Title of Invention	PROCESS FOR PRODUCTION OF PROPANEDIOL
Abstract	The present invention is related to the process of production of lower alcohols by selective catalytic hydrogenolysis of polyhydroxy alcohols. In the present process, hydrogenolysis of glycerol is carried out in the presence of a heterogeneous catalyst containing metal incorporated in manganese octahedral molecular sieve type-2 (M-OMS-2). Hydrogenolysis of glycerol to propanediol is performed at temperatures above 50 °C and hydrogen pressure of at least 10 bar while maintaining good conversions and high selectivities towards desired products.

Title of Invention

PROCESS FOR PRODUCTION OF PROPANEDIOL

Abstract

The present invention is related to the process of production of lower alcohols by selective catalytic hydrogenolysis of polyhydroxy alcohols. In the present process, hydrogenolysis of glycerol is carried out in the presence of a heterogeneous catalyst containing metal incorporated in manganese octahedral molecular sieve type-2 (M-OMS-2). Hydrogenolysis of glycerol to propanediol is performed at temperatures above 50 °C and hydrogen pressure of at least 10 bar while maintaining good conversions and high selectivities towards desired products.

Full Text	F0RM2 THE PATENTS ACT, 1970 (39 of 1970) PROVISIONAL SPECIFICATION (See section 10 and rule 13) 1. TITLE OF THE INVENTION 'PROCESS FOR PRODUCTION OF PROPANEDIOL" 2. APPLICANT 1. NAME : YADAV GANAPATI DADASAHEB (Last Name/Surname) (First Name) (Father's Name/Middle Name) 2. NATIONALITY: INDIAN 3. ADDRESS : CHEMICAL ENGINEERING DEPARTMENT, INSTITUTE OF CHEMICAL TECHNOLOGY (DEEMED UNIVERSITY), NATHALAL PARIKH MARG, MATUNGA (EAST), MUMBAI 400 019 INDIA The following specification describes invention FIELD OF THE INVENTION: The present invention is related to process production of propanediols by selective catalytic hydrogenolysis of glycerol. In the present process hydrogenolysis of glycerol is carried out in the presence of a heterogeneous catalyst containing metals on octahedral molecular sieves. Hydrogenolysis of glycerol to propanediols is performed at temperatures above 180 °C and hydrogen pressure of at least 200 psi while maintaining high seJectivities and good conversions. BACKGROUND OF INVENTION: Catalytic conversion of renewable feedstocks and chemicals has increased interest of green technologist. Such catalytic conversion can promote the utilization of renewable energy sources- and cam by renewa6/e resources. Recently, it has been proposed that glycerol is regarded as one of the building blocks in the biorefmery feedstocks. It is expected that glycerol can be supplied abundantly from the process of the biodiesel production from vegetable oils. Attention has been recently paid to the catalytic conversion of glycerol to petrochemicals, such as propanediols, acrolein and glyceric acid. 1,2-prepanediol also known as propylene glycol or l,2-dihydroxy propane is a valuable and market demanding molecule for its applications as an antifreeze, deicing compound, monomer in polymer industry, synthetic intermediate and a solvent. The conversion of glycerol to 1, 2-propanediol by both heterogeneous and homogeneous catalyst is disclosed in prior art and can be discussed with their merits and demerits. US patent US5616817 discloses a process for the preparation of 1,2-propanediol by catalytic hydrogenation of glycerol at elevated temperature and pressure, comprises using glycerol having a water content of up to 20% by weight and a catajyst comprising the metals cobalt, copper, manganese and molybdenum in amounts of, based on the total weight of the catalyst, from 40 to 70% by weight of cobalt, from 10 to 20% by weight of copper, from 0 to 10% by weight of manganese and from 0 to 10% by weight of molybdenum, where this catalytically active material may additionally contain inorganic poIyaeids and/or heteropolyacids in an amount of up to 10% by weight, based on the total weight of the catalyst. The disclosed process is gas phase hydrogenation. 2 DE 4302464 patent discloses process for catalytic conversion using metal or metal oxides of group VII elements as a catalyst. Preferably the catalyst is copper chromite, Cu-AI203, Cu-ZnO, Cu-Si02 process uses temperature between 150 °C to 320 °C and 20 to 300 bar pressure preferably between 100 to 250 bar. 30-40% Cu, 23-30 % Cr with smaller amount of Mn/ Si/ Zr/ Ba are the catalyst compositions used. WO/2007/099161 patent discloses process for preparation of 1,2-propanediol in the gas phase by hydrogenation of glycerol using the catalyst used is 23-35% wt of Cu in oxide or elemental form Cu- Ti, Cu- Zr, Cu- Mn, Cu-AI, Cu- Ni, Cu-Mn, Cu- Al, with at least one further metal selected from La, W, Mo, Mn, Zn, Ti, Zr, Sn, Ni, Co Cu3 Zn, Zr Cu, Cr, Ca Cu, Cr, C Cu, Al, Mn optionally Zr are claimed. European patent EP0523014 discloses ruthenium supported on activated carbon catalyst, with a percentage of ruthenium on the substrate of between 0.5 and 7% in the presence of sulphide ions and the ratio of sulphide ions to ruthenium in the catalyst is between 0.2 and 5, preferably between 0.5 and 2. The reaction is being carried out at least at 200 °C temperature. The similar type of catalyst is also been claimed in US4476331 for hydrogenolysis of carbohydrates particularly glycerol. German patent DE-PS-54362 discloses process for the hydrogenation of glycerol with a nickel-based catalyst to form 1, 2-propanediol. With the use of nickel as the catalyst, satisfactory yields of glycerol conversion can be achieved only at higher temperatures of about 270 °C, at which temperatures considerable quantities of unwanted gaseous hydrocarbons, mainly methane is produced. European patent EP-A-72629 discloses a catalytic method of hydrogenating glycerol with the use of Ni, Pd and Pt. According to this document, a key factor for achieving high conversion rates and selectivity towards the formation of diol, is the presence of a promoter constituted by one of the basic inorganic hydroxides. US Patent 5,214,219 discloses hydrogenation of aqueous glycerol to propanediol using copper-zinc catalyst at a pressure of at least 200 psi and temperature 220 to 280 °C. 3 Patent WO095536 discloses a reactive-separation process converts glycerin into lower alcohols, having boiling points less than 200 °C, at high yields. Conversion of natural glycerin to propylene glycol through an acetol intermediate is achieved at temperatures from 150 -250 °C at a pressure ranging from 1-25 bar. The preferred catalyst for this process is a copper-chromium powder. The heterogeneous catalyst was selected from the group consisting of palladium, nickel, rhodium, copper, zinc, chromium and combinations thereof. CN101012149 patent discloses a continuous synthetic method of 1, 2-propanediol comprising of adapting copper, zinc and manganese and or aluminum as a catalyst; aerating glycerin and hydrogen continuously from the top of reactor; hydrogenating glycerin at 200-250 °C under 2.5-5 MPa. US 4624394 discloses a process for the production of propanediol which comprises reacting glycerol, carbon monoxide and hydrogen in an aprotic organic amide solvent medium in contact with a soluble catalyst composition containing tungsten and Group VIII metal compounds, at a temperature between about 100 - 200 °C and a pressure between about 500-10,000 psi to yield a product mixture comprising 1,2-propanediol and 1,3-propanediol. EP1836147 patent discloses process for vapor phase hydrogenation of glycerol in the presence of a catalyst at a temperature from about 160 °C to 260 °C, a pressure of about 10 to about 30 bar. a hydrogen to glycerol ratio of from 400: 1 to about 600: 1 and a residence time of from about 0.01 to about 2.5 h uses Copper/zinc catalyst and Cobalt, copper, manganese and molybdenum catalyst supported on carbon, alumina and silica. US patent US6291725 discloses the catalyst and process for the preparation of glycerol, propylene glycol, and ethylene glycol from sugar alcohols such as sorbitol or xylitol, with the metal catalyst comprising ruthenium deposited on an alumina, titania, or carbon support. The dispersion of the ruthenium on the support increases during the hydrogenolysis reaction. The above cited references mentions wide variety of catalysts for the hydrogenolysis of carbohydrates more particularly glycerol, but none of the above references describes the use of octahedral molecular sieve doped with metal for the desired conversion. Particularly, octahedral manganese molecular sieves, more specifically OMS-2 having tunnel structure doped with silver is not reported for the process of hydrogenolysis of glycerol to propanediol. 4 The present invention is intended to improve the conversion of glycerol by a novel catalytic route to propanediols with greater selectivity. DESCRIPTION OF INVENTION 1,2-propanediol also known as propylene glycol or 1,2-dihydroxy propane is a valuable and market demanding molecule for its applications as an antifreeze, deicing compound, monomer in polymer industry, synthetic intermediate and a solvent. In the present invention glycerol is selectively converted to 1, 2-propanediol using heterogeneous catalyst M-OMS-2 where OMS-2 is doped with different transition metals (M) preferably silver, palladium, nickel, copper and vanadium at pressure ranging between 280 to 400 psi and temperature between 180 to 250 °C. More particularly this invention specifies the higher conversion of glycerol to produce diols, which are of greater commercial value using heterogeneous catalysts with greater selectivity to the desired 1,2-propanediol. In the present process for hydrogenolysis of solution of glycerol in an alcoholic solvent, is carried out at relatively lower temperature and pressure conditions using M-OMS-2 as a heterogeneous catalyst. The hydrogenolysis is carried out in an autoclave reactor at pressure ranging between 280 to 400 psi and temperature of 180 to 220 °C. The process gives good conversions of glycerol and good selectivity towards 1,2 -propanediol. One of embodiment of the present invention is that the present catalytic process is related to the selective hydrogenolysis of glycerol to 1,2-propanediol. One of embodiment of the present invention is that the present process uses the catalyst which is octahedral molecular sieve type-2 for the desired reaction. The catalyst composed of doping of OMS with metal, more particularly silver metal in a particular concentration. The silver concentration in the catalyst ranges from 1% to 50%, more particularly 10% to 30% of manganese oxide. Another embodiment of the present invention is that Glycerol supplied to the hydrogenation reactor is generally between 20 to 40 weight % in 2-propanol as a solvent and reactions are performed at 190 °C and 200 °C and hydrogen pressure of 350 psi. 5 In process of the invention, reaction is carried out in any suitable type of apparatus which enables intimate contact of the reactants and control of the operating conditions and which is suitable for high pressure involved. The process may be carried out in batch, semi-continuous and continuous operation. Batch operation in conventional high pressure autoclave gives excellent results. One of embodiment of present invention is that catalytic process is carried out in reactor which is equipped with a four blade pitched turbine impeller under the hydrogen pressure using heterogeneous catalyst. One of embodiment of present invention is that reaction temperature is in the range of between 100 to 250 °C, more preferably between 150 to 200 °C and hydrogen pressure up to I00 bars for upto 12 hours. The solvent used for the reaction is selected from the alcohols, sulpholanes, N-Methyl pyrollidone more particularly 2-propanol and/or mixtures thereof. One of embodiment of present invention is that in present catalytic process one or more alkali or alkaline earth metal hydroxide and/ or mixtures thereof are added as a promoter to the reaction mixture to the basic conditions improves the conversion. The quantity of the promoter can be from 0.01% to 10% of the glycerol weight. One of embodiment of present invention is that solvent used for the reaction are selected from the alcohols, sulpholanes, N-Methyl pyrollidone, more preferably 2-propanol. The invention is further illustrated by means of the following non-limiting examples. Example 1 Preparation of M-OMS-2 catalyst 21.0 g manganese acetate is dissolved in 67.5 ml distilled water; 9.8 ml of concentrated nitric acid was added to it. *?.971 g silver nitrate is dissolved in 50 ml distilled water and added to acidic manganese acetate solution at room temperature. 13.3 g KMn04 in 275 ml distilled water is added to the above solution dropwise at 70 °C. The resulting black precipitate is refluxed at 100°C for 24 h under stirring. The precipitate is washed several times with 6 distilled water to attain neutral pH, filtered and dried at 120 °C for 12 h to obtain about 15.8 g 30% Ag-OMS-2. 30%o Ag-OMS catalyst is characterized by the following methods. 2. TPR analysis of catalysts: 7 1. SEM images of the catalysts: - Following are the SEM images of the catalysts at different magnifications. Experiment 1: TPR of 30%Ag-OMS-2(Uncal) with 10%H2-Ar(after Oxi) Analysis Type: Temperature Programmed Reduction Calibration: (292__0Q0O) TCD Calib TPR Dt 15-9-06 Measured Flow Rate: 50.13 ml STP/min Signal Offset: 0.00000 Signal inverted: Yes Peak Temperature Volume Peak Number at Maximum (mL/g STP) Concentration (°C) (%) 1 144.6 106.80314 6.75 Example 2-4 8 A 100 ml autoclave with pitch bladed stirrer system, is loaded with 10.0 g glycerol solution in 51.0 ml 2-propanol, 0.5 g desired Ag-OMS-2 catalyst and the 0.1 g of Ca(OH)2 as a promoter. There after autoclave is heated to 200 °C and pressurized with hydrogen to 50 bar and kept under these conditions for 8 hours. The autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis. The liquid is analysed by gas chromatography in a Chemito 1000 model equipped with 30 m BPX-20 capillary column and a flame ionization detector. Table 1 The %Ag Catalyst Promoter Selectivity Example in loading Quantity Conversion (%) No. (wt % of (%) 1,2- catalyst glycerol) (wt %) PDO Acetol Others 2. 10 5 1 47.81 89.51 3.81 6.68 3. 15 5 1 56.89 90.41 2.66 6.93 4. 30 5 I 69.27 91.59 2.2 5.31 symbols used in table 1 have the following meanings: 1,2-PDO: 1,2-propanediol; Others: This includes propan-1-ol, ethylene glycol and some unidentified byproducts . Example 5-7 A 100 m! autoclave with pitch bladed stirrer system, is loaded with 10.0 g glycerol solution in 51.0 ml 2-propanol, 0.5 g 30% Ag-OMS-2 catalyst and the desired quantity of Ca(OH)2 as a promoter. There after autoclave is heated to 200 °C and pressurized with hydrogen up to 50 bar and kept under these conditions for 8 hours. The autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis. The liquid is analyzed by gas chromatography in a Chemito 1000 model equipped with 30 m BPX-20 capillary column and a flame ionization detector. Table 2 Catalyst % Ag Promoter Example loading Conversion in Quantity No. (wt % of (%) catalyst (wt %) glycerol) 1,2-PDO Selectivity (%) Acetol Others 9 5. 30 5 0 63 84.6 3.9 11.5 6. 30 5 0.5 64.19 80.62 2.11 17.27 7. 30 5 1.5 69.16 92.54 1.45 6.01 The symbols used in table 1 have the following meanings: 1,2-PDO: 1, 2-propanediol; Others: This includes propan-1-ol, ethylene glycol and some unidentified byproducts. Example 8-11 A 100 ml autoclave with pitch bladed stirrer system, is loaded with 10.0 g glycerol solution in 51.0 ml 2-propanol, the desired quantity of 30% Ag-OMS-2 catalyst and of 0.1 g Ca(OH)2 as a promoter. There after autoclave is heated to 200 °C and pressurized with hydrogen to 50 bar and kept under these conditions for 8 hours. The autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis. The liquid is analyzed by gas chromatography in a Chemito 1000 model equipped with 30 m BPX-20 capillary column and a flame ionization detector. Table 3 Catalyst Selectivity %Ag Promoter Example in loading Quantity Conversion (%) No. (wt % of (%) catalyst glycerol) (wt %) 1,2-PDO Acetol Others 8. 30 2 1 ■ 36.71 85.19 3.89 10.92 9. 30 3.5 1 51.39 84.52 2.10 13.38 10. 30 5 1 69.27 91.59 2.2 6.21 11. 30 6.5 1 67.89 92.81 1.28 5.91 The symbols used in table 1 have the following meanings: 1,2-PDO: 1, 2-propanediol; Others: This includes propan-1-ol, ethylene glycol and some unidentified by-products. 10 Example 12-15 A 100 ml autoclave with pitch bladed stirrer system, is loaded with 10.0 g glycerol solution in 51.0 ml 2-propanol, 0.5 g of 30% Ag-OMS-2 catalyst and of 0.1 g Ca(OH)2 as a promoter. There after autoclave is heated to 200 °C and pressurized with hydrogen to desired level and kept under these conditions for 8 hours. The autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis. The liquid is analyzed by gas chromatography in a Chemito 1000 model equipped with 30 m BPX-20 capillary column and a flame ionization detector. Table 4 The Example No. in catalyst Hydrogen Pressure (bar) Promoter Quantity (wt %) Conversion 1,2-PDO Selectivity (%) Acetol Others 12. 30 30 44.4 69.85 2.59 27.56 13. 30 40 55.39 88.05 2.49 9.46 14. 30 50 69.27 91.59 2.2 6.21 15. 30 60 59.81 91.92 0.9 7.18 sed in table 1 have the following me anings: 1,2-PDO: 1,2-propanediol; Others: This includes propan-I-ol, ethylene glycol and some unidentified byproducts . Example 16-18 A 100 ml autoclave with pitch bladed stirrer system, is loaded with glycerol solution in a desired quantity of 2-propanol, the amount equivalent to 5 wt% of glycerol of 30% Ag-OMS-2 catalyst and the amount equivalent to 1 wt% of glycerol of Ca(OH)2 as a promoter. There after autoclave is heated to 200 °C and pressurized with hydrogen to 50 bar and kept under these conditions for 8 hours. The autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis. The liquid is analyzed by gas chromatography in a Chemito 1000 model equipped with 30 m BPX-20 capillary column and a flame ionization detector. 11 Table 5 The Example No. Catalyst Quantity (g) Glycerol Concentration (%) Promoter Quantity (wt %) Conversion (%) 1,2-PDO Selectivity (%) Acetol Others 16. 0,25 10 0.5 32.64 88.41 1.76 9.83 17. 0.5 20 I 69.27 91.59 2.2 6.21 18. 0.75 30 1.5 43.31 86.64 1.5 11.86 symbols used in table 1 have the following meanings: 1,2-PDO: 1,2-propanediol; Others: This includes propan-1-ol, ethylene glycol and some unidentified byproducts . Example 19-22 A 100 ml autoclave with pitch bladed stirrer system, is loaded with 10.0 g glycerol solution in 51.0 ml 2-propanoI, 0.5 g of 30% Ag-OMS-2 catalyst and of 0.1 g Ca(OH)2 as a promoter. There after autoclave is heated to the desired temperature and pressurized with hydrogen to 50 bar and kept under these conditions for 8 hours. The autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis. The liquid is analyzed by gas chromatography in a Chemito 1000 model equipped with 30 m BPX-20 capillary column and a flame ionization detector. Table 6 The Example No. %Ag in catalyst Temperature (°C) Promoter Quantity (wt %) Conversion (%) 1,2-PDO Selectivity (%) Acetol Others 19. 30 180 1 30.32 92.07 0.98 6.95 20. 30 190 1 47.6 91.19 1.36 7.45 21. 30 200 1 69.27 91.59 2.2 6.21 22. 30 210 1 83.77 83.8 2.66 13.54 symbols used in table 1 have the following meanings: 1,2-PDO: 1,2-propanediol; Others: This includes propan-1-ol, ethylene glycol and some unidentified byproducts . 12 Dated this 15th day of June, 2009. Slgnature Name: YADAV GANAPATI DADASAHEB (Last Name/Surname) (First Name) (Father's Name/Middle Name)

Full Text

F0RM2
THE PATENTS ACT, 1970 (39 of 1970)
PROVISIONAL SPECIFICATION (See section 10 and rule 13)
1. TITLE OF THE INVENTION
'PROCESS FOR PRODUCTION OF PROPANEDIOL"

2. APPLICANT
1. NAME : YADAV GANAPATI DADASAHEB
(Last Name/Surname) (First Name) (Father's Name/Middle Name)
2. NATIONALITY: INDIAN
3. ADDRESS : CHEMICAL ENGINEERING DEPARTMENT,
INSTITUTE OF CHEMICAL TECHNOLOGY (DEEMED UNIVERSITY), NATHALAL PARIKH MARG,
MATUNGA (EAST), MUMBAI 400 019 INDIA
The following specification describes invention

FIELD OF THE INVENTION:
The present invention is related to process production of propanediols by selective catalytic hydrogenolysis of glycerol. In the present process hydrogenolysis of glycerol is carried out in the presence of a heterogeneous catalyst containing metals on octahedral molecular sieves. Hydrogenolysis of glycerol to propanediols is performed at temperatures above 180 °C and hydrogen pressure of at least 200 psi while maintaining high seJectivities and good conversions.
BACKGROUND OF INVENTION:
Catalytic conversion of renewable feedstocks and chemicals has increased interest of green technologist. Such catalytic conversion can promote the utilization of renewable energy sources- and cam by renewa6/e resources. Recently, it has been proposed that glycerol is regarded as one of the building blocks in the biorefmery feedstocks. It is expected that glycerol can be supplied abundantly from the process of the biodiesel production from vegetable oils. Attention has been recently paid to the catalytic conversion of glycerol to petrochemicals, such as propanediols, acrolein and glyceric acid.
1,2-prepanediol also known as propylene glycol or l,2-dihydroxy propane is a valuable and market demanding molecule for its applications as an antifreeze, deicing compound, monomer in polymer industry, synthetic intermediate and a solvent. The conversion of glycerol to 1, 2-propanediol by both heterogeneous and homogeneous catalyst is disclosed in prior art and can be discussed with their merits and demerits.
US patent US5616817 discloses a process for the preparation of 1,2-propanediol by catalytic hydrogenation of glycerol at elevated temperature and pressure, comprises using glycerol having a water content of up to 20% by weight and a catajyst comprising the metals cobalt, copper, manganese and molybdenum in amounts of, based on the total weight of the catalyst, from 40 to 70% by weight of cobalt, from 10 to 20% by weight of copper, from 0 to 10% by weight of manganese and from 0 to 10% by weight of molybdenum, where this catalytically active material may additionally contain inorganic poIyaeids and/or heteropolyacids in an amount of up to 10% by weight, based on the total weight of the catalyst. The disclosed process is gas phase hydrogenation.
2

DE 4302464 patent discloses process for catalytic conversion using metal or metal oxides of group VII elements as a catalyst. Preferably the catalyst is copper chromite, Cu-AI203, Cu-ZnO, Cu-Si02 process uses temperature between 150 °C to 320 °C and 20 to 300 bar pressure preferably between 100 to 250 bar. 30-40% Cu, 23-30 % Cr with smaller amount of Mn/ Si/ Zr/ Ba are the catalyst compositions used.
WO/2007/099161 patent discloses process for preparation of 1,2-propanediol in the gas phase by hydrogenation of glycerol using the catalyst used is 23-35% wt of Cu in oxide or elemental form Cu- Ti, Cu- Zr, Cu- Mn, Cu-AI, Cu- Ni, Cu-Mn, Cu- Al, with at least one further metal selected from La, W, Mo, Mn, Zn, Ti, Zr, Sn, Ni, Co Cu3 Zn, Zr Cu, Cr, Ca Cu, Cr, C Cu, Al, Mn optionally Zr are claimed.
European patent EP0523014 discloses ruthenium supported on activated carbon catalyst, with a percentage of ruthenium on the substrate of between 0.5 and 7% in the presence of sulphide ions and the ratio of sulphide ions to ruthenium in the catalyst is between 0.2 and 5, preferably between 0.5 and 2. The reaction is being carried out at least at 200 °C temperature. The similar type of catalyst is also been claimed in US4476331 for hydrogenolysis of carbohydrates particularly glycerol.
German patent DE-PS-54362 discloses process for the hydrogenation of glycerol with a nickel-based catalyst to form 1, 2-propanediol. With the use of nickel as the catalyst, satisfactory yields of glycerol conversion can be achieved only at higher temperatures of about 270 °C, at which temperatures considerable quantities of unwanted gaseous hydrocarbons, mainly methane is produced.
European patent EP-A-72629 discloses a catalytic method of hydrogenating glycerol with the use of Ni, Pd and Pt. According to this document, a key factor for achieving high conversion rates and selectivity towards the formation of diol, is the presence of a promoter constituted by one of the basic inorganic hydroxides.
US Patent 5,214,219 discloses hydrogenation of aqueous glycerol to propanediol using copper-zinc catalyst at a pressure of at least 200 psi and temperature 220 to 280 °C.
3

Patent WO095536 discloses a reactive-separation process converts glycerin into lower alcohols, having boiling points less than 200 °C, at high yields. Conversion of natural glycerin to propylene glycol through an acetol intermediate is achieved at temperatures from 150 -250 °C at a pressure ranging from 1-25 bar. The preferred catalyst for this process is a copper-chromium powder. The heterogeneous catalyst was selected from the group consisting of palladium, nickel, rhodium, copper, zinc, chromium and combinations thereof.
CN101012149 patent discloses a continuous synthetic method of 1, 2-propanediol comprising of adapting copper, zinc and manganese and or aluminum as a catalyst; aerating glycerin and hydrogen continuously from the top of reactor; hydrogenating glycerin at 200-250 °C under 2.5-5 MPa.
US 4624394 discloses a process for the production of propanediol which comprises reacting glycerol, carbon monoxide and hydrogen in an aprotic organic amide solvent medium in contact with a soluble catalyst composition containing tungsten and Group VIII metal compounds, at a temperature between about 100 - 200 °C and a pressure between about 500-10,000 psi to yield a product mixture comprising 1,2-propanediol and 1,3-propanediol.
EP1836147 patent discloses process for vapor phase hydrogenation of glycerol in the presence of a catalyst at a temperature from about 160 °C to 260 °C, a pressure of about 10 to about 30 bar. a hydrogen to glycerol ratio of from 400: 1 to about 600: 1 and a residence time of from about 0.01 to about 2.5 h uses Copper/zinc catalyst and Cobalt, copper, manganese and molybdenum catalyst supported on carbon, alumina and silica.
US patent US6291725 discloses the catalyst and process for the preparation of glycerol, propylene glycol, and ethylene glycol from sugar alcohols such as sorbitol or xylitol, with the metal catalyst comprising ruthenium deposited on an alumina, titania, or carbon support. The dispersion of the ruthenium on the support increases during the hydrogenolysis reaction.
The above cited references mentions wide variety of catalysts for the hydrogenolysis of carbohydrates more particularly glycerol, but none of the above references describes the use of octahedral molecular sieve doped with metal for the desired conversion. Particularly, octahedral manganese molecular sieves, more specifically OMS-2 having tunnel structure doped with silver is not reported for the process of hydrogenolysis of glycerol to propanediol.
4

The present invention is intended to improve the conversion of glycerol by a novel catalytic route to propanediols with greater selectivity.
DESCRIPTION OF INVENTION
1,2-propanediol also known as propylene glycol or 1,2-dihydroxy propane is a valuable and market demanding molecule for its applications as an antifreeze, deicing compound, monomer in polymer industry, synthetic intermediate and a solvent.
In the present invention glycerol is selectively converted to 1, 2-propanediol using heterogeneous catalyst M-OMS-2 where OMS-2 is doped with different transition metals (M) preferably silver, palladium, nickel, copper and vanadium at pressure ranging between 280 to 400 psi and temperature between 180 to 250 °C. More particularly this invention specifies the higher conversion of glycerol to produce diols, which are of greater commercial value using heterogeneous catalysts with greater selectivity to the desired 1,2-propanediol.
In the present process for hydrogenolysis of solution of glycerol in an alcoholic solvent, is carried out at relatively lower temperature and pressure conditions using M-OMS-2 as a heterogeneous catalyst. The hydrogenolysis is carried out in an autoclave reactor at pressure ranging between 280 to 400 psi and temperature of 180 to 220 °C. The process gives good conversions of glycerol and good selectivity towards 1,2 -propanediol.
One of embodiment of the present invention is that the present catalytic process is related to the selective hydrogenolysis of glycerol to 1,2-propanediol.
One of embodiment of the present invention is that the present process uses the catalyst which is octahedral molecular sieve type-2 for the desired reaction. The catalyst composed of doping of OMS with metal, more particularly silver metal in a particular concentration. The silver concentration in the catalyst ranges from 1% to 50%, more particularly 10% to 30% of manganese oxide.
Another embodiment of the present invention is that Glycerol supplied to the hydrogenation reactor is generally between 20 to 40 weight % in 2-propanol as a solvent and reactions are performed at 190 °C and 200 °C and hydrogen pressure of 350 psi.
5

In process of the invention, reaction is carried out in any suitable type of apparatus which enables intimate contact of the reactants and control of the operating conditions and which is suitable for high pressure involved. The process may be carried out in batch, semi-continuous and continuous operation. Batch operation in conventional high pressure autoclave gives excellent results.
One of embodiment of present invention is that catalytic process is carried out in reactor which is equipped with a four blade pitched turbine impeller under the hydrogen pressure using heterogeneous catalyst.
One of embodiment of present invention is that reaction temperature is in the range of between 100 to 250 °C, more preferably between 150 to 200 °C and hydrogen pressure up to I00 bars for upto 12 hours. The solvent used for the reaction is selected from the alcohols, sulpholanes, N-Methyl pyrollidone more particularly 2-propanol and/or mixtures thereof.
One of embodiment of present invention is that in present catalytic process one or more alkali or alkaline earth metal hydroxide and/ or mixtures thereof are added as a promoter to the reaction mixture to the basic conditions improves the conversion. The quantity of the promoter can be from 0.01% to 10% of the glycerol weight.
One of embodiment of present invention is that solvent used for the reaction are selected from the alcohols, sulpholanes, N-Methyl pyrollidone, more preferably 2-propanol.
The invention is further illustrated by means of the following non-limiting examples.
Example 1 Preparation of M-OMS-2 catalyst
21.0 g manganese acetate is dissolved in 67.5 ml distilled water; 9.8 ml of concentrated nitric acid was added to it. *?.971 g silver nitrate is dissolved in 50 ml distilled water and added to acidic manganese acetate solution at room temperature. 13.3 g KMn04 in 275 ml distilled water is added to the above solution dropwise at 70 °C. The resulting black precipitate is refluxed at 100°C for 24 h under stirring. The precipitate is washed several times with
6

distilled water to attain neutral pH, filtered and dried at 120 °C for 12 h to obtain about 15.8 g
30% Ag-OMS-2.
30%o Ag-OMS catalyst is characterized by the following methods.
2. TPR analysis of catalysts:
7
1. SEM images of the catalysts: - Following are the SEM images of the catalysts at different magnifications.

Experiment 1: TPR of 30%Ag-OMS-2(Uncal) with 10%H2-Ar(after Oxi)
Analysis Type: Temperature Programmed Reduction Calibration: (292__0Q0O) TCD Calib TPR Dt 15-9-06 Measured Flow Rate: 50.13 ml STP/min Signal Offset: 0.00000 Signal inverted: Yes
Peak Temperature Volume Peak
Number at Maximum (mL/g STP) Concentration
(°C) (%)

1

144.6 106.80314

6.75

Example 2-4

8

A 100 ml autoclave with pitch bladed stirrer system, is loaded with 10.0 g glycerol solution in 51.0 ml 2-propanol, 0.5 g desired Ag-OMS-2 catalyst and the 0.1 g of Ca(OH)2 as a promoter. There after autoclave is heated to 200 °C and pressurized with hydrogen to 50 bar and kept under these conditions for 8 hours. The autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis. The liquid is analysed by gas chromatography in a Chemito 1000 model equipped with 30 m BPX-20 capillary column and a flame ionization detector.
Table 1

The

%Ag Catalyst Promoter Selectivity
Example in loading Quantity Conversion (%)
No. (wt % of (%) 1,2-
catalyst glycerol) (wt %) PDO Acetol Others
2. 10 5 1 47.81 89.51 3.81 6.68
3. 15 5 1 56.89 90.41 2.66 6.93
4. 30 5 I 69.27 91.59 2.2 5.31

symbols used in table 1 have the following meanings:
1,2-PDO: 1,2-propanediol;
Others: This includes propan-1-ol, ethylene glycol and some unidentified byproducts .
Example 5-7
A 100 m! autoclave with pitch bladed stirrer system, is loaded with 10.0 g glycerol solution in 51.0 ml 2-propanol, 0.5 g 30% Ag-OMS-2 catalyst and the desired quantity of Ca(OH)2 as a promoter. There after autoclave is heated to 200 °C and pressurized with hydrogen up to 50 bar and kept under these conditions for 8 hours. The autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis. The liquid is analyzed by gas chromatography in a Chemito 1000 model equipped with 30 m BPX-20 capillary column and a flame ionization detector.
Table 2

Catalyst
% Ag Promoter
Example loading Conversion
in Quantity
No. (wt % of (%)
catalyst (wt %)
glycerol)

1,2-PDO

Selectivity (%)
Acetol Others

9

5. 30 5 0 63 84.6 3.9 11.5
6. 30 5 0.5 64.19 80.62 2.11 17.27
7. 30 5 1.5 69.16 92.54 1.45 6.01
The symbols used in table 1 have the following meanings:
1,2-PDO: 1, 2-propanediol;
Others: This includes propan-1-ol, ethylene glycol and some unidentified byproducts.
Example 8-11
A 100 ml autoclave with pitch bladed stirrer system, is loaded with 10.0 g glycerol solution in 51.0 ml 2-propanol, the desired quantity of 30% Ag-OMS-2 catalyst and of 0.1 g Ca(OH)2 as a promoter. There after autoclave is heated to 200 °C and pressurized with hydrogen to 50 bar and kept under these conditions for 8 hours. The autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis. The liquid is analyzed by gas chromatography in a Chemito 1000 model equipped with 30 m BPX-20 capillary column and a flame ionization detector.
Table 3

Catalyst Selectivity
%Ag Promoter
Example in loading Quantity Conversion (%)
No. (wt % of (%)
catalyst glycerol) (wt %) 1,2-PDO Acetol Others
8. 30 2 1 ■ 36.71 85.19 3.89 10.92
9. 30 3.5 1 51.39 84.52 2.10 13.38
10. 30 5 1 69.27 91.59 2.2 6.21
11. 30 6.5 1 67.89 92.81 1.28 5.91
The symbols used in table 1 have the following meanings:
1,2-PDO: 1, 2-propanediol;
Others: This includes propan-1-ol, ethylene glycol and some unidentified by-products.
10

Example 12-15
A 100 ml autoclave with pitch bladed stirrer system, is loaded with 10.0 g glycerol solution in 51.0 ml 2-propanol, 0.5 g of 30% Ag-OMS-2 catalyst and of 0.1 g Ca(OH)2 as a promoter. There after autoclave is heated to 200 °C and pressurized with hydrogen to desired level and kept under these conditions for 8 hours. The autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis. The liquid is analyzed by gas chromatography in a Chemito 1000 model equipped with 30 m BPX-20 capillary column and a flame ionization detector.
Table 4

The

Example No. in catalyst Hydrogen
Pressure
(bar) Promoter
Quantity
(wt %) Conversion 1,2-PDO Selectivity (%)
Acetol Others
12. 30 30 44.4 69.85 2.59 27.56
13. 30 40 55.39 88.05 2.49 9.46
14. 30 50 69.27 91.59 2.2 6.21
15. 30 60 59.81 91.92 0.9 7.18
sed in table 1 have the following me anings:

1,2-PDO: 1,2-propanediol;
Others: This includes propan-I-ol, ethylene glycol and some unidentified byproducts .
Example 16-18
A 100 ml autoclave with pitch bladed stirrer system, is loaded with glycerol solution in a desired quantity of 2-propanol, the amount equivalent to 5 wt% of glycerol of 30% Ag-OMS-2 catalyst and the amount equivalent to 1 wt% of glycerol of Ca(OH)2 as a promoter. There after autoclave is heated to 200 °C and pressurized with hydrogen to 50 bar and kept under these conditions for 8 hours. The autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis. The liquid is analyzed by gas chromatography in a Chemito 1000 model equipped with 30 m BPX-20 capillary column and a flame ionization detector.
11

Table 5

The

Example No. Catalyst
Quantity
(g) Glycerol
Concentration
(%) Promoter
Quantity
(wt %) Conversion (%) 1,2-PDO Selectivity (%)
Acetol Others
16. 0,25 10 0.5 32.64 88.41 1.76 9.83
17. 0.5 20 I 69.27 91.59 2.2 6.21
18. 0.75 30 1.5 43.31 86.64 1.5 11.86
symbols used in table 1 have the following meanings:
1,2-PDO: 1,2-propanediol;
Others: This includes propan-1-ol, ethylene glycol and some unidentified byproducts .
Example 19-22
A 100 ml autoclave with pitch bladed stirrer system, is loaded with 10.0 g glycerol solution in 51.0 ml 2-propanoI, 0.5 g of 30% Ag-OMS-2 catalyst and of 0.1 g Ca(OH)2 as a promoter. There after autoclave is heated to the desired temperature and pressurized with hydrogen to 50 bar and kept under these conditions for 8 hours. The autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis. The liquid is analyzed by gas chromatography in a Chemito 1000 model equipped with 30 m BPX-20 capillary column and a flame ionization detector.
Table 6

The

Example
No. %Ag
in catalyst Temperature
(°C) Promoter
Quantity
(wt %) Conversion
(%) 1,2-PDO Selectivity (%)
Acetol Others
19. 30 180 1 30.32 92.07 0.98 6.95
20. 30 190 1 47.6 91.19 1.36 7.45
21. 30 200 1 69.27 91.59 2.2 6.21
22. 30 210 1 83.77 83.8 2.66 13.54

symbols used in table 1 have the following meanings:
1,2-PDO: 1,2-propanediol;
Others: This includes propan-1-ol, ethylene glycol and some unidentified byproducts .
12

Dated this 15th day of June, 2009.
Slgnature
Name: YADAV GANAPATI DADASAHEB
(Last Name/Surname) (First Name) (Father's Name/Middle Name)

Documents:

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Patent Number

279597

Indian Patent Application Number

1435/MUM/2009

PG Journal Number

05/2017

Publication Date

03-Feb-2017

Grant Date

27-Jan-2017

Date of Filing

15-Jun-2009

Name of Patentee

YADAV GANAPATI DADASAHEB

Applicant Address

CHEMICAL ENGINEERING DEPARTMENT, INSTITUTE OF CHEMICAL TECHNOLOGY (DEEMED UNIVERSITY) NATHALAL PARIKH MARG, MATUNGA (EAST) MUMBAI 400 019, INDIA

Inventors:

#	Inventor's Name	Inventor's Address
1	YADAV GANAPATI DADASAHEB	CHEMICAL ENGINEERING DEPARTMENT, INSTITUTE OF CHEMICAL TECHNOLOGY (DEEMED UNIVERSITY) NATHALAL PARIKH MARG, MATUNGA (EAST) MUMBAI 400 019, INDIA
2	CHANDAN PAYAL ARVIND	CHEMICAL ENGINEERING DEPARTMENT, INSTITUTE OF CHEMICAL TECHNOLOGY (DEEMED UNIVERSITY) NATHALAL PARIKH MARG, MATUNGA (EAST) MUMBAI 400 019, INDIA

PCT International Classification Number

C07C29/60; C07C29/90; C07C31/20

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA