Title of Invention	A PROCESS FOR THE PREPARATION OF FUNCTIONAL ALIPHATIC HYDROCARBONS FROM VOLATILE LIQUID HYDROCARBONS FOR INDUSTRIAL APPLICATIONS
Abstract	The invention provides a process for the preparation of functional aliphatic hydrocarbons from volatile liquid hydrocarbons using activated carbon and metal impregnated activated carbon under oxic atmosphere at a temperature not exceeding 400°C. The formation of the simpler hydrocarbons ensures a significant decrease in emission of total carbon-di-oxide in the atmosphere, thereby providing a solution to reduce global warming problem. Moreover, the hydrocarbons, produced by the process of the invention, find several industrial applications.

Title of Invention

A PROCESS FOR THE PREPARATION OF FUNCTIONAL ALIPHATIC HYDROCARBONS FROM VOLATILE LIQUID HYDROCARBONS FOR INDUSTRIAL APPLICATIONS

Abstract

The invention provides a process for the preparation of functional aliphatic hydrocarbons from volatile liquid hydrocarbons using activated carbon and metal impregnated activated carbon under oxic atmosphere at a temperature not exceeding 400°C. The formation of the simpler hydrocarbons ensures a significant decrease in emission of total carbon-di-oxide in the atmosphere, thereby providing a solution to reduce global warming problem. Moreover, the hydrocarbons, produced by the process of the invention, find several industrial applications.

Full Text	Field of the Invention The present invention relates to a process for the preparation of functional aliphatic hydrocarbons from volatile liquid hydrocarbons. More particularly, the invention provides a process to convert volatile liquid hydrocarbons into functional aliphatic hydrocarbons using thermal resistant mesoporous activated carbon and metal impregnated activated carbon under oxic environment. The most important application of the process of the present invention is envisaged to be in processing industries for the purpose of minimizing the pollution load by converting toxic aromatic hydrocarbons into simpler aliphatic hydrocarbons. For example, leather processing industry, which is associated with environmental pollution due to the emission of volatile hydrocarbons, is envisaged to be a potential user of the process. Besides, the process finds several other industrial applications. It has enormous potential applications as catalytic converters in automobile industry to minimize exhaust emissions. It may also find application in the energy sectors as an important sustainable source of hydrogen, required for fuel cells in mobile and stationery applications. Moreover, the process is envisaged to have application in petroleum industries for the purpose of oxidation of liquid hydrocarbons in refinery streams. Further, the process may find application in chemical industries for the synthesis of fine chemicals from bulky organic substances. Background of the Invention & Description of Prior Art In recent years, emissions of volatile liquid hydrocarbons (VOCs) into the atmosphere have contributed significantly to air pollution. Emissions of VOC into the atmosphere seriously contribute to the global pollution of the environment. Diseases such as bronchitis, pneumonia, as well as other alterations of the immunologic system, are related to the atmospheric pollution. The control of their emissions has therefore become imperative . It leads to a need to develop efficient technologies for the removal of VOCs. There are many different methods for the removal of VOCs, such as adsorption, absorption, biofiltration, thermal incineration (combustion), and catalyst incineration. Although thermal incineration is widely practiced, the catalytic incineration is also preferred as it can lower the combustion temperature remarkably. The catalysts mainly used in the catalytic incinerators for the oxidation of VOCs are either supported by noble metals (Pt, Pd, Rh, Au) or transition-metals (Mn, Co, Cu, Fe, Ni). In general, noble metal catalysts have higher activities than other metal catalysts. However, their manufacturing costs are high. The major limitation associated with the thermal incineration and catalytic incineration of VOCs is release of CO2 into the atmosphere as a result of complete combustion process. This emission of carbon dioxide into the atmosphere creates a global warming problem and becomes a matter of serious public concern. It has been recognized that the increase in global temperatures causes rise in sea level, increase in intensity of weather events, changes in agricultural yields, glacier retreat, species extinctions, and increase in ranges of disease vectors . Therefore complete conversion of VOC into CO2 is not advisable and appropriate in the present scenario and its control has been recognized to be necessary to remedy the global warming problem. This prompts the necessity to provide a process for conversion of VOCs into intermediate or value added products rather than going for the complete conversion of VOCs into CO2. Parvulescu et al (Catalysis Today 78, 477-485, 2003) oxidized hydrocarbons such as benzene and toluene into benzaldehyde using mono (V, Nb) or bimetallic (V-Ti, Nb-Ti) ions modified MCM-41 (Mobile Crystalline Material of silicate) in the presence of hydrogen peroxide at 616°C. Reference can be made to Hsiao-Chang et al (Applied Catalysis A: General 211, 159-165, 2001) who adopted the oxidation of propene and propane into water and carbon dioxide in the presence of CO at 300°C using noble rnetals such as palladium and platinum supported on alumina and zirconia. This method suffers for its restricted commercial application due to high cost in developing the catalyst and where no value added products were produced. This high cost would severely affect the economy of the process when commercially upscaled. In the above mentioned literatures, it can be found that one of the most interesting metals seems to be platinum, and a wide range of materials, including zeolites, AI203, SiO2, TiO2 , have been used as catalyst supports. This has prompted researchers to explore possibilities to economise the process by using low cost catalytic sources. Our co-pending Indian patent application (320 DEL 2004) provides a process for the synthesis of transition metal complexes impregnated activated carbon. The preparation of materials involves the use of metal complexes in the form of acetylacetonates, pyridine, picoline, hexafluoroacetylacetone, oxime of Cu, Co, Ni, and insitu impregnation of the same on activated carbon having Surface area : 392 - 430 m2/g, Carbon : 37.96 - 39.36 %, Hydrogen : 2.46 - 3.41 %, Nitrogen : 0.50 -0.71 %, Moisture :8 - 15%, Ash : 40 - 50% followed by curing at optimized temperatures. Drago et. al (Applied! Catalysis B. environmental 6, 155-168,1995) reported the complete oxidation of hydrocarbons at around 250°C using metal oxides supported on carbonaceous materials. The metal oxides used were manganese and cobalt. Vivekanand et al, (Carbon 43, 3041-3053, 2005) reported the catalytic oxidation of toluene and m-xylene using a phenolic resin based activated carbon fiber (ACF) impregnated with nitrates of Co, Cr, Ni, and Cu at the reaction temperatures at around 300° C. These methods has a major limitation that the hydrocarbons used such as hexane, butane and toluene were oxidized completely into Carbon dioxide and water and does not provide any value added products of industrial use. The combination of carbon adsorption with catalytic complete oxidation of n-hexane, 2,3-dimethylbutane, cyclohexane and benzene at 300 °C using activated carbons prepared with almond shells and impregnated with CoO, Co3O4 and CrOs were also reported by Alvim Ferraz et al. (Fuel 78 1567-1573, 1999). Chi-Yuan Lu et al., (Applied Catalysis A: General 325 163-174, 2007) prepared a transition-metal catalyst by the polyol method, and subsequently to evaluate the feasibility of the catalytic incineration of volatile liquid hydrocarbons (styrene, toluene and benzene). Activated carbon was selected as the support material, and copper, cobalt, iron, and nickel were used as the catalytic active phases. The major limitation associated with these processes is that they involve only a partial or complete oxidation of VOCs without yielding any kind of intermediate or functional aliphatic compounds, useful for industrial application. Objectives of the invention The main objective of the present invention is to provide a process for the preparation of functional aliphatic hydrocarbons from volatile liquid hydrocarbons which obviates the limitations as stated above. Another objective of the present invention is to provide a process for the conversion of aromatic hydrocarbon into functional aliphatic hydrocarbon at temperature in the range of 150 to 400 degree C in oxic environment. Yet another objective of the present invention is to provide a process to convert aromatic hydrocarbon into functional aliphatic hydrocarbon whereby value added products are obtained for industrial use. Still another objective of the present invention is to use Cu, Ni and Co supported activated carbon, as herein described, as catalyst for the conversion of aromatic hydrocarbon. Yet another objective of the present invention is to use mesoporous carbon, having the following characteristics (non metal supported), as catalyst for the conversion of aromatic hydrocarbon and aliphatic hydrocarbons. Surface area : 392 - 430 m2/g, Carbon : 37.96 - 39.36 %, Hydrogen : 2.46 - 3.41 % Nitrogen : 0.50 - 0.71 %, Moisture :8-15%, Ash : 40 - 50%. Yet another objective of the present invention is to use metal impregnated activated carbon having the following characteristics, as catalyst for the conversion of aromatic hydrocarbon and aliphatic hydrocarbons. The copper impregnated in the mesoporous activated carbon is in the form of copper oxides - Cu2O and CuO. The nickel impregnated in the mesoporous activated carbon is in the form of nickel oxide - NiO. The cobalt impregnated in the mesoporous activated carbon is in the form of cobalt oxide - CoO. Summary of the Invention The invention provides a process for the preparation of functional aliphatic hydrocarbons by heating the volatile liquid hydrocarbons (VOC) and passing this vapor on to activated carbon and metal impregnated activated carbon under air and inert gas. Accordingly, the present invention provides a process for the preparation of functional aliphatic hydrocarbon from volatile liquid hydrocarbon, which comprises i) subjecting volatile liquid hydrocarbon to a temperature in the range 150-300°C at a flow rate ranging between 0.5 - 2 ml per minute to get hydrocarbon vapor, ii) exposing the hydrocarbon vapor, as obtained in step (i), to 50 - 200% by weight, based on the vapour volume , of activated carbon or metal impregnated activated carbon, exhibiting characteristics, as herein described, at a temperature in the range of 150-400°C in the presence of air and inert gas to obtain functional aliphatic hydrocarbon vapor, iii) adjusting the temperature of the aliphatic hydrocarbon vapor, as formed in step (ii), to not exceeding 10°C to obtain the liquid aliphatic hydrocarbon product. In an embodiment of the present invention, the volatile liquid hydrocarbon may be such as benzene, toluene, kerosene, hexane, cyclohexane either individually or in any combination. In another embodiment of the present invention, the metal used in the metal impregnated activated carbon may be selected from copper, nickel, cobalt. In yet another embodiment of the present invention, the amount of copper in the metal impregnated activated carbon may be in the range of 1.0 to 2.0 %. In still another embodiment of the present invention, the amount of nickel in the metal impregnated activated carbon may be in the range of 1.5 to 3.0 %. In yet another embodiment of the present invention, the amount of cobalt in the metal impregnated activated carbon may be in the range of 0.10 to 0.30%. In still another embodiment of the present invention, the inert gas used may be selected from nitrogen, argon. In yet another embodiment of the present invention, the air may be flowed at a rate not more than 100 ml per minute. In still another embodiment of the present invention, the inert gas may be flowed at a rate not more than 30 ml per minute. Detailed description of the invention The process of the present invention is described below in detail. The preparation of metal impregnated activated carbon involves the use of metal complexes in the form of acetylacetonates, pyridine, picoline, hexafluoroacetylacetone, oxime of Cu, Co, Ni, and insitu impregnation of the same on activated carbon having Surface area : 392 - 430 m2/g, Carbon : 37.96 - 39.36 %, Hydrogen : 2.46 -- 3.41 %, Nitrogen : 0.50 - 0.71 %, Moisture :8 - 15%, Ash : 40 - 50% followed by curing at optimized temperatures. The relative percentage of the metal impregnated in the activated carbon matrix is in the range 0.10 - 3.0% w/w to that of the total activated carbon matrix. The resulting metal impregnated activated carbon is used for the purpose of the present invention, as furnished below. Volatile liquid hydrocarbon, at a flow rate ranging between 0.5 - 2 ml per minute, is heated at a temperature in the range of 150 - 300°C to get hydrocarbon vapor. This vapor is exposed to 50 - 200% by weight, based on the vapour volume, of activated carbon or metal impregnated activated carbon, exhibiting characteristics, as herein described, at a temperature in the range of 150-400°C in the presence of air and inert gas to promote conversion reactions. The temperature of the resulting functional aliphatic hydrocarbon vapor is adjusted at not exceeding 10°C to obtain the liquid aliphatic hydrocarbon product. The inventiveness of the present invention lies in the treatment with activated carbon and metal impregnated activated carbon, exhibiting specified characteristics, thereby enabling formation of value added products of industrial importance in the form of functional aliphatic hydrocarbons. The heterogeneous regions of the carbon matrix containing the pi boned electrons may be considered as the active sites for the conversion of volatile liquid hydrocarbons into functional aliphatic hydrocarbons. The following examples are given by way if illustration only and therefore should not be construed to limit the scope of the present invention. Example 1 Benzene at a flow rate of 0.5 ml per minute was heated to 300°C in a pre heater. 10 ml of total resulting benzene vapor was passed into the reactor containing 10 g of 2.5 % nickel impregnated activated carbon, which was set at a temperature of 375°C. Oxygen and nitrogen at a flow rate of 100ml and 30 ml per minute respectively were passed into the reactor chamber to promote conversion reactions. The resulting adipic acid ester vapor was cooled at a temperature of 5°C to obtain adipic acid in liquid form. The liquid was collected in glass tube and stored in an air tight container for further use. Example 2 Toluene at a flow rate of 0.75 ml per minute was heated to 300°C in a pre heater. 15 ml of total resulting toluene vapor was passed into the reactor containing 10 g of 1.5% copper impregnated activated carbon, which was set at a temperature of 350°C. Oxygen and nitrogen at a flow rate of 90ml and 25 ml per minute respectively were passed into the reactor chamber to promote conversion reactions. This resulting vapour mixture of oxirane, tridecane and adipic acid ester was cooled at a temperature of 7°C to obtain the product mixture in liquid form. The liquid was collected in glass tube and stored in an air tight container for further use. Example 3 Cyclohexane at a flow rate of 1 ml per minute was heated to 250°C in a pre heater. 20 ml of total resulting cyclohexane vapor was passed into the reactor containing 10 g of 0.2% cobalt impregnated activated carbon, which was set at a temperature of 300°C. Oxygen and nitrogen at a flow rate of 80ml and 20 ml per minute respectively were passed into the reactor chamber to promote conversion reactions. The resulting methyl methoxy acetate acid vapor was cooled at a temperature of 5°C to obtain methoxyacetate in liquid form. The liquid was collected in glass tube and stored in an air tight container for further use. Example 4 Hexane at a flow rate of 1.5 ml per minute was heated to 220°C in a pre heater. 12 ml of total resulting hexane vapor was passed into the reactor containing 10 g of 1.25 % nickel impregnated activated carbon, which was set at a temperature of 200°C. Oxygen and argon at a flow rate of 85ml and 23 ml per minute respectively were passed into the reactor chamber to promote conversion reactions. The resulting adipic acid ester vapor was cooled at a temperature of 5°C to obtain adipic acid ester in liquid form. The liquid was collected in glass tube and stored in an air tight container for further use. Example 5 Kereosene at a flow rate of 1 ml per minute was heated to 200°C in a pre heater. 18 ml of total resulting kerosene vapor was passed into the reactor containing 10 g of 1.1 % copper impregnated activated carbon, which was set at a temperature of 350°C. Oxygen and nitrogen at a flow rate of 75ml and 15 ml per minute respectively were passed into the reactor chamber to promote conversion reactions. The resulting methyl acetate acid vapor was cooled at a temperature of 6°C to obtain methylacetate in liquid form. The liquid was collected in glass tube and stored in an air tight container for further use. Example 6 Benzene at a flow rate of 1.5 ml per minute was heated to 170°C in a pre heater. 12 ml of total resulting benzene vapor was passed into the reactor containing 10 g of mesoporous activated carbon, which was set at a temperature of 350°C. Oxygen and nitrogen at a flow rate of 100ml and 30 ml per minute respectively were passed into the reactor chamber to promote conversion reactions. The resulting adipic acid ester vapor was cookjd at a temperature of 12°C to obtain adipic acid ester in liquid form. The liquid was collected in glass tube and stored in an air tight container for further use. Example 7 Toluene at a flow rate of 1.25 ml per minute was heated to 225°C in a pre heater. 20 ml of total resulting toluene vapor was passed into the reactor containing 10 g of mesoporous activated carbon, which was set at a temperature of 300°C. Oxygen and nitrogen at a flow rate of 95ml and 20 ml per minute respectively were passed into the reactor chamber to promote conversion reactions. The resulting vapour mixture of oxirane, tridecane and adipic acid ester was cooled at a temperature of 5°C to obtain the product mixture in liquid form. The liquid was collected in glass tube and stored in an air tight container for further use. Example 8 Cyclohexane at a flow rate of 2 ml per minute was heated to 250°C in a pre heater. 16 ml of total resulting cyclohexane vapor was passed into the reactor containing 10 g of mesoporous activated carbon, which was set at a temperature of 200°C. Oxygen and argon at a flow rate of 100 ml and 15 ml per minute respectively were passed into the reactor chamber to promote conversion reactions. This resulting methyl methoxy acetate acid vapor was cooled at a temperature of 4°C to obtain methyl methoxyacetate in liquid form. The liquid was collected in glass tube and stored in an air tight container for further use. Example 9 Hexane at a flow rate of 1.75 ml per minute was heated to 220°C in a pre heater. 10 ml of total resulting hexane vapor was passed into the reactor containing 10 g of mesoporous activated carbon, which was set at a temperature of 250°C. Oxygen and nitrogen at a flow rate of 75ml and 21 ml per minute respectively were passed into the reactor chamber to promote conversion reactions. This resulting adipic acid ester vapor was cooled at a temperature of 5°C to obtain adipic acid ester in liquid form. The liquid was collected in glass tube and stored in an air tight container for further use. Example 10 Kerosene at a flow rate of 2 ml per minute was heated to 350°C in a pre heater. 13 ml of total resulting kerosene vapor was passed into the reactor containing 10 g of mesoporous activated carbon, which was set at a temperature of 250°C. Oxygen and nitrogen at a flow rate of 70 ml and 10 ml per minute respectively were passed into the reactor chamber to promote conversion reactions. This resulting methyl acetate acid vapor' was cooled at a temperature of 5°C to obtain methylacetate in liquid form. The liquid was collected in glass tube and stored in an air tight container for further use. Advantages of the Invention: The main advantages of the present invention are the following. 1. The process is simple and economical. 2. Aromatic hydrocarbons can be converted to adipic acid ester, oxirane, tridecane and methyl methoxyacetate by simple means. 3. Aliphatic hydrocarbons can be converted to functional hydrocarbons 4. The operation temperature of the process is very low when compared to the existing processes available in public domain, thereby ensuring economy of the process. 5. Transition metals can be supported on to carbon to enhance the reactions while the existing method involves noble metals. 6. The process enables 100 % conversion of the hydrocarbon 7. The activated carbon and metal impregnated activated carbon can be used as catalytic converters. 8. The activated carbon and metal impregnated activated carbon catalyst has a very long life period where it can be used for several cycles. 9. The formation of the simpler hydrocarbons ensures a significant decrease in emission of total carbon-di-oxide in the atmosphere. 10.The process provides an effective solution to convert volatile liquid hydrocarbons without adding to the problem relating to global warming. We Claim: 1. A process for the preparation of functional aliphatic hydrocarbons from volatile liquid hydrocarbons, wherein the steps comprise: a) subjecting volatile liquid hydrocarbons to a temperature in the range 150 to 300 degree C at a flow rate ranging between 0.5 to 2.0 ml per minute to get hydrocarbon vapor; b) exposing the hydrocarbon vapor as obtained in step (a) to 50 to 200% by weight; based on the vapour volume, of activated carbon or metal impregnated activated carbon, exhibiting characteristics, of the kind such as herein described, at a temperature in the range of 150 to 400 degree C in the presence of air and inert gas to obtain functional aliphatic hydrocarbon vapor; c) adjusting the temperature of the aliphatic hydrocarbon vapor as formed in step (b), to not exceeding 10 degree C to obtain the liquid aliphatic hydrocarbon product. 2. A process as claimed in claim 1, wherein the volatile liquid hydrocarbon is selected from the group consisting of benzene, toluene, kerosene, hexane, cyclohexane either individually or in any combination. 3. A process as claimed in claim 1, wherein the metal used in the metal impregnated activated carbon is selected from copper, nickel, cobalt. 4. A process as claimed in claim 1, wherein the amount of copper in the metal impregnated activated carbon is in the range of 1.0 to 2.0 %. 5. A process as claimed in claim 1, wherein the amount of nickel in the metal impregnated activated carbon is in the range of 1 .5 to 3.0%. 6. A process as claimed in claim 1, wherein the amount of cobalt in the metal impregnated activated carbon is in the range of 0.10 to 0.30%. 7. A process as claimed in claim 1, wherein the inert gas used is selected from nitrogen, argon, 8. A process as claimed in claim 1 , wherein the air is flowed at a rate not more than 100 ml per minute. 9. A process as claimed in claim 1, wherein the activated carbon or metal impregnated activated carbon exhibits the following characteristics: Surface area : 392 - 430 m2/g, Carbon: 37.96 -39.36%, Hydrogen : 2.46 -3.41 % Nitrogen : 0.50 - 0.71 %, Moisture :8-15%, Ash : 40 - 50%. 10. A process for the preparation of functional aliphatic hydrocarbons from volatile liquid hydrocarbons substantially as herein described with reference to the foregoing examples.

Full Text

Field of the Invention
The present invention relates to a process for the preparation of functional aliphatic hydrocarbons from volatile liquid hydrocarbons. More particularly, the invention provides a process to convert volatile liquid hydrocarbons into functional aliphatic hydrocarbons using thermal resistant mesoporous activated carbon and metal impregnated activated carbon under oxic environment. The most important application of the process of the present invention is envisaged to be in processing industries for the purpose of minimizing the pollution load by converting toxic aromatic hydrocarbons into simpler aliphatic hydrocarbons. For example, leather processing industry, which is associated with environmental pollution due to the emission of volatile hydrocarbons, is envisaged to be a potential user of the process. Besides, the process finds several other industrial applications. It has enormous potential applications as catalytic converters in automobile industry to minimize exhaust emissions. It may also find application in the energy sectors as an important sustainable source of hydrogen, required for fuel cells in mobile and stationery applications. Moreover, the process is envisaged to have application in petroleum industries for the purpose of oxidation of liquid hydrocarbons in refinery streams. Further, the process may find application in chemical industries for the synthesis of fine chemicals from bulky organic substances.
Background of the Invention & Description of Prior Art
In recent years, emissions of volatile liquid hydrocarbons (VOCs) into the atmosphere have contributed significantly to air pollution. Emissions of VOC into

the atmosphere seriously contribute to the global pollution of the environment. Diseases such as bronchitis, pneumonia, as well as other alterations of the immunologic system, are related to the atmospheric pollution. The control of their emissions has therefore become imperative . It leads to a need to develop efficient technologies for the removal of VOCs. There are many different methods for the removal of VOCs, such as adsorption, absorption, biofiltration, thermal incineration (combustion), and catalyst incineration. Although thermal incineration is widely practiced, the catalytic incineration is also preferred as it can lower the combustion temperature remarkably.
The catalysts mainly used in the catalytic incinerators for the oxidation of VOCs are either supported by noble metals (Pt, Pd, Rh, Au) or transition-metals (Mn, Co, Cu, Fe, Ni). In general, noble metal catalysts have higher activities than other metal catalysts. However, their manufacturing costs are high. The major limitation associated with the thermal incineration and catalytic incineration of VOCs is release of CO2 into the atmosphere as a result of complete combustion process. This emission of carbon dioxide into the atmosphere creates a global warming problem and becomes a matter of serious public concern. It has been recognized that the increase in global temperatures causes rise in sea level, increase in intensity of weather events, changes in agricultural yields, glacier retreat, species extinctions, and increase in ranges of disease vectors . Therefore complete conversion of VOC into CO2 is not advisable and appropriate in the present scenario and its control has been recognized to be necessary to remedy the global

warming problem. This prompts the necessity to provide a process for conversion of VOCs into intermediate or value added products rather than going for the complete conversion of VOCs into CO2.
Parvulescu et al (Catalysis Today 78, 477-485, 2003) oxidized hydrocarbons such as benzene and toluene into benzaldehyde using mono (V, Nb) or bimetallic (V-Ti, Nb-Ti) ions modified MCM-41 (Mobile Crystalline Material of silicate) in the presence of hydrogen peroxide at 616°C. Reference can be made to Hsiao-Chang et al (Applied Catalysis A: General 211, 159-165, 2001) who adopted the oxidation of propene and propane into water and carbon dioxide in the presence of CO at 300°C using noble rnetals such as palladium and platinum supported on alumina and zirconia. This method suffers for its restricted commercial application due to high cost in developing the catalyst and where no value added products were produced. This high cost would severely affect the economy of the process when commercially upscaled. In the above mentioned literatures, it can be found that one of the most interesting metals seems to be platinum, and a wide range of materials, including zeolites, AI203, SiO2, TiO2 , have been used as catalyst supports. This has prompted researchers to explore possibilities to economise the process by using low cost catalytic sources.
Our co-pending Indian patent application (320 DEL 2004) provides a process for the synthesis of transition metal complexes impregnated activated carbon. The preparation of materials involves the use of metal complexes in the form of

acetylacetonates, pyridine, picoline, hexafluoroacetylacetone, oxime of Cu, Co, Ni, and insitu impregnation of the same on activated carbon having Surface area : 392 - 430 m2/g, Carbon : 37.96 - 39.36 %, Hydrogen : 2.46 - 3.41 %, Nitrogen : 0.50 -0.71 %, Moisture :8 - 15%, Ash : 40 - 50% followed by curing at optimized temperatures.
Drago et. al (Applied! Catalysis B. environmental 6, 155-168,1995) reported the complete oxidation of hydrocarbons at around 250°C using metal oxides supported on carbonaceous materials. The metal oxides used were manganese and cobalt. Vivekanand et al, (Carbon 43, 3041-3053, 2005) reported the catalytic oxidation of toluene and m-xylene using a phenolic resin based activated carbon fiber (ACF) impregnated with nitrates of Co, Cr, Ni, and Cu at the reaction temperatures at around 300° C. These methods has a major limitation that the hydrocarbons used such as hexane, butane and toluene were oxidized completely into Carbon dioxide and water and does not provide any value added products of industrial use. The combination of carbon adsorption with catalytic complete oxidation of n-hexane, 2,3-dimethylbutane, cyclohexane and benzene at 300 °C using activated carbons prepared with almond shells and impregnated with CoO, Co3O4 and CrOs were also reported by Alvim Ferraz et al. (Fuel 78 1567-1573, 1999). Chi-Yuan Lu et al., (Applied Catalysis A: General 325 163-174, 2007) prepared a transition-metal catalyst by the polyol method, and subsequently to evaluate the feasibility of the catalytic incineration of volatile liquid hydrocarbons (styrene, toluene and benzene). Activated carbon was selected as the support material, and copper, cobalt, iron,

and nickel were used as the catalytic active phases. The major limitation associated with these processes is that they involve only a partial or complete oxidation of VOCs without yielding any kind of intermediate or functional aliphatic compounds, useful for industrial application.
Objectives of the invention
The main objective of the present invention is to provide a process for the
preparation of functional aliphatic hydrocarbons from volatile liquid hydrocarbons
which obviates the limitations as stated above.
Another objective of the present invention is to provide a process for the conversion
of aromatic hydrocarbon into functional aliphatic hydrocarbon at temperature in the
range of 150 to 400 degree C in oxic environment.
Yet another objective of the present invention is to provide a process to convert
aromatic hydrocarbon into functional aliphatic hydrocarbon whereby value added
products are obtained for industrial use.
Still another objective of the present invention is to use Cu, Ni and Co supported
activated carbon, as herein described, as catalyst for the conversion of aromatic
hydrocarbon.
Yet another objective of the present invention is to use mesoporous carbon, having
the following characteristics (non metal supported), as catalyst for the conversion of
aromatic hydrocarbon and aliphatic hydrocarbons.
Surface area : 392 - 430 m2/g, Carbon : 37.96 - 39.36 %,

Hydrogen : 2.46 - 3.41 % Nitrogen : 0.50 - 0.71 %, Moisture :8-15%, Ash : 40 - 50%. Yet another objective of the present invention is to use metal impregnated activated
carbon having the following characteristics, as catalyst for the conversion of
aromatic hydrocarbon and aliphatic hydrocarbons.
The copper impregnated in the mesoporous activated carbon is in the form of
copper oxides - Cu2O and CuO.
The nickel impregnated in the mesoporous activated carbon is in the form of nickel
oxide - NiO.
The cobalt impregnated in the mesoporous activated carbon is in the form of
cobalt oxide - CoO.
Summary of the Invention
The invention provides a process for the preparation of functional aliphatic hydrocarbons by heating the volatile liquid hydrocarbons (VOC) and passing this vapor on to activated carbon and metal impregnated activated carbon under air and inert gas.
Accordingly, the present invention provides a process for the preparation of functional aliphatic hydrocarbon from volatile liquid hydrocarbon, which comprises

i) subjecting volatile liquid hydrocarbon to a temperature in the range 150-300°C at a flow rate ranging between 0.5 - 2 ml per minute to get hydrocarbon vapor,
ii) exposing the hydrocarbon vapor, as obtained in step (i), to 50 - 200% by weight, based on the vapour volume , of activated carbon or metal impregnated activated carbon, exhibiting characteristics, as herein described, at a temperature in the range of 150-400°C in the presence of air and inert gas to obtain functional aliphatic hydrocarbon vapor,
iii) adjusting the temperature of the aliphatic hydrocarbon vapor, as formed in step (ii), to not exceeding 10°C to obtain the liquid aliphatic hydrocarbon product.
In an embodiment of the present invention, the volatile liquid hydrocarbon may be
such as benzene, toluene, kerosene, hexane, cyclohexane either individually or in
any combination.
In another embodiment of the present invention, the metal used in the metal
impregnated activated carbon may be selected from copper, nickel, cobalt.
In yet another embodiment of the present invention, the amount of copper in the
metal impregnated activated carbon may be in the range of 1.0 to 2.0 %.
In still another embodiment of the present invention, the amount of nickel in the
metal impregnated activated carbon may be in the range of 1.5 to 3.0 %.
In yet another embodiment of the present invention, the amount of cobalt in the
metal impregnated activated carbon may be in the range of 0.10 to 0.30%.

In still another embodiment of the present invention, the inert gas used may be
selected from nitrogen, argon.
In yet another embodiment of the present invention, the air may be flowed at a rate
not more than 100 ml per minute.
In still another embodiment of the present invention, the inert gas may be flowed at
a rate not more than 30 ml per minute.
Detailed description of the invention
The process of the present invention is described below in detail. The preparation of metal impregnated activated carbon involves the use of metal complexes in the form of acetylacetonates, pyridine, picoline, hexafluoroacetylacetone, oxime of Cu, Co, Ni, and insitu impregnation of the same on activated carbon having Surface area : 392 - 430 m2/g, Carbon : 37.96 - 39.36 %, Hydrogen : 2.46 -- 3.41 %, Nitrogen : 0.50 - 0.71 %, Moisture :8 - 15%, Ash : 40 - 50% followed by curing at optimized temperatures. The relative percentage of the metal impregnated in the activated carbon matrix is in the range 0.10 - 3.0% w/w to that of the total activated carbon matrix. The resulting metal impregnated activated carbon is used for the purpose of the present invention, as furnished below.
Volatile liquid hydrocarbon, at a flow rate ranging between 0.5 - 2 ml per minute, is heated at a temperature in the range of 150 - 300°C to get hydrocarbon vapor. This vapor is exposed to 50 - 200% by weight, based on the vapour volume, of activated carbon or metal impregnated activated carbon, exhibiting characteristics,

as herein described, at a temperature in the range of 150-400°C in the presence of air and inert gas to promote conversion reactions. The temperature of the resulting functional aliphatic hydrocarbon vapor is adjusted at not exceeding 10°C to obtain the liquid aliphatic hydrocarbon product.
The inventiveness of the present invention lies in the treatment with activated carbon and metal impregnated activated carbon, exhibiting specified characteristics, thereby enabling formation of value added products of industrial importance in the form of functional aliphatic hydrocarbons. The heterogeneous regions of the carbon matrix containing the pi boned electrons may be considered as the active sites for the conversion of volatile liquid hydrocarbons into functional aliphatic hydrocarbons.
The following examples are given by way if illustration only and therefore should not be construed to limit the scope of the present invention.
Example 1
Benzene at a flow rate of 0.5 ml per minute was heated to 300°C in a pre heater. 10 ml of total resulting benzene vapor was passed into the reactor containing 10 g of 2.5 % nickel impregnated activated carbon, which was set at a temperature of 375°C. Oxygen and nitrogen at a flow rate of 100ml and 30 ml per minute respectively were passed into the reactor chamber to promote conversion reactions. The resulting adipic acid ester vapor was cooled at a temperature of 5°C to obtain

adipic acid in liquid form. The liquid was collected in glass tube and stored in an air tight container for further use.
Example 2
Toluene at a flow rate of 0.75 ml per minute was heated to 300°C in a pre heater. 15 ml of total resulting toluene vapor was passed into the reactor containing 10 g of 1.5% copper impregnated activated carbon, which was set at a temperature of 350°C. Oxygen and nitrogen at a flow rate of 90ml and 25 ml per minute respectively were passed into the reactor chamber to promote conversion reactions. This resulting vapour mixture of oxirane, tridecane and adipic acid ester was cooled at a temperature of 7°C to obtain the product mixture in liquid form. The liquid was collected in glass tube and stored in an air tight container for further use.
Example 3
Cyclohexane at a flow rate of 1 ml per minute was heated to 250°C in a pre heater. 20 ml of total resulting cyclohexane vapor was passed into the reactor containing 10 g of 0.2% cobalt impregnated activated carbon, which was set at a temperature of 300°C. Oxygen and nitrogen at a flow rate of 80ml and 20 ml per minute respectively were passed into the reactor chamber to promote conversion reactions. The resulting methyl methoxy acetate acid vapor was cooled at a temperature of 5°C to obtain methoxyacetate in liquid form. The liquid was collected in glass tube and stored in an air tight container for further use.

Example 4
Hexane at a flow rate of 1.5 ml per minute was heated to 220°C in a pre heater. 12 ml of total resulting hexane vapor was passed into the reactor containing 10 g of 1.25 % nickel impregnated activated carbon, which was set at a temperature of 200°C. Oxygen and argon at a flow rate of 85ml and 23 ml per minute respectively were passed into the reactor chamber to promote conversion reactions. The resulting adipic acid ester vapor was cooled at a temperature of 5°C to obtain adipic acid ester in liquid form. The liquid was collected in glass tube and stored in an air tight container for further use.
Example 5
Kereosene at a flow rate of 1 ml per minute was heated to 200°C in a pre heater. 18 ml of total resulting kerosene vapor was passed into the reactor containing 10 g of 1.1 % copper impregnated activated carbon, which was set at a temperature of 350°C. Oxygen and nitrogen at a flow rate of 75ml and 15 ml per minute respectively were passed into the reactor chamber to promote conversion reactions. The resulting methyl acetate acid vapor was cooled at a temperature of 6°C to obtain methylacetate in liquid form. The liquid was collected in glass tube and stored in an air tight container for further use.
Example 6
Benzene at a flow rate of 1.5 ml per minute was heated to 170°C in a pre heater. 12 ml of total resulting benzene vapor was passed into the reactor containing 10 g of mesoporous activated carbon, which was set at a temperature of 350°C. Oxygen and nitrogen at a flow rate of 100ml and 30 ml per minute respectively were passed

into the reactor chamber to promote conversion reactions. The resulting adipic acid ester vapor was cookjd at a temperature of 12°C to obtain adipic acid ester in liquid form. The liquid was collected in glass tube and stored in an air tight container for further use.
Example 7
Toluene at a flow rate of 1.25 ml per minute was heated to 225°C in a pre heater. 20 ml of total resulting toluene vapor was passed into the reactor containing 10 g of mesoporous activated carbon, which was set at a temperature of 300°C. Oxygen and nitrogen at a flow rate of 95ml and 20 ml per minute respectively were passed into the reactor chamber to promote conversion reactions. The resulting vapour mixture of oxirane, tridecane and adipic acid ester was cooled at a temperature of 5°C to obtain the product mixture in liquid form. The liquid was collected in glass tube and stored in an air tight container for further use.
Example 8
Cyclohexane at a flow rate of 2 ml per minute was heated to 250°C in a pre heater. 16 ml of total resulting cyclohexane vapor was passed into the reactor containing 10 g of mesoporous activated carbon, which was set at a temperature of 200°C. Oxygen and argon at a flow rate of 100 ml and 15 ml per minute respectively were passed into the reactor chamber to promote conversion reactions. This resulting methyl methoxy acetate acid vapor was cooled at a temperature of 4°C to obtain methyl methoxyacetate in liquid form. The liquid was collected in glass tube and stored in an air tight container for further use.

Example 9
Hexane at a flow rate of 1.75 ml per minute was heated to 220°C in a pre heater. 10 ml of total resulting hexane vapor was passed into the reactor containing 10 g of mesoporous activated carbon, which was set at a temperature of 250°C. Oxygen and nitrogen at a flow rate of 75ml and 21 ml per minute respectively were passed into the reactor chamber to promote conversion reactions. This resulting adipic acid ester vapor was cooled at a temperature of 5°C to obtain adipic acid ester in liquid form. The liquid was collected in glass tube and stored in an air tight container for further use.
Example 10
Kerosene at a flow rate of 2 ml per minute was heated to 350°C in a pre heater. 13 ml of total resulting kerosene vapor was passed into the reactor containing 10 g of mesoporous activated carbon, which was set at a temperature of 250°C. Oxygen and nitrogen at a flow rate of 70 ml and 10 ml per minute respectively were passed into the reactor chamber to promote conversion reactions. This resulting methyl acetate acid vapor' was cooled at a temperature of 5°C to obtain methylacetate in liquid form. The liquid was collected in glass tube and stored in an air tight container for further use.
Advantages of the Invention:
The main advantages of the present invention are the following. 1. The process is simple and economical.

2. Aromatic hydrocarbons can be converted to adipic acid ester, oxirane,
tridecane and methyl methoxyacetate by simple means.
3. Aliphatic hydrocarbons can be converted to functional hydrocarbons
4. The operation temperature of the process is very low when compared to the
existing processes available in public domain, thereby ensuring economy of
the process.
5. Transition metals can be supported on to carbon to enhance the reactions
while the existing method involves noble metals.
6. The process enables 100 % conversion of the hydrocarbon
7. The activated carbon and metal impregnated activated carbon can be used
as catalytic converters.
8. The activated carbon and metal impregnated activated carbon catalyst has
a very long life period where it can be used for several cycles.
9. The formation of the simpler hydrocarbons ensures a significant decrease in
emission of total carbon-di-oxide in the atmosphere.
10.The process provides an effective solution to convert volatile liquid hydrocarbons without adding to the problem relating to global warming.

We Claim:
1. A process for the preparation of functional aliphatic hydrocarbons from
volatile liquid hydrocarbons, wherein the steps comprise:
a) subjecting volatile liquid hydrocarbons to a temperature in the range
150 to 300 degree C at a flow rate ranging between 0.5 to 2.0 ml per
minute to get hydrocarbon vapor;
b) exposing the hydrocarbon vapor as obtained in step (a) to 50 to 200%
by weight; based on the vapour volume, of activated carbon or metal
impregnated activated carbon, exhibiting characteristics, of the kind
such as herein described, at a temperature in the range of 150 to 400
degree C in the presence of air and inert gas to obtain functional
aliphatic hydrocarbon vapor;
c) adjusting the temperature of the aliphatic hydrocarbon vapor as formed
in step (b), to not exceeding 10 degree C to obtain the liquid aliphatic
hydrocarbon product.

2. A process as claimed in claim 1, wherein the volatile liquid hydrocarbon is
selected from the group consisting of benzene, toluene, kerosene, hexane,
cyclohexane either individually or in any combination.
3. A process as claimed in claim 1, wherein the metal used in the metal
impregnated activated carbon is selected from copper, nickel, cobalt.
4. A process as claimed in claim 1, wherein the amount of copper in the metal
impregnated activated carbon is in the range of 1.0 to 2.0 %.

5. A process as claimed in claim 1, wherein the amount of nickel in the metal
impregnated activated carbon is in the range of 1 .5 to 3.0%.
6. A process as claimed in claim 1, wherein the amount of cobalt in the metal
impregnated activated carbon is in the range of 0.10 to 0.30%.
7. A process as claimed in claim 1, wherein the inert gas used is selected from
nitrogen, argon,
8. A process as claimed in claim 1 , wherein the air is flowed at a rate not more
than 100 ml per minute.
9. A process as claimed in claim 1, wherein the activated carbon or metal
impregnated activated carbon exhibits the following characteristics:
Surface area : 392 - 430 m2/g, Carbon: 37.96 -39.36%, Hydrogen : 2.46 -3.41 % Nitrogen : 0.50 - 0.71 %, Moisture :8-15%, Ash : 40 - 50%.
10. A process for the preparation of functional aliphatic hydrocarbons from
volatile liquid hydrocarbons substantially as herein described with reference to the foregoing examples.

Documents:

http://ipindiaonline.gov.in/patentsearch/GrantedSearch/viewdoc.aspx?id=kZtO+cOeanc7nlhFrd66gg==&loc=+mN2fYxnTC4l0fUd8W4CAA==

« Previous Patent

Next Patent »

Patent Number

268578

Indian Patent Application Number

709/DEL/2008

PG Journal Number

36/2015

Publication Date

04-Sep-2015

Grant Date

04-Sep-2015

Date of Filing

20-Mar-2008

Name of Patentee

COUNCIL OF SCIENTIFIC & INDUSTRIAL RESEARCH

Applicant Address

ANUSANDHAN BHAWAN, RAFI MARG, NEW DELHI-110 001,INDIA.

Inventors:

#	Inventor's Name	Inventor's Address
1	BALASUBRAMANI RAVINDRAN	CENTRAL LEATHER RESEARCH INSTITUTE CHENNAI
2	ARULDASS UDAYA	CENTRAL LEATHER RESEARCH INSTITUTE CHENNAI
3	GANESAN SEKARAN	CENTRAL LEATHER RESEARCH INSTITUTE CHENNAI
4	LOURDUSAMY KENNEDY	CENTRAL LEATHER RESEARCH INSTITUTE CHENNAI
5	JOHN JUDITH VIJAYA	CENTRAL LEATHER RESEARCH INSTITUTE CHENNAI

PCT International Classification Number

C08G18/68; C08G18/08

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA