centrifugation. In a preferred embodiment, hydrogenated mass is contacted with methanol and sulphuric acid at a temperature of 85 °C for a period in the range of 60 min to obtain a methyl ester of hydrogenated mass.

[0053] In an embodiment, during skeletal reaction, water acts as a co-catalyst to allow more accessibility of Bronsted sites over zeolites and TPP acts as a selectivity enhancer to improve the selectivity of BUFA during process.

[0054] EXAMPLES

[0055] Example 1: Synthesis of template free ferrierite zeolite:

[0056] The initial gel mixture was prepared using a molar gel composition of 0.3 Na2O: 0.04 AI2O3: S1O2: 20 H2O and 10% seed (Ferrierite, Si / Al = 10). Initially, Solution A of aluminium sulphate was prepared by dissolving the 0.37 kg of aluminium sulphate octadecahydrate into 1 L DI (deionized) water and kept for stirring till the complete dissolution of aluminium sulphate in the water. Solution B was prepared by dissolving 3 kg Sodium silicate in 1 L DI water and then added slowly into Solution A under vigorous stirring. Stirring was continued for 1 h. Solution C, prepared by dissolving 0.028 kg NaOH in 1.099 L water, was added into a mixture of A and B. Finally, FER seed (10 wt% with respect to silica source) was added and stirred for another 2 h to achieve homogeneity of the reaction mixture. The final reaction mixture was transferred into a 20 L SS autoclave and subjected to hydrothermal crystallization at 150 °C for 48 h. After 48 h hydrothermal crystallization, the solid product was filtered out from the mother liquor and thoroughly washed with D.I. water until the filtrate’s pH fell below 10. The product was dried overnight at 100 °C for 12 h.

[0057] The dried sample thus obtained was further subjected for repetitive ion exchange using 1 M ammonium chloride solution (in the proportion 10 ml per gram of solid) for 3 times at 85°C for 3 h. Excess salt was washed by deionized water until there was no detectable chloride ions and the solid was dried at 100°C. These samples were further subjected to calcination at 500°C for 5 h under flowing air to convert them into corresponding protonic forms.

[0058] Characterization of prepared template free ferrierite zeolite was carried out. The powder X-ray diffraction of pure and well crystalline ferrierite phase is shown in Figure 1. Further, FESEM image of the aggregated plate like morphology as shown in Figure 2. BET analysis of the template free ferrierite zeolite is as shown in Table 1. Table 1: BET analysis

[0059] Example 2: Conversion of Oleic Acid to Isostearic acid

[0060] Skeletal Isomerisation- It was carried out in Batch reactor at 250 °C-300 °C, 10-24 hrs, using Oleic acid feed 25g, synthesized template free ferrierite zeolite as a catalyst. Catalyst Loading was 5 to 12.5 wt % w.r.to feed, water (4 to 12 wt% w.r.to feed), Triphenyl Phosphine commonly known as a TPP (5 to 10 % w.r.to Ferrite Catalyst) in Batch reactor, N2(g)-10 bar, stirring at 250 rpm resultant reaction mass have Unsaturated Branched Fatty acids (UBFA desired Product) and other products were predominant trans isomers mainly. Water which was added in the reaction mass as a co-catalyst were separated using a separating funnel and the catalyst was recovered using centrifugation. Such obtained reaction mass was further subjected to hydrogenation.

[0061] Hydrogenation of reaction mass obtained in skeletal isomerization- The resultant reaction mass obtained in skeletal isomerization was hydrogenated using 10 wt% Pd / C w.r.to reaction mass feed in the Batch reactor at 180 °C, for 3 hrs. After hydrogenation, the Pd / C catalyst was separated by centrifugation.

[0062] To quantify products in GC-MS, hydrogenated mass was converted into their respective methyl esters through esterification where methanol was taken in excess and H2SO4 as mineral acid catalyst. This mixture was esterified at 85 °C for 1 h and the organic layer was extracted in Dichloromethane (DCM). Resultant Methyl esters of hydrogenated mass extracted in DCM then studied over GC-MS with FAME column (10mm length for qualitative and quantitative analysis). GC-MS chromatogram of reaction mass after skeletal isomerization of commercial Oleic Feed catalyzed by indigeous Ferrite catalyst are shown in Figure 3. Characterization of Reaction Products were carried out over GC-MS, Products were analyzed and confirmed using Std FAME Column and Mass fragments patterns of corresponding peak in Table 2.

[0063] Table 2: GC-MS chromatogram and confirmation of molecule.

[0064] During Skeletal reaction, water acts as a co-catalyst to allow more accessibility of Bronsted sites over zeolites and TPP acts as a selectivity enhancer to improve the selectivity of BUFA during process. Skeletal isomerization of oleic acids are given in Table 3. Table 3: Conversion of oleic acid, selectivity of isostearic acid.

[0065] Commercial Feed - 25g, All reactions were carried out in batch reactor of 100 ml, 10 Bar of N2 (g), Catalyst is taken w.r.t Feed, Water is taken w.r.to Feed and TPP is w.r.to catalyst (H-Ferrierite), Conversion is based on GC-MS

[0066] Comparison between commercial oleic acid feed & distillated more pure oleic acid feed are given in Table 4.

[0067] Table 4: Conversion of oleic acid, selectivity of isostearic acid and yield.

[0068] Isomerisation Reaction -commercial feed - 25 grams, Catalyst - 2.5 gms (10 wt% wrt feed)

[0069] TPP (10 wt% wrt catalyst) - 0.25 grams, Water (8 wt% wrt feed) - 2gms,

[0070] Time-15hrs, Temp -270 deg C, N2(g) Pressure - 10 bar, conversion is based on GC-MS. ADVANTAGES OF THE INVENTION

[0071] • Raw material used are Sodium silicate and aluminum sulphate are quite inexpensive and are not used in the prior arts.

[0072] • First time, the present disclosure provides low Si to Al ratio of 12.5 Ferrites without any organic template for conversion of commercial grade oleic acid (72% purity) to isostearic acid.

[0073] • Seeds used during Crystallization are comprised of ferrites with of low Si to Al ratio 10 which enables crystallite resultant ferrites in the least possible crystalline time of 48hrs.

[0074] • Commercial grade oleic acid conversion of 85% and isostearic acid selectivity of 86% is obtained.

Claims

WE CLAIM:

1. A template free ferrierite zeolite for a conversion of unsaturated linear acid into saturated linear or branched acid, wherein said template free ferrierite zeolite has Si / Al ratio in the range of 12-13, particle size in the range of 0.5 to 2 micrometer, external surface area in the range of 250 m2 / g to 350 m2 / g, pore volume in the range of 0.15 cc / g to 0.25 cc / g, and have a sheet or platelet like morphology.

2. The template free ferrierite zeolite as claimed in claim 1, wherein said template free ferrierite zeolite has a Si / Al ratio of 12.5, particle size in 1.

5. to 2pm micrometer, external surface of 300 m2 / g and pore volume of 0.21 cc / g.

3. A method of preparation of a template free ferrierite zeolite as claimed in claim 1, wherein said method comprises: a) dissolving aluminum source in water under stirring to obtain a solution A; b) dissolving silica source in water under stirring to form a solution B; c) adding the solution B obtained at step b) into the solution A obtained at step a) under vigorous stirring for a period in the range of 30 to 90 minutes to form a first mixture; d) dissolving sodium hydroxide in water to form a solution C; e) adding the solution C obtained at step d) in the first mixture obtained at step c) to form a second mixture; f) adding 5 to 15 % wt. of ferrierite zeolite seed in the second mixture obtained at step e) with stirring for a period in the range of 1 to 3 h to obtain a homogeneity of the reaction mixture; g) transferring the reaction mixture obtained at step f) into an autoclave and subjected to hydrothermal crystallization at a temperature in the range of 130 to 170 °C for a period in the range of 16 to 74 h to obtain a slurry; h) filtering the slurry obtained at step g) to obtain solid particles followed by washing with water until the filtrate’s pH achieves below 10; and drying at atemperature in the range of 80 to 120 °C for a period in the range of 10 to 14 h to obtain a template free ferrierite zeolite.

4. The method as claimed in claim 3, wherein the silica source is a fumed silica or a sodium silicate, and the aluminium source is aluminium sulphate or sodium aluminate.

5. The method as claimed in claim 4, wherein the silica source is sodium silicate and aluminium source is aluminium sulphate.

6. The method as claimed in claim 3, wherein the method further comprises the steps of: i. subjecting the dried template free ferrierite zeolite for repetitive ion exchange using ammonium chloride solution for at least 3 times at a temperature in the range of 80 to 90 °C for a period in the range of 2 to 4 h; ii. washing excess salt by deionized water until there is no detectable chloride ions; and iii. drying the solid at a temperature in the range of 80 to 120 °C and further calcinating at a temperature in the range of 400 to 600 °C for a period in the range of 4 to 6 h under flowing air to convert them into corresponding protonic forms.

7. A process of conversion of unsaturated linear acid into saturated linear or branched acid, wherein said process comprises the steps of: a) contacting unsaturated linear acid as a feed with 3 to 12.5 wt % of template free ferrierite zeolite as claimed in claim 1 with respect to feed, 4 to 12 wt % of water with respect to feed, and 5 to 10 wt. % of triphenyl phosphine with respect to ferrierite zeolite in a reactor at a temperature in the range of 250 to 300 °C for a period in the range of 10 to 24 h under stirring at a speed in the range of 100 to 200 rpm and a nitrogen gas at a pressure in the range of 5 to 15 bar to obtain a reaction mass having unsaturated branched fatty acids as a product and trans isomer products as other products; b) separating the water from the reaction mass obtained at step a) and removing thecatalyst using centrifugation to obtain a reaction mass; c) subjecting the reaction mass obtained at step b) to hydrogenation using 4 to 15 wt. % Pd / C with respect to reaction mass feed at a temperature in the range of 120 to 200 °C for a period in the range of 2 to 24 h to obtain a hydrogenated mass and Pd / C catalyst is separated by centrifugation; d) contacting the hydrogenated mass obtained at step c) with methanol and sulfuric acid at a temperature in the range of 40 to 90 °C for a period in the range of 30 min to 120 min to obtain a methyl ester of hydrogenated mass; and e) extracting the methyl ester of hydrogenated mass obtained at step d) with dichloromethane to obtain rated linear or branched acid.

8. The process as claimed in claim 7, wherein the unsaturated linear acid is selected from C 15 to C20 containing unsaturated linear acid.

9. The process as claimed in claim 7, wherein the saturated linear or branched acid is selected from C15 to C20 containing saturated linear or branched acid.

10. A process of conversion of oleic acid to iso-stearic acid comprising: a) contacting oleic acid as a feed with 3 to 12.5 wt % of template free ferrierite zeolite as claimed in claim 1 with respect to feed, 4 to 12 wt % of water with respect to feed, and 5 to 10 wt % of Triphenyl Phosphine with respect to modified ferrierite zeolite in a reactor at a temperature in the range of 250 to 300 °C for a period in the range of 10 to 24 hrs with stirring at a speed in the range of 100 to 200 rpm and under nitrogen gas at a pressure in the range of 5 to 15 bar to obtain a resultant reaction mass have Unsaturated Branched Fatty acids (BUFA desired Product) and other products were predominant trans isomers; b) separating the water from the reaction mass obtained at step a) and removing the catalyst using centrifugation to obtain a reaction mass; c) subjecting the reaction mass obtained at step b) to hydrogenation using 4 to 15 wt % Pd / C with respect to reaction mass feed at a temperature in the range of 120 to 200 °C for a period in the range of 2 to 24 hrs to obtain a hydrogenatedmass and Pd / C catalyst is separated by centrifugation; d) contacting the hydrogenated mass obtained at step c) with methanol and sulphuric acid at a temperature in the range of 40 to 90 °C for a period in the range of 30 min to 120 min to obtain a methyl ester of hydrogenated mass; and e) extracting the methyl ester of hydrogenated mass obtained at step d) with dichloromethane to obtain iso-stearic acid.

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