Patent Grant
9409836
This application is a U.S. national stage application filed under 35 U.S.C. §371 from International Application Serial No. PCT/IB2013/000076, which was filed Jan. 24, 2013, and published as WO 2013/110995 on Aug. 1, 2013, and which claims priority to India Application No. 218/DEL/2012, filed Jan. 25, 2012, and to India Application No. 1361/DEL/2012, filed May 4, 2012, which applications and publication are incorporated by reference as if reproduced herein and made a part hereof in their entirety, and the benefit of priority of each of which is claimed herein.
The present invention relates to a process for hydrogenation of olefinic or acetylenic bonds. Particularly, the present invention relates to a process for the selective hydrogenation of olefinic or acetylenic bonds using supported acidic metal oxide catalyst and the process for the preparation thereof. More particularly, the present invention provides a process for hydrogenation of olefinic or acetylenic bonds using metal supported on acidic metal oxide/modified acidic metal oxides at moderate conditions. The present invention also relates to the preparation of metal oxide based catalyst for hydrogenation reactions under mild conditions.
Several catalysts have been tried for hydrogenation reactions. These catalysts are usually based on metals such as palladium, platinum and nickel supported on different oxides like silica, different carbon supports like carbon nanotubes, and charcoal as well as several polymers. Out of all these catalysts, palladium on charcoal is the most frequently used catalyst in industries and academia.
Though Pd/C is frequently used by the industry, it has some drawbacks such as pyrophoric nature when in contact with dry methanol. Normally hydrogenation reactions are carried out at melting temperature and high hydrogen pressure. Conventionally triglycerides and unsaturated fatty acids are hydrogenated using noble metal based catalysts or copper chromite or copper cadmium catalysts at melting temperature in the range of 150 to 250° C. and high hydrogen pressure. Specifically oils like castor oils are hydrogenated using nickel based catalysts at melting temperature (150-250° C.) and high pressure (up to 20 bar). Under these severe conditions, highly dispersed palladium or platinum particles sinter leading to loss of catalytic activity. Many times the noble metal loading in industrial catalyst varies from 1% to 10% of the support and higher loading leads to increase in the catalyst cost.
To overcome the severe reaction conditions and to evolve a cheaper catalyst for hydrogenation reactions is the need of the time.
The main object of the present invention is to provide a process for hydrogenation of olefinic or acetylenic bonds.
Another object of the present invention is to provide a process for hydrogenation of olefinic or acetylenic bonds using modified acidic metal oxide catalyst and the process for the preparation thereof.
Another object of the present invention is to provide a simple, economical, efficient process for hydrogenation of olefinic or acetylenic bonds using metal oxide based catalyst or modified acidic metal oxide catalyst under mild conditions.
Another object of the invention is to provide a process for the preparation of metal oxide based supported catalyst for hydrogenation of olefinic and acetylenic bonds under mild conditions.
Accordingly, the present invention provides a process for hydrogenation of olefinic or acetylenic bonds, said process comprising:
In an embodiment of the present invention the catalyst used in step (a) is solid acidic support comprising a metal oxide, mixed metal oxides or modified metal oxides.
In one embodiment of the present invention metals selected from group II A, IIIA, IVA, IB, IVB, VIB, and VIIIB.
In another embodiment of the present invention at least one elemental metal dispersed on said support wherein the elemental metal is selected from group VIB, IB or VIIIB metals in an amount up to 0.1-1.0 weight percent based upon the total weight of metal and support.
In yet another embodiment of the present invention yield and selectivity of desired product is up to 100%.
In yet another embodiment of the present invention the solvent is selected from toluene, methanol, and carbon tetra chloride.
In still another embodiment of the present invention a process for preparation of a catalyst for hydrogenation comprising:
In still another embodiment of the present invention the acidity of the catalyst with modified magnesium oxide support ranges from 0.1-3.0 mmol/g of NH3.
In still another embodiment of the present invention the specific surface area of the metal oxide based solid acid catalyst supports is in the range between 50 to 500 m2/gm.
In still another embodiment of the present invention the specific acidity of the metal oxide based solid acid catalyst supports is in the range of 0.1 to 3.0 mmol/g of NH3.
In the present invention a simple process for hydrogenation of olefinic and acetylene bonds using metal oxide based supported catalysts is disclosed.
In the invention selective hydrogenation of olefinic, acetylenic including edible and non edible triglycerides is carried out at room temperature (20-30° C.) and atmospheric pressure by bubbling hydrogen gas through the oil, using palladium based catalysts with up to 1% Pd loading on the acidic metal oxide support.
The catalyst of the invention comprises a metal selected from noble metals and metals from group VIIIB, IB and VIB. In a preferred embodiment of the invention the metals are selected from Ni, Cu, Cr, Pd, Pt, Rh, and Au. The metals of the invention have been uniformly dispersed on metal oxide based solid acid supports. The acidity of the catalyst ranges from 0.1-3.0 mmol/g of NH3. Table 1 lists the different metal oxide based solid acid catalyst supports with specific surface area and specific acidity.
In the process of hydrogenation of olefinic and acetylenic bonds of the invention comprises:
List of active metals supported on solid acidic support: Pd, Pt, Cu, Ni, Rh, Au, Cr
The process of hydrogenation of olefinic and acetylenic bonds is catalyzed by a novel modified magnesium oxide catalyst prepared by a process comprising:
The ratio of magnesium to fluoride varies from 1:0.1 to 1:2.
The modified magnesium oxide catalyst of the invention can be prepared replacing magnesium with calcium, strontium, barium or aluminium. The modified magnesium catalyst of the invention comprises a metal selected from noble metals and metals from group VIIIB, IB and VIB.
In the invention the metals are selected from Ni, Cu, Cr, Pd, Pt, Rh and Au.
In another aspect of the invention, the modified magnesium catalyst of the invention is characterized by XRD studies.
In the process of the invention, no leaching of palladium is observed and catalyst of the invention is recyclable.
The modified magnesium catalyst is used for catalysis for the process of hydrogenation of olefinic and acetylenic bonds as given in the following examples.
The metal oxide based catalyst may be further used for selective hydrogenation of olefinic double bonds under very mild conditions for various industrially important molecules including pharmaceuticals.
The invention can be better understood by the following non-limiting examples. The examples given are mere an illustration of the instant invention and should not be construed as limiting the scope of the present invention in any manner.
The 50 mg 1% Pd-20% MoO3/SiO2 (impregnated) was activated for the period up to 0.5 h under the constant flow of hydrogen of 2 ml/min in the toluene (10 mL) with constant stirring at room temperature 27° C. To this solution 0.0.5 g styrene was added. The reaction was continued for 3 h. The samples were collected after specified time interval and analyzed by GC. The reaction was monitored by GC analysis. The products were confirmed by GC and GCMS analysis. In this reaction only product obtained was ethyl benzene with 100% conversion and >99.5% selectivity.
The 50 mg 1% Pd-20% MoO3/SiO2 (impregnated) was activated for the period up to 0.5 h under the constant flow of hydrogen of 2 ml/min in the toluene (10 mL) with constant stirring at room temperature 27° C. To this solution 0.0.5 g Cinnamaldehyde was added. The reaction was continued for 3 h. The samples were collected after specified time interval and analyzed by GC. The reaction was monitored by GC analysis. The products were confirmed by GC and GCMS analysis. In this reaction only product obtained is 3-phenylpropanol with >99% selectivity and 95% conversion.
The 50 mg 1% Pd-20% MoO3/SiO2 (impregnated) was activated for the period up to 0.5 h under the constant flow of hydrogen of 2 ml/min in the methanol (10 mL) with constant stirring at room temperature 27° C. To this solution 0.5 g palm oil was added. The reaction was continued for 1.5 h. The samples were collected after specified time and analyzed by titration method by determination its Iodine value. At the end of reaction white solid was obtained which is palm wax (or hydrogenated palm oil) having Iodine value less than 12 and acid value up to 2 (same as that of the initial palm oil).
The 50 mg 1% Pd-20% MoO3/SiO2 (impregnated) was activated for the period up to 0.5 h under the constant flow of hydrogen of 2 ml/min in the methanol (10 mL) with constant stirring at room temperature 27° C. To this solution 0.5 g castor oil was added. The reaction was continued for 1.5 h. The samples were collected after specified time and analyzed by titration method by determination its Iodine value. At the end of reaction white solid was obtained which castor wax (or hydrogenated castor oil) is having Iodine value around 14 and acid value up to 2 (same as that of the initial castor oil
The 50 mg 1% Pd-20% MoO3/SiO2 (impregnated) was activated for the period up to 0.5 h under the constant flow of hydrogen of 2 ml/min in the methanol (10 mL) with constant stirring at room temperature 27° C. To this solution was added 0.5 g oleic acid. The reaction was continued for 1 h. The samples were collected after specified time and analyzed by titration method by determination its Iodine value. At the end of reaction white solid was obtained which is stearic acid having Iodine value <1. The product was also confirmed by FTIR analysis which shows absence of double bond frequency.
The 50 mg 1% Pd—Al2O3 (acidic) was activated for the period up to 0.5 h under the constant flow of hydrogen of 2 ml/min in the methanol (10 mL) with constant stirring at room temperature 27° C. To this solution 0.5 g castor oil was added. The reaction was continued for 6 h. The samples were collected after specified time and analyzed by titration method by determination its Iodine value. At the end of reaction white solid was obtained which is castor wax having Iodine value ˜12 and acid value up to 2.
The 50 mg 1% Pd-20% MoO3/SiO2 (impregnated) was activated for the period up to 0.5 h under the constant flow of hydrogen of 2 ml/min in the methanol (10 mL) with constant stirring at room temperature 27° C. To this solution 0.0.5 g castor oil was added. The reaction was continued for 3 h. The samples were collected after specified time and analyzed by titration method by determination its Iodine value. At the end of reaction white solid was obtained which is castor wax having Iodine value ˜12 and acid value up to 2.
The 50 mg 1% Pd-20% MoO3/SiO2 (sol gel) was activated for the period up to 0.5 h under the constant flow of hydrogen of 2 ml/min in the methanol (10 mL) with constant stirring at room, temperature 27° C. To this solution 0.5 g castor oil was added. The reaction was continued for 8 h. The samples were collected after specified time and analyzed by titration method by determination its Iodine value. At the end of reaction white solid was obtained which is castor wax having Iodine value ˜30 and acid value up to 2.
The 50 mg 1% Pd-resin (Amberlite IRS-120) was activated for the period up to 0.5 h under the constant flow of hydrogen of 2 ml/min in the methanol (10 mL) with constant stirring at room temperature 27° C. To this solution 0.0.5 g castor oil was added. The reaction was continued for 3 h. The samples were collected after specified time and analyzed by titration method by determination its Iodine value. At the end of reaction white solid was obtained which is castor wax having Iodine value ˜15 and acid value up to 2.
In 100 mL beaker, 4.0 g commercial magnesium oxide was added to 40 mL distilled water to form suspension at room temperature. This suspension was reacted with 10.0 mL aqueous hydrofluoric acid (commercial, 40%) with stirring at up to 1400 RPM. After the complete addition of hydrofluoric acid the reaction mixture was allowed to stir for 3 h. To this solution 5.0 mL acidic solution (1N HCl) of palladium chloride (0.103 g, 1 wt %) was added drop wise. The reaction mixture was kept under stirring for 16 h. The water was allowed to evaporate from the reaction by simply drying at 100° C. using hot plate with magnetic stirrer followed by heating at 150° C. in oven for 3 h. Catalyst yield was about 100%. Catalyst was characterized by PXRD.
In 100 mL beaker, 4.0 g commercial magnesium oxide was added to 40 mL distilled water to form suspension at room temperature. This suspension was reacted with 10.0 mL aqueous hydrofluoric acid (commercial, 40%) with stirring at up to 1400 RPM. After the complete addition of hydrofluoric acid the reaction mixture was allowed to stir for 3 h. To this solution 5.0 mL acidic solution (1N HCl) of palladium chloride (0.052 g, 0.5 wt %) was added drop wise. The reaction mixture was kept under stirring for 16 h. The water was allowed to evaporate from the reaction by simply drying at 100° C. using hot plate with magnetic stirrer followed by heating at 150° C. in oven for 3 h. Catalyst yield was about 100%. Catalyst was characterized by PXRD.
In 100 mL beaker, 4.0 g commercial magnesium oxide was added to 40 mL distilled water to form suspension at room temperature. This suspension was reacted with 10.0 mL aqueous hydrofluoric acid (commercial, 40%) with stirring at up to 1400 RPM. After the complete addition of hydrofluoric acid the reaction mixture was allowed to stir for 3 h. To this solution 5.0 mL acidic solution (1N HCl) of palladium chloride (0.0102 g, 0.1 wt %) was added drop wise. The reaction mixture was kept under stirring for 16 h. The water was allowed to evaporate from the reaction by simply drying at 100° C. using hot plate with magnetic stirrer followed by heating at 150° C. in oven for 3 h. Catalyst yield was about 100%. Catalyst was characterized by PXRD.
In 100 mL beaker, 4.0 g commercial magnesium oxide was added to 40 mL distilled water to form suspension at room temperature. This suspension was reacted with 10.0 mL aqueous hydrofluoric acid (commercial, 40%) with stirring at up to 1400 RPM. After the complete addition of hydrofluoric acid the reaction mixture was allowed to stir for 3 h. To this solution 5.0 mL acidic solution (1N HCl) of palladium chloride (0.206 g, 2 wt %) was added drop wise. The reaction mixture was kept under stirring for 16 h. The water was allowed to evaporate from the reaction by simply drying at 100° C. using hot plate with magnetic stirrer followed by heating at 150° C. in oven for 3 h. Catalyst yield was about 100%. Catalyst was characterized by PXRD.
In 100 mL beaker, 4.0 g commercial magnesium oxide was added to 40 mL distilled water to form suspension at room temperature. This suspension was reacted with 10.0 mL aqueous hydrofluoric acid (commercial, 40%) with stirring at up to 1400 RPM. After the complete addition of hydrofluoric acid the reaction mixture was allowed to stir for 3 h. To this solution 5.0 mL acidic solution (1N HCl) of palladium chloride (0.515 g, 5 wt %) was added drop wise. The reaction mixture was kept under stirring for 16 h. The water was allowed to evaporate from the reaction by simply drying at 100° C. using hot plate with magnetic stirrer followed by heating at 150° C. in oven for 3 h. Catalyst yield was about 100%. Catalyst was characterized by PXRD.
In 100 mL beaker, 4.0 g commercial magnesium oxide was added to 40 mL distilled water to form suspension at room temperature. This suspension was reacted with 10.0 mL aqueous hydrofluoric acid (commercial, 40%) with stirring at up to 1400 RPM. After the complete addition of hydrofluoric acid the reaction mixture was allowed to stir for 3 h. To this solution 5.0 mL acidic solution (1N HCl) of palladium chloride (0.0206 g, 0.2 wt %) was added drop wise. The reaction mixture was kept under stirring for 16 h. The water was allowed to evaporate from the reaction by simply drying at 100° C. using hot plate with magnetic stirrer followed by heating at 150° C. in oven for 3 h. Catalyst yield was about 100%. Catalyst was characterized by PXRD.
In 100 mL beaker, 4.0 g commercial magnesium oxide was added to 40 mL distilled water to form suspension at room temperature. This suspension was reacted with 10.0 mL aqueous hydrofluoric acid (commercial, 40%) with stirring at up to 1400 RPM. After the complete addition of hydrofluoric acid the reaction mixture was allowed to stir for 3 h. To this solution 5.0 mL acidic solution (1N HCl) of palladium chloride (0.031 g, 0.3 wt %) was added drop wise. The reaction mixture was kept under stirring for 16 h. The water was allowed to evaporate from the reaction by simply drying at 100° C. using hot plate with magnetic stirrer followed by heating at 150° C. in oven for 3 h. Catalyst yield was about 100%. Catalyst was characterized by PXRD.
The 50 mg 1% Pd—MgO modified with HF as prepared in Example 10 was activated for the period up to 0.5 h under the constant flow of hydrogen of 2 mL/min in the toluene (10 mL) with constant stirring at room temperature 27° C. To this solution 0.0.5 g styrene was added. The reaction was continued for 3 h. The samples were collected after specified time interval and analyzed by GC. The reaction was monitored by GC analysis. The products were confirmed by GC and GCMS analysis. In this reaction only product obtained was ethyl benzene with 100% conversion and >99.5% selectivity.
The 50 mg 1% Pd—MgO modified with HF as prepared in Example 10 was activated for the period up to 0.5 h under the constant flow of hydrogen of 2 mL/min in the methanol (10 ml) with constant stirring at temperature 27° C. To this solution 500 mg styrene was added. The reaction was continued for 3 h. The samples were collected after specified time interval and analyzed by GC. The reaction was monitored by GC analysis. The products were confirmed by GC and GCMS analysis. In this reaction only product obtained was ethyl benzene with 100% conversion and >99.5% selectivity.
The 50 mg 1% Pd—MgO modified with HF as prepared in Example 10 was activated for the period up to 0.5 h under the constant flow of hydrogen of 2 mL/min in the toluene (10 mL) with constant stirring at room temperature 27° C. To this solution 0.5 g Cinnamldehyde was added. The reaction was continued for 3 h. The samples were collected after specified time interval and analyzed by GC. The reaction was monitored by GC analysis. The products were confirmed by GC and GCMS analysis. In this reaction only product obtained is 3-phenylpropanol with >99% selectivity and 95% conversion.
The 50 mg 1% Pd—MgO modified with HF as prepared in Example 10 was activated for the period up to 0.5 h under the constant flow of hydrogen of 2 mL/min in the methanol (10 mL) with constant stirring at room temperature 27° C. To this solution was added 0.5 g palm oil. The reaction was continued for 1.5 h. The samples were collected after specified time and analyzed by titration method by determination its Iodine value. At the end of reaction white solid was obtained which is palm wax (or hydrogenated palm oil) having Iodine value <12 and acid value ˜2 (same as that of the initial palm oil).
The 50 mg 1% Pd—MgO modified with HF as prepared in Example 10 was activated for the period up to 0.5 h under the constant flow of hydrogen of 2 mL/min in the methanol (10 mL) with constant stirring at temperature 27° C. To this solution 0.5 g castor oil was added. The reaction was continued for 1.5 h. The samples were collected after specified time and analyzed by titration method for determination of iodine value. At the end of reaction white castor wax (or hydrogenated castor oil) with iodine value around 14 and acid value up to 2 (same as that of the initial castor oil) was obtained.
The 50 mg 1% Pd—MgO modified with HF as prepared in Example 10 was activated for the period up to 0.5 h under the constant flow of hydrogen of 2 mL/min in the methanol (10 mL) with constant stirring at room temperature 27° C. To this solution 0.5 g oleic acid was added. The reaction was continued for 1 h. The samples were collected after specified time and analyzed by titration method by determination its Iodine value. At the end of reaction white solid was obtained which is stearic acid having Iodine value <1. The product was also confirmed by FTIR analysis which shows absence of double bond frequency.
The 50 mg 1% Pd—MgO modified with HF as prepared in Example 10 was activated for the period up to 0.5 h under the constant flow of hydrogen of 10 mL/min in the methanol (10 mL) with constant stirring at mentioned temperature. To this solution was added 0.5 g of various substrates as given in table 2. The reaction was continued for specified time. The samples were collected intermittently and analyzed by GC and GCMS. The product was also confirmed by FTIR analysis which shows absence of olefinic C═C bond frequency. The reaction conditions and results are given in table 2.
A 50 mL high pressure autoclave was charged with 20.0 g of castor oil and required amount of catalyst from example 10 and hydrogen gas pressure 10 bar. The reaction mixture was stirred with 1800 RPM speed at required temperature. During the reaction the hydrogen gas pressure slowly decreased which was maintained using external gas pressure reservoir. The reaction was allowed to continue for the specific time. Once the reaction completed the product was separated from the catalyst and subjected for analysis. The white castor wax was analyzed using iodine value and melting point. The results are tabulated in table 3.
54#
#with solvent methanol (1:10 oil:solvent),
@with solvent methanol (3:1 oil:solvent)
A 50 mL high pressure reactor charged with 20 g sunflower oil, 1 g catalyst from example 10 as prepared in example 10 and hydrogen gas pressure 10 bar. The reaction mixture was stirred with 1800 RPM speed at room temperature for 3 h. During the reaction the hydrogen gas pressure slowly decreased which was maintained using external gas pressure reservoir. Once the reaction was complete the product was separated from the catalyst and subjected for analysis. The iodine value of the white sunflower wax was found to be 56.
A 50 mL high pressure autoclave was charged with 20 g sunflower oil 1 g catalyst from example 10 as prepared in example 10. Hydrogen gas was bubbled with 10 mL per min with constant stirring (1800 RPM speed) at room temperature for 7 h. The flow rate of hydrogen gas was kept constant by using external reservoir. Once the reaction was completed the product was separated from the catalyst and subjected for analysis. The iodine value of the white sunflower wax was found to be 64
A 50 mL high pressure autoclave was charged with 20 g rape seed oil, 1 g catalyst from example 10 and hydrogen gas pressure 10 bar. The reaction mixture was stirred with 1800 RPM speed at 100° C. for 3 h. During the reaction the hydrogen gas pressure slowly decreased which was maintained using external gas pressure reservoir. The reaction was allowed to continue for 6 h. Once the reaction was complete the product was separated from the catalyst and subjected for analysis. The iodine value and melting point of the whitish yellow rape seed wax was found to be 32 and 59° C. respectively.
A 50 mL high pressure autoclave was charged with 20 g rape seed fatty acid, 1 g catalyst from example 16, and hydrogen gas pressure 10 bar. The reaction mixture was stirred with 1800 RPM speed at 90° C. for 5 h. During the reaction the hydrogen gas pressure decreased slowly which was maintained using external gas pressure reservoir. The reaction was continued for 6 h. Once the reaction was complete the product was separated from the catalyst and subjected to analysis. The iodine value of the whitish saturated rape seed fatty acid was found to be 39. Also the partial reduction of olefinic double bond was confirmed by FTIR spectroscopy.
The advantages of the invention are:
| Number | Date | Country | Kind |
|---|---|---|---|
| 218/DEL/2012 | Jan 2012 | IN | national |
| 1361/DEL/2012 | May 2012 | IN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/IB2013/000076 | 1/24/2013 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2013/110995 | 8/1/2013 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 2930766 | Lacey | Mar 1960 | A |
| 4094821 | McVicker et al. | Jun 1978 | A |
| 20120136176 | Yamada et al. | May 2012 | A1 |
| Number | Date | Country |
|---|---|---|
| 814003 | May 1959 | GB |
| 1033414 | Jun 1966 | GB |
| WO-2005052093 | Jun 2005 | WO |
| WO-2013110995 | Aug 2013 | WO |
| Entry |
|---|
| “International Application No. PCT/1B2013/000076, Article 34 Amendment mailed Jan. 30, 2014”, (Jan. 30, 2014), 11 pgs. |
| “International Application No. PCT/IB2013/000076, International Search Report mailed Oct. 30, 2013”, (Oct. 30, 2013), 6 pgs. |
| Fernandez, M. B, et al., “Hydrogenation of edible oil over Pd-Me/Al2O3 catalysts (Me = Mo, V and Pb)”, Journal of Molecular Catalysis A: Chemical, 233(1-2), (May 24, 2005), 133-139. |
| Mahata, N., et al., “Phenol hydrogenation over palladium supported on magnesia: Relationship between catalyst structure and performance”, Phys. Chem. Chem. Phys., 3(13), (2001), 2712-2719. |
| Nijhuis, T. A, et al., “Optimized palladium catalyst systems for the selective liquid-phase hydrogenation of functionalyzed alkynes”, Applied Catalysis A: General, 238(2), (Jan. 20, 2003), 259-271. |
| Number | Date | Country | |
|---|---|---|---|
| 20150239821 A1 | Aug 2015 | US |
