Title of Invention

A NOVEL CATLYST FOR THE SYNTHESIS OF GLYCIDOL DIRECTLY FROM GLYCEROL AND PROCESS THEREOF

Abstract

Heterogeneous solid base catalyst comprising supported mixed oxide base catalyst has been disclosed herein. The catalyst of the invention comprising at least 0.1 to 50 mass percent of alkali and/or alkaline earth metal ions and 5 to 50 mass percent of zirconia, titania and/or mixture thereof of the total mass percent of the catalyst wherein said heterogeneous solid base catalyst has specific surface area in the range 10 m2/g to 600 m2/g. Application side of the said catalyst has shown remarkable improvement in process of producing glycerol carbonate and glycidol from glycerol. It comprises of reacting glycerol and dimethyl carbonate in a solvent by using a heterogeneous reusable solid base catalyst. This catalyst is highly active, separable, regenerable and reusable, providing high conversion and selectivity towards glycerol carbonate and/or glycidol

Full Text

FORM2 THE PATENTS ACT, 1970 (39 of 1970) COMPLETE SPECIFICATION (See section 10 and rule 13) 1. TITLE OF THE INVENTION: "A PROCESS FOR THE SYNTHESIS OF GLYCIDOL DIRECTLY FROM GLYCEROL AND CATALYST THEREFOR" 2. APPLICANT NAME NATIONALITY: ADDRESS : YADAV GANAPATI DADASAHEB (Last Name/Surname) (First Name) (Father's Name/Middle Name) INDIAN CHEMICAL ENGINEERING DEPARTMENT, INSTITUTE OF CHEMICAL TECHNOLOGY (DEEMED UNIVERSITY), NATHALAL PARIKH MARG, MATUNGA (EAST), MUMBAI 400 019, INDIA The following specification particularly describes the invention and the manner in which is to be performed. FIELD OF THE INVENTION The present invention is related to heterogeneous solid base catalyst comprising supported mixed oxide wherein said heterogeneous solid base catalyst has specific surface area in the range 10 m /g to 600 m /g. A process of producing glycidol directly from glycerol in a single step comprises of reacting glycerol and dimethyl carbonate in a solvent by using a heterogeneous reusable solid base catalyst. This catalyst is highly active, separable, regenerable and reusable, providing high conversion and selectivity towards glycidol. BACKGROUND OF THE INVENTION Heterogeneous solid catalyst are always been great area of interest to researcher. Thus many efforts have been made to design of better heterogeneous solid catalyst with high specific area which can be easily separable, regenerable and reusable. Many inventors claim for better heterogeneous catalyst with various support but they have their own drawbacks for different reaction system. Numerous catalytic reactions have been identified in past few years, in which solid base catalysts have proved to be capable of producing interesting results in terms of performance. The catalytic properties of solid base catalysts are mainly associated with the quantity and the strength of the base sites existing on the surface. United States Patent 7341973 relates to solid base catalysts consisting of an amorphous material obtained from silica or alumina gel containing an alkaline, earth-alkaline or transition metal (M), characterized by a molar ratio between metal (M) and Si or Al ranging from 30:1 to 0.0001:1, a surface area ranging from 100 to 600 m2/g, an overall pore volume ranging from 0.1 to 1.1 ml/g. Said catalysts can be conveniently used in base catalysis reactions. US patent application 20070189955, claims for catalyst composition based on cerium oxide and zirconium oxide in an atomic proportion Ce/Zr of at least 1, and has a reducibility rate of at least 70% and a surface area of at least 15 m2/g. Glycidol has the advantage of being a current commercial, albeit specialty product. High cost and large market demand for glycidol indicates the need for the convenient route of its synthesis. There is no known process which gives glycidol in high state of purity with minimum energy requirement and minimum waste. The increasing production of glycerol and growth of bio-diesel plants has resulted in an abundant supply of glycerol leading to its price decline. Glycerol carbonate can split off carbon dioxide yielding glycidol. It is well known that glycidol has a big impact on the environment. Glycidol is reasonably anticipated to be a human carcinogen based on sufficient evidence of carcinogenicity in experimental animals, Glycidol is soluble in water and in case of leakage can be harmful to fish. Glycidol also known as 2-(Hydroxymethyl)oxirane, allyl alcohol oxide, 3-hydroxypropylene oxide, 2,3-epoxy-l-propanol, oxirane methanol, 3-hydroxy-l,2-epoxypropane having boiling point of 166 °C is incompatible with strong acids or bases, salts (e.g., aluminum chloride, iron(III) chloride, tin(IV) chloride) or metals (e.g., copper, zinc). Glycidol is used as an additive for oil and synthetic hydraulic fluids, and as a diluent in some epoxy resins. Glycidol also falls into the generalized category of chiral epoxides. These chiral epoxides or glycidols can be used as reagents in a number of pharmaceutical and fine chemical applications that includes pesticides and herbicides, flavors and fragrances, chiral polymers, and liquid crystals. It is used as a stabilizer for natural oils and vinyl polymers, demulsifier, dye-leveling agent. It is used in surface coatings, sanitary chemicals and sterilizing milk of magnesia, as a gelatin agent in solid propellants. Only few routes of synthesis of glycidol are described in the literature. The main routes for the synthesis of glycidol are as follows: 1. Epoxidation of Allyl alcohol 2. Decarboxylation of Glycerol carbonate 3. Dehydrochlorination of chloroglycerol using base catalyst Japanese patent WO 2007145278 discloses the process of producing glycidol from glycerol carbonate which was in turn obtained from the reaction of glycerol and urea in the presence of zinc sulphate as a catalyst. The glycerol carbonate obtained by further distillation was then subjected to sulphate heating at 180 °C temp for 3 h at 400 psi in the presence of anhydrous sodium to obtain glycidol. In the paper "Studies in Surface Science and Catalysis (2001), 135, 3806-3813", the catalytic synthesis of glycidol from glycerol carbonate in presence of zeolite A is reported. The reaction takes place in two steps: cationic/anionic ring opening-dimerization of glycerol carbonate and cyclization of the dimer to glycidol and CO2. Zeolite A is bifunctional (acidic and basic) and catalyzes both steps. The yield of glycidol is approximately 72% with zeolite A and glycerol, compared with 25% in absence of catalyst and initiator. Continuous feeding of glycerol carbonate to maintain a high concentration gives 86% yield of glycidol. According to Chemical Papers (2001), 55(3), 185-191 on "Influence of acetone and acetonitrile content on the epoxidation of allyl alcohol with hydrogen peroxide over TS-1 catalyst", a decrease in acetone content results in increasing selectivity for glycerol synthesis and a decrease in selectivity for glycidol and allyl glycidyl ether. Higher selectivity for glycidol and allyl glycidyl ether is achieved when the process is run in the presence of acetone as a solvent. Russian patent RU 2130452 reports the preparation of glycidol by treatment of glycerol monochlorohydrin with basic reagent in organic solvent. According to patent WO 9840371 by ONIDOL, titled "Method and apparatus for producing an epoxide, notably glycidol" discloses the synthesis of glycidol by heating glycerol carbonate at 165° C under reduced pressure to produce ring contraction with elimination of CO2. The reaction is effected in a solid/liquid system in the presence of a polyol and a solid catalyst consisting of a type-A zeolite or y-alumina. US Patent 3954815 discloses glycidol (I) and glycerol (by hydrolysis of I) synthesis via epoxidation of allyl alcohol with 5-40% AcOOH in anhydrous inert solvents, especially diisobutyl ketone. Also according to JP 49025643 for oxidation of allylic alcohols, glycidol and glycerin are prepared by oxidation of allyl alcohol with H2O2 in the presence of catalysts and a phenolic substance. According to SU 288742 and Journal of the American Chemical Society (1930), 52 1521-1527, glycidol is prepared by treating glycerol monochlorohydrin. DE 1226554 reports the preparation of glycidol from glycerol monochlorohydrin using K2CO3 as a base. GB 971633 discloses the process for preparation of glycerol by passing aqueous solutions of acrolein-derived halohydrins (0.05%) through a strongly basic anion exchange resin at 20-60° and at atmospheric pressure to yield glycidol and then passing the glycidol solution through a catalytic amount of a cation exchange resin to yield a diluted solution of relatively pure glycerol. Thermal decomposition of glyceryl carbonates as reported in Journal of American Chemical Society (1952), 74 2100-2101 mentions convenient method for preparing glycidol in 60-85% yield from glycerol. In the process of production of glycidol from glycerol, the glycerol carbonate is first been prepared in pure form by either of the reported process and then decarboxylated. This is highly cost effective and not economic for industrial scale production of glycidol. There is no direct process for the conversion of glycerol to glycidol in a single step which will have enormous implications for glycidol and its family of products. In fact the reverse is reported extensively in which glycidol is hydrated to give glycerol. This process in the present invention relates to the preparation of glycidol. OBJECTIVE OF THE INVENTION Objective of the present invention is to design heterogeneous solid base catalyst which can be easily separable, regenerable and reusable. Another objective of the present invention is to specific selection of metal ions for the heterogeneous solid base catalyst. Another objective of the present invention is to design catalyst having specific surface area in the range 10 m2/g to 800 m2/g. Another objective of the present invention is to develop various reactions catalysed by heterogeneous solid base catalyst developed herein, with high selectivity and conversion. One more objective of the present invention is to develop a process for manufacture of glycerol carbonate from glycerol in the presence of said heterogeneous solid base catalyst with or without solvent. The objective of the present invention is to develop a process for manufacture of glycidol directly from glycerol in the presence of said heterogeneous solid base catalyst with or without solvent. Another objective of the present invention is to develop an efficient process for production of glycidol which is now in demand and have wide area of applications. Another objective of the present invention is to utilize the cheap renewable resources for the manufacturing of glycerol carbonate and glycidol to lower the process economy. Yet another objective of the present invention is to provide a simple process for manufacturing glycidol at a low cost to validate the possibility of its extrapolation to industry. One more objective of the present invention is to provide preliminary information for evaluating an alternative strategy to utilize waste material glycerol for the production of glycidol using a novel heterogeneous reusable base catalyst. Another objective of the present invention is to develop process which utilizes minimum energy and gives minimum waste for production of glycidol with high purity. Yet another objective of the present invention is to develop process for production of glycerol carbonate and glycidol with minimum total reaction time. Yet another objective of the present invention is to develop process for production of glycerol carbonate and glycidol under mild conditions which utilizes minimum or no solvent in the reaction system. One more objective of the present invention is to develop a process for the production of glycidol which utilizes dimethyl carbonate as reagent which is now being positioned as a green replacement for phosgene in the production of polycarbonates and polyurethanes, also glycerol and dimethyl carbonate are environmentally benign and renewable reagents. SUMMARY OF INVENTION In the present invention solid base catalyst is designed and developed comprising at least 0.1 to 50 mass percent of alkali or alkaline earth metal supported on different forms of titania, zirconia and/or mixtures thereof. In a group of invention, a convenient process for manufacturing of glycerol carbonate and glycidol has been designed and developed wherein glycerol is reacted with dimethyl carbonate in the presence of heterogeneous solid base catalyst of the present invention with or without solvent. Further, products are separated from the reaction mixture by distillation under vacuum. In the present process solvent is selected from group of dimethyl formamide, dimethyl sulphoxide, dimethyl acetamide, N-methyl pyrrolidone and methanol, ethanol, isopropanol, butanol and a like and/or mixtures thereof. BRIEF DESCRIPTION OF DRAWINGS Drawing 1: Scanning Electron Microscope images of one of the catalyst at various magnifications Drawing 2: TPD Data for CO2 Desorption of one of the catalyst Drawing 3: FT-IR graph for one of the catalyst Drawing 4: XRD image for one of the catalyst DETAILED DESCRIPTION OF INVENTION In accordance with process of the present invention, a method of utilizing heterogeneous reusable solid base catalyst for conversion of glycerol to glycerol carbonate and glycidol is described. In the present invention, synthesis is carried out under mild conditions with or without any solvent. Glycerol and dimethyl carbonate used in the present invention are environmentally benign and renewable reagents. In the present invention, heterogeneous solid base catalyst has been designed and developed which comprises alkali or alkaline earth metal incorporated or supported on titania, zirconia, and/or mixture thereof with specific surface area in the range 10 m2/g to 800 m2/g. Thus, the catalyst of the present invention is heterogeneous solid base catalyst which comprising at least 0.1 to 50 mass percent of alkali or alkaline earth metal and/or mixture thereof incorporated or supported on the different forms of titania, zirconia, and/or mixture thereof. Thus, metal can be metal ion selected from alkali group consisting of Li+, Na+, K+, Rb+, Cs+ or alkaline earth metal Mg++, Ca+, Sr+, Ba+. One of embodiments of the invention is the heterogeneous solid base catalyst which comprises of alkali or alkaline earth metal ion in 0.1 to 50 mass percent of the total mass percent of the catalyst according to type of solid catalysed reaction. One of embodiments of the invention is that in the heterogeneous solid base catalyst, divalent metal can be selected from the group consisting of Li+, Na+, K+, Rb+, Cs+ or alkaline earth metal Mg^, Ca+, Sr+, Ba++. One of embodiments of the invention is that in the heterogeneous solid base catalyst, metal is preferably selected from Li+, Na+, K+, Mg++ and/or mixture thereof. One of embodiments of the invention is that in the heterogeneous solid base catalyst, metal salt used for the synthesis of catalyst can be in the form of nitrate, chloride, carbonate, acetate isopropoxide, sulphate or hydroxide. One of the embodiments of heterogeneous solid base catalyst is that the support can be present in the form of its oxides, hydroxides and /or in its metal compound form according to the type of solid catalysed reaction. One of the embodiments of heterogeneous solid base catalyst is that metals can be incorporated or supported on different forms of zirconia, titania and/or mixture thereof. One of further embodiments of present invention is that heterogeneous solid base catalyst is calcinated alkali metal ion supported on zirconia, titania and/or mixture thereof. The catalyst is found to have excellent activity towards synthesis of glycerol carbonate and glycidol. Also this catalyst can be activated and reused for the same or different reactions. Thus resultant heterogeneous solid base catalyst has pore diameter in the range of 1 nm to 20 nm and pore volume in the range of 0.01 cm3/g to 1 cm3/g. Heterogeneous solid base catalyst synthesis comprises of either co-precipitation method or wet-impregnation method. General method for production of heterogeneous solid base catalyst by wet-impregnation method comprises synthesis of hydroxides of zirconium or titanium and/or mixture thereof. The dried resultant hydroxide can also be calcined at high temperature to give catalyst support or can be used as such. These catalyst support with or without calcinations is impregnated with aqueous solutions of alkali or alkaline earth metal salts slowly under constant stirring. Vigorous stirring may be continued until a dry material is obtained which is further dried at 120 °C temperature and calcined at temperature of atleast 300 °C temp for a minimum of 2 to 20 hours to get active catalyst. General method for production of heterogeneous solid base catalyst by co-precipitation method comprises mixing aqueous alkali or alkaline earth metal salt solution with aqueous salt solution of zirconium or titanium precursor in a particular ratio. This clear liquid solution is then co-precipitated under constant stirring to get its hydroxides. The resultant precipitated solution is kept for aging for minimum of 0.25 to 30 hours at temperature between 20 to 100 °C. The precipitate is then filtered, washed with distilled water until neutral pH, dried in oven at 120 °C temperature and finally calcined at atleast 300 °C temperature for a minimum of 2 to 20 hours to give active catalyst. In further accord with the present invention, the catalyst comprises of mixed oxides of zirconia, titania and/or mixture thereof with alkali or alkaline earth metals. This heterogeneous catalyst is separated from the reaction mixture by simple filtration technique. The catalyst is found to have excellent activity towards glycerol carbonate and glycidol synthesis. Also this catalyst can be activated and reused for the same or different reaction. In the process, glycidol is manufactured using heterogeneous solid base catalyst to give excellent conversion of glycerol with high efficiency and selectivity. Heterogeneous solid base catalyst is easily separable, regenerable and reusable in glycidol manufacturing process. The amount of catalyst employed is typically about 0.001 to 50% based on weight of the glycerol in the reaction mixture. More preferably the amount employed is 2 to 15% based on weight of the glycerol in the reaction. In the present process for manufacturing of glycerol carbonate and glycidol, wherein glycerol is reacted with dimethyl carbonate in the presence of heterogeneous solid base catalyst which has been disclosed earlier and then further separation of products from final reaction mixture by distillation under vacuum. The process of the invention may be carried out at desired temperature range of 0 °C to 200 °C, preferably in the range 20 °C to 120 °C and at pressures less than, greater than or equal to atmospheric pressure. The reaction catalysed by heterogeneous solid base catalyst may be performed without solvent or in the presence of an inert solvent such as dimethyl formamide, dimethyl acetamide, N-methyl pyrollidone, dimethyl sulphoxide, methanol, ethanol, isopropanol, butanol and a like and/or mixture thereof. More preferably N-methyl pyrrolidone is employed as a solvent. One of the embodiments of the present invention for process of manufacture of glycerol carbonate and glycidol is that heterogeneous solid base catalyst is used in the range of about 0.001 to 50% of the glycerol weight % for the reaction. One of the embodiments of the present invention for process of manufacturing glycerol carbonate and glycidol is that reaction of glycerol with dimethyl carbonate is carried out in the temperature range of 0 °C to 200 °C, preferably in the range 20 °C to 120 °C. One of the embodiments of the present invention for process of manufacturing glycerol carbonate and glycidol is that the reaction of glycerol with dimethyl carbonate is carried out for reaction time of 8 hours, preferably for 15 to 300 minutes depending upon the type of solvent used. One of the embodiment of the present invention for process of manufacturing glycerol carbonate and glycidol, wherein the reaction of glycerol with dimethyl carbonate can be carried out in presence of solvent selected from group of dimethyl formamide, dimethyl sulphoxide, dimethyl acetamide, N-methyl pyrrolidone and methanol ethanol, isopropanol, butanol and a like and/or mixtures thereof. One more embodiment of the present invention for process of manufacturing glycerol carbonate and glycidol is that the molar ratio of glycerol to dimethyl carbonate is in the range of 1 : 1 to 1 : 10. Present invention for convenient process of manufacturing glycerol carbonate and glycidol from glycerol and dimethyl carbonate with or without solvent under mild conditions using heterogeneous reusable solid base as a catalyst as follows: Dimethyl Carbonate In methanol as a solvent, reaction gives good conversion of glycerol but more selectivity towards glycerol carbonate is obtained. Further continuation of this reaction to get glycidol is not achieved, as the amount of methanol in the reaction mixture is responsible for the formation of impurities such as methylated ethers. By utilization of N-methyl pyrrolidone as a solvent for the reaction, no formation of impurities is observed. The reactions are carried out in a glass reactor equipped with four equally spaced baffles and six bladed turbine impeller. The analysis of the products is done by gas chromatography equipped with flame ionization detector. The products glycerol carbonate and glycidol can be separated from the reaction mixture by simple distillation technique. In a preferred process of the invention, glycerol carbonate and glycidol is prepared by heating dimethyl carbonate with glycerol in N-methyl pyrrolidone as a solvent in the presence of a heterogeneous solid base catalyst at a temperature of about 20 °C to 120 °C for a sufficient reaction time. Therefore, the foregoing examples are considered as illustrative only of the principles of the invention. Moreover numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and method described, and accordingly. All suitable modifications and equivalents may be resorted to, falling within the scope of the invention for catalyst preparation and process for manufacture of glycidol are listed below. Example 1: Synthesis of K-Zr Catalyst by Wet-impregnation method Zirconium hydroxide is prepared from hydrolysis of 4 gm zirconium oxychloride with aqueous ammonia solution. The precipitate is aged for 2 hrs, filtered, washed with distilled water until neutral pH and dried in oven at 120 °C temperature for 12 hrs. This support is impregnated with aqueous solutions of 1 gm potassium carbonate. The excess solution is evaporated at room temperature with constant vigorous stirring. The catalyst is then dried at 110 °C and calcined at 600 °C in flowing air for 4 hours. The prepared catalyst is characterized completely by the following techniques: Scanning Electron Microscope images of the catalyst at various magnifications as shown in Drawing 1 TPD Data for CO2 Desorption of the catalyst as shown in Drawing 2 FT-IR graph for the catalyst as shown in Drawing 3 XRD graph for the catalyst as shown in Drawing 4 EDAX results are as follows: Compound Mass% K20 5.06 Zr02 94.94 Example 2: Synthesis of K-Zr Catalyst by Co-precipitation method 4 gm zirconium oxychloride, 1 g potassium carbonate is mixed and diluted with 50 ml distilled water. This clear solution is co-precipitated by drop wise addition of aqueous ammonia solution under vigorous stirring. The precipitate is aged for 12 hrs, filtered, washed with distilled water until neutral pH and dried in oven at 120 °C temperature for 12 hrs. The catalyst is then calcined at 600 °C in flowing air for 4 hours. Example 3: Synthesis of K-Ti Catalyst by Co-precipitation method 4 g titanium chloride, 1 g potassium carbonate is mixed and diluted with 50 ml distilled water. This clear solution is co-precipitated by dropwise addition of aqueous ammonia solution under vigorous stirring. The precipitate is aged for 12 hrs, filtered, washed with distilled water until neutral pH and dried in oven at 120 °C temperature for 12 hrs. The catalyst is then calcined at 600 °C in flowing air for 4 hours. Example 4-7: A series of reactions for synthesizing glycidol are carried out using 50 ml glass reactor, in which 5 g glycerol, 14.66 g dimethyl carbonate and 10 ml N-methyl pyrrolidone are mixed and heated to 90 °C temperature. Specified amount of catalyst (mentioned in Table 1) is added to the reaction mixture at this temperature. The quantity of catalyst is varied in these examples. After 2 h, reaction mixture is filtered to remove catalyst and then analyzed by Gas Chromatography equipped with FID detector using BP-20 capillary column. Table -1 Example Catalyst loading (wt % of glycerol) Duration (h) Conversion of glycerol (%) Selectivity to glycidol (%) Selectivity to glycerol carbonate (%) 4 2 2 82.50 64.18 33.3 5 5 2 93.08 69.61 26.81 6 10 2 95.73 80.26 15.72 7 15 2 93.67 78.74 18.72 * Selectivity of glycidol is calculated based on glycerol conversion Example 8-10: A series of reactions for synthesizing glycidol are carried out using 50 ml glass reactor, in which 5 g glycerol, specified quantity of dimethyl carbonate (mentioned in Table 2) and 10 ml N-methyl pyrrolidone are mixed and heated to 90 °C temperature. 0.5 gm (10% wt of glycerol) catalyst is added to the reaction mixture at this temperature. The quantity of dimethyl carbonate is varied in these examples. After 2 h, reaction mixture is filtered to remove catalyst and then analyzed by Gas Chromatography equipped with FID detector using BP-20 capillary column. Table - 2 Example mole ratio Duration (h) Conversion of Selectivity to glycerol glycidol (%) (%) Selectivity to glycerol carbonate (%) 8 1:2 2 63.34 84.06 13.72 9 1:3 2 98.13 82.7 13.09 10 1:4 2 98.67 75.65 16.81 * Selectivity of glycidol is calculated based on glycerol conversion Example 11-14: A series of reactions for synthesizing glycidol are carried out using 50 ml glass reactor, in which 5 gm glycerol, 14.66 gm dimethyl carbonate and 10 ml N-methyl pyrrolidone are mixed and heated to specified temperature (mentioned in Table 3). 0.5 gm (10% wt of glycerol) catalyst is added to the reaction mixture at this temperature. The temperatures of the reaction are varied in these examples. After the specified reaction time, reaction mixture is filtered to remove catalyst and then analyzed by Gas Chromatography equipped with FID detector using BP-20 capillary column. Table - 3 Example Temperature (°C) Duration (h) Conversion of glycerol glycidol (%) Selectivity to glycerol carbonate (%) 11 100 1 99.00 78.84 15.48 12 90 2 98.13 82.7 13.09 13 80 2 76.93 72.47 24.66 14 70 2 49.39 66.53 30.28 : Selectivity of glycidol is calculated based on glycerol conversion Example 15-16: A series of reactions for synthesizing glycerol carbonate are carried out using 50 ml glass reactor, in which 5 g glycerol, 14.66 g dimethyl carbonate and 10 ml methanol are mixed and heated to specified temperature (mentioned in Table 4). 0.50 g (10% wt of glycerol) catalyst is added to the reaction mixture at this temperature. The temperatures of the reaction are varied in these examples. After the specified reaction time, reaction mixture is filtered to remove catalyst and then analyzed by Gas Chromatography equipped with FID detector using BP-20 capillary column. TabJe - 4 Example Temperature (°C) Duration (h) Conversion of glycerol (%) Selectivity to glycidol (%) Selectivity to glycerol carbonate (%) Selectivity to other impurities (%) 15 60 5 75.23 10.26 68.12 21.62 16 50 5 62.16 5.69 73.98 20.33 CLAIMS We claim: 1. Heterogeneous solid base catalyst comprising at least 0.1 to 50 mass percent of alkali and/or alkaline earth metal ion and 5 to 50 mass percent of zirconia, titania and/or mixture thereof of the total mass percent of the catalyst wherein catalyst specific surface area is in the range 10 m2/g to 600 m2/g. 2. Heterogeneous solid base catalyst as claimed in claim 1 wherein alkali and alkaline earth metal is selected from the group consisting of Li+ , Na+, K+, Rb+, Cs+, Mg**, Ca++, Sr++, Ba++. 3. Heterogeneous solid base catalyst as claimed in claim 2 wherein metal ions are preferably selected from Li+, Na+, K+, Mg++ and/or mixture thereof. 4. Heterogeneous solid base catalyst as claimed in claim 1, 2 and 3 wherein in alkali or alkaline earth metal salt is in form of its nitrate, chloride, carbonate, acetate, sulphate and hydroxide. 5. Heterogeneous solid base catalyst as claimed in claim 1 wherein at least one of the zirconia, titania and/or mixture thereof acts as a support. 6. Heterogeneous solid base catalyst as claimed in claim 1 and 5 wherein titanium or zirconium ion is in form of oxide, nitrate, chloride, carbonate, acetate, isopropoxide, sulphate, hydroxide salts of metal ions. 7. Heterogeneous solid base catalyst as claimed in claim 1 has pore diameter in the range of 1 nm to 20 nm and pore volume in the range of 0.01 cm3/g to 1 cm3/g. 8. Heterogeneous solid base catalyst as claimed in claim 1 is prepared by wet impregnation method or co-precipitation method. 9. Heterogeneous solid base catalyst as claimed in claim 1 to 8 is prepared by impregnation of aqueous solutions of metal salts on zirconia or zirconium hydroxides or titania or titanium hydroxide and/or mixture thereof and is dried at minimum of 100 °C and calcined at temperature of at least 300 °C for a minimum of 2 hours. 10. Process for manufacture of Glycerol carbonate and/or Glycidol using catalyst as claimed in claims 1 to 9 comprises steps of: (a) reacting glycerol with dimethyl carbonate in the presence of said Heterogeneous solid base catalyst with or without solvent. (b) separation of products from final reaction mixture. 11. Process for manufacture of Glycerol carbonate and/or Glycidol claimed in claim 10 wherein Heterogeneous solid base catalyst is used in the range of about 0.001 to 50% of the glycerol weight %. 12. Process for manufacture of Glycerol carbonate and/or Glycidol as claimed in claim 10 wherein reaction of glycerol with dimethyl carbonate is carried out in the temperature range of 0 °C to 200 °C, preferable in the range of 20 °C to 120 °C. 13. Process for manufacture of Glycerol carbonate and/or Glycidol as claimed in claim 10 wherein the reaction is carried out at least for 8 hours, preferably for 15 to 300 minutes. 14. Process for manufacture of Glycerol carbonate and/or Glycidol as claimed in claim 10 wherein solvent used is selected from group of dimethyl formamide, dimethyl sulphoxide, dimethyl acetamide, N-methyl pyrrolidone, methanol, ethanol, isopropanol, butanol and a like and/or mixture thereof. 15. Process for manufacture of Glycerol carbonate and/or Glycidol as claimed in claim 10 wherein reaction of dimethyl carbonate with glycerol is carried out in a molar ratio in the range of 1 : 1 to 10 : 1. 16. Process for manufacture of Glycidol as claimed in claim 10 wherein separation of pure glycidol from final reaction mixture is carried out by distillation under vacuum. 17. Process for manufacture of Glycerol carbonate as claimed in claim 10 wherein separation of pure glycidol from final reaction mixture is carried out by distillation under vacuum.

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2033-MUM-2009--CLAIMS(AMENDED)-(10-7-2014).pdf

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