CA2601929A1 - Production processes, production systems, and catalyst compositions - Google Patents
Production processes, production systems, and catalyst compositions Download PDFInfo
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- CA2601929A1 CA2601929A1 CA002601929A CA2601929A CA2601929A1 CA 2601929 A1 CA2601929 A1 CA 2601929A1 CA 002601929 A CA002601929 A CA 002601929A CA 2601929 A CA2601929 A CA 2601929A CA 2601929 A1 CA2601929 A1 CA 2601929A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
- B01J37/0223—Coating of particles by rotation
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Embodiments of the disclosure provide catalyst compositions that can include a substrate, chromium, and at least one alkali metal Production processes are provided for removing a catalyst composition from a solution with the catalyst composition comprising the alkali metal composition and the substrate.
Production processes are also provided that can include exposing a compound to a reagent in the presence of the catalyst composition. Production systems are also provided that can include a reactor coupled to both a reactant reservoir and a reagent reservoir with the reactor containing a catalyst composition comprising chromium and at least one alkali metal.
Production processes are also provided that can include exposing a compound to a reagent in the presence of the catalyst composition. Production systems are also provided that can include a reactor coupled to both a reactant reservoir and a reagent reservoir with the reactor containing a catalyst composition comprising chromium and at least one alkali metal.
Description
PRODUCTION PROCESSES, PRODUCTION SYSTEMS, AND
CATALYST COMPOSITIONS
CLAIM FOR PRIORITY
This application claims priority to United States Provisional Patent Application Serial No. 60/656,600 entitled "Halogenation Processes" filed on February 25, 2005, which is incorporated by reference herein.
TECHNICAL FIELD
The disclosure pertains to production processes, production systems, and catalyst compositions, including halogenation processes, systems, and halogenation catalyst compositions.
BACKGROUND OF THE INVENTION
Chemical production processes can include the use of catalyst compositions to enhance the production process. The catalyst compositions may not only facilitate the reaction of reactants themselves, the catalyst compositions can, in some instances, enhance the efficiency of the reaction of reactants providing a higher purity product more efficiently, for example. Halogenation processes, including halogenation exchange, as well as, combination halogenation exchange and elimination reactions, are reactions that can utilize catalyst compositions.
Catalyst compositions can aid in the efficiency of these halogenation processes by, for example, allowing for the exchange of halogens to produce fluorinated compounds from chlorinated compounds, and/or chlorinated compounds from brominated compounds, brominated compounds from iodinated compounds, fluorinated compounds from iodinated compounds, and even fluorinated compounds from brominated compounds.
Exemplary catalyzed reactions can take place at temperatures in which the reactants are in the gas-phase. These catalyzed gas-phase reactions can degrade catalyst compositions requiring the frequent reactivation and/or replacement of the composition in order to meet reaction efficiency requirements, thus requiring production processes to cease during catalyst reactivation and/or replacement.
Catalyst compositions that can facilitate the efficient reaction of reactants with less frequent reactivation and/or replacement are useful during production processes.
SUMMARY
Embodiments of the disclosure provide catalyst compositions that can include a substrate, chromium, and at least one alkali metal.
Production processes can include preparing a first solution that inciudes an alkali metal composition, and exposing the first solution to a substrate to form a second solution with the second solution including the substrate and the alkali metal composition. The process can further include removing a catalyst composition from the second solution with the catalyst composition comprising the alkali metal composition and the substrate.
Production processes are also provided that can include exposing a compound to a reagent in the presence of a catalyst composition with the catalyst composition including a substrate, chromium, and at least one alkali metal.
According to exemplary embodiments, a C-3 compound can be exposed to a reagent in the presence of a catalyst composition with the catalyst composition comprising at least one alkali metal.
Production systems are also provided that can inciude a reactor coupled to both a reactant reservoir and a reagent reservoir with the reactor containing a catalyst composition comprising chromium and at least one alkali metal.
BRIEF DESCRIPTION OF THE FIGURE
The Figure is a diagram of a system according to an exempiary embodiment of an exemplary aspect of the invention.
DESCRIPTION OF THE EMBODIMENTS
Catalyst compositions, production processes and systems are described with reference to the Figure. Referring to the Figure, a production system 10 is shown that includes a reactor 12 coupled to both a reactant reservoir 14 and a reagent reservoir 16. Reactor 12 is also coupled to a product reservoir 18 and in the exemplary embodiment, reactor 12 contains a catalyst composition 20. System 10 can be configured as an industrial chemical production system. For example, the flow of reactants from reactant reservoir 14 and reagents from reagent reservoir 16 can be controlled with flow meters, and these reactants can also be passed through vaporizers where system 10 is configured to expose reagents to reactants in the gas-phase. Reactor 12 can also be referred to as a reaction chamber, the reaction chamber having an interior portion defining a volume of the chamber. As such, reactor 12 of system 10 can be configured to maintain a temperature of the contents of reactor 12. Such temperatures can be maintained through jacketing of reactor 12 with steam heat jackets, for example. Product flowing to product reservoir 18 from reactor 12 can be controlled via the cooling of gasses of reactor 12 within a condenser, for example.
As shown in the exemplary Figure, system 10 is configured with reservoirs 14 and 16 coupled to reactor 12 from the lower portion of reactor 12, and product being removed from the upper portion of reactor 12. This should not be considered the only configuration of system 10. System 10 can also be configured to flow reactants and/or reagents downward from the upper portion of reactor 12 with the product being removed from the lower portion of reactor 12. Reactants of reactant reservoir 14 and reagents of reagent reservoir 16 can be also fed into or provided to reactor 12 via a pressure differentiation between that within reactor 12 and that within reservoirs 14 and 16. According to exemplary embodiments, reservoirs 14 and 16 can be maintained at a higher pressure, either through a backing gas, for example, nitrogen, which can provide a higher pressure and then fed to reactor 12 which is maintained at a lower pressure, with the pressure differentiation driving the flow of reactants. For example, in certain configurations, reactor 12 can be maintained at a pressure of 687kPa.
According to an alternative embodiment, system 10 may also include an oxidizing reagent reservoir 22, coupled to reactor 12. The oxidizing reagent of oxidizing reagent reservoir 22 can be fed at a predetermined feed rate along with the reactants of reactant reservoir 14 and the reagents of reagent reservoir 16.
Oxidizing reagent reservoir 22 can be coupled directly to reactant 12, or it may be coupled to the conduits coupling reactant reservoir 14 and reagent reservoir 16 to reactor 12. According to exemplary embodiments, all reactant and reservoir conduits coupled to Reactor 12 may be coupled to one another prior to coupling to reactor 12. The oxidizing reagent can include 0 and/or Cl in the form of 02 and/or CI2, respectively. The oxidizing reagent can be fed to reactor 12 as a mole percentage of the reactants and reagents. For example the mole percentage of the oxidizing reagent can be at least about 0.1% of the combined total of the oxidizing reagent, the reagent, and the reactant provided to reactor 12. As another example, the mole percentage of the oxidizing reagent can be from about 0.1 % to about 0.3%.
The oxidizing reagent may be provided during activation and/or preparation of catalyst composition 20, and/or provided after the activation of catalyst composition 20 in combination with the reactant.
As shown in the exemplary Figure, catalyst composition 20 is contained within reactor 12. In the shown embodiment, catalyst composition 20 resides within the volume of reactor 12. However, catalyst composition 20 may also reside along the walls of reactor 12 or within the center of reactor 12, for example. According to exemplary embodiments, reactor 12 may be formed of stainless steel and may take a tubular form such as a pipe. According to other exemplary implementations, reactor 12 may be formed of inconel , monel , carbon steel, and/or nickel. At the lower portion of reactor 12 a mesh screen (not shown) may be provided.
Composition 20 may be provided to within reactor 12 over this mesh screen, for example.
Catalyst composition 20 can include chromium and at least one alkali metal. Catalyst composition 20 may also include a substrate. The substrate can include the interior walls of reactor 12 as well as carbon and/or other substrates known to those of ordinary skill in the art.
According to exemplary embodiments, the substrate can include activated carbon. In particular embodiments, for example, the substrate of catalyst composition 20 can include Takeda Brand activated carbon (Takeda Chemical Industries, LTD., 12-10, Nihonbashi 2-chome Chuo-ku, Tokyo 103-8868, Japan) and/or Calgon Brand carbon (Calgon Carbon Corpoation, 400 Calgon Carbon Drive Pittsburgh, PA. 15205). The alkali metal can include potassium, for example, as well as other alkali metals of Group I of the periodic table of elements. In exemplary embodiments, a mole ratio of the chromium to the one alkali metal of the catalyst composition can be at least about 50:1.
CATALYST COMPOSITIONS
CLAIM FOR PRIORITY
This application claims priority to United States Provisional Patent Application Serial No. 60/656,600 entitled "Halogenation Processes" filed on February 25, 2005, which is incorporated by reference herein.
TECHNICAL FIELD
The disclosure pertains to production processes, production systems, and catalyst compositions, including halogenation processes, systems, and halogenation catalyst compositions.
BACKGROUND OF THE INVENTION
Chemical production processes can include the use of catalyst compositions to enhance the production process. The catalyst compositions may not only facilitate the reaction of reactants themselves, the catalyst compositions can, in some instances, enhance the efficiency of the reaction of reactants providing a higher purity product more efficiently, for example. Halogenation processes, including halogenation exchange, as well as, combination halogenation exchange and elimination reactions, are reactions that can utilize catalyst compositions.
Catalyst compositions can aid in the efficiency of these halogenation processes by, for example, allowing for the exchange of halogens to produce fluorinated compounds from chlorinated compounds, and/or chlorinated compounds from brominated compounds, brominated compounds from iodinated compounds, fluorinated compounds from iodinated compounds, and even fluorinated compounds from brominated compounds.
Exemplary catalyzed reactions can take place at temperatures in which the reactants are in the gas-phase. These catalyzed gas-phase reactions can degrade catalyst compositions requiring the frequent reactivation and/or replacement of the composition in order to meet reaction efficiency requirements, thus requiring production processes to cease during catalyst reactivation and/or replacement.
Catalyst compositions that can facilitate the efficient reaction of reactants with less frequent reactivation and/or replacement are useful during production processes.
SUMMARY
Embodiments of the disclosure provide catalyst compositions that can include a substrate, chromium, and at least one alkali metal.
Production processes can include preparing a first solution that inciudes an alkali metal composition, and exposing the first solution to a substrate to form a second solution with the second solution including the substrate and the alkali metal composition. The process can further include removing a catalyst composition from the second solution with the catalyst composition comprising the alkali metal composition and the substrate.
Production processes are also provided that can include exposing a compound to a reagent in the presence of a catalyst composition with the catalyst composition including a substrate, chromium, and at least one alkali metal.
According to exemplary embodiments, a C-3 compound can be exposed to a reagent in the presence of a catalyst composition with the catalyst composition comprising at least one alkali metal.
Production systems are also provided that can inciude a reactor coupled to both a reactant reservoir and a reagent reservoir with the reactor containing a catalyst composition comprising chromium and at least one alkali metal.
BRIEF DESCRIPTION OF THE FIGURE
The Figure is a diagram of a system according to an exempiary embodiment of an exemplary aspect of the invention.
DESCRIPTION OF THE EMBODIMENTS
Catalyst compositions, production processes and systems are described with reference to the Figure. Referring to the Figure, a production system 10 is shown that includes a reactor 12 coupled to both a reactant reservoir 14 and a reagent reservoir 16. Reactor 12 is also coupled to a product reservoir 18 and in the exemplary embodiment, reactor 12 contains a catalyst composition 20. System 10 can be configured as an industrial chemical production system. For example, the flow of reactants from reactant reservoir 14 and reagents from reagent reservoir 16 can be controlled with flow meters, and these reactants can also be passed through vaporizers where system 10 is configured to expose reagents to reactants in the gas-phase. Reactor 12 can also be referred to as a reaction chamber, the reaction chamber having an interior portion defining a volume of the chamber. As such, reactor 12 of system 10 can be configured to maintain a temperature of the contents of reactor 12. Such temperatures can be maintained through jacketing of reactor 12 with steam heat jackets, for example. Product flowing to product reservoir 18 from reactor 12 can be controlled via the cooling of gasses of reactor 12 within a condenser, for example.
As shown in the exemplary Figure, system 10 is configured with reservoirs 14 and 16 coupled to reactor 12 from the lower portion of reactor 12, and product being removed from the upper portion of reactor 12. This should not be considered the only configuration of system 10. System 10 can also be configured to flow reactants and/or reagents downward from the upper portion of reactor 12 with the product being removed from the lower portion of reactor 12. Reactants of reactant reservoir 14 and reagents of reagent reservoir 16 can be also fed into or provided to reactor 12 via a pressure differentiation between that within reactor 12 and that within reservoirs 14 and 16. According to exemplary embodiments, reservoirs 14 and 16 can be maintained at a higher pressure, either through a backing gas, for example, nitrogen, which can provide a higher pressure and then fed to reactor 12 which is maintained at a lower pressure, with the pressure differentiation driving the flow of reactants. For example, in certain configurations, reactor 12 can be maintained at a pressure of 687kPa.
According to an alternative embodiment, system 10 may also include an oxidizing reagent reservoir 22, coupled to reactor 12. The oxidizing reagent of oxidizing reagent reservoir 22 can be fed at a predetermined feed rate along with the reactants of reactant reservoir 14 and the reagents of reagent reservoir 16.
Oxidizing reagent reservoir 22 can be coupled directly to reactant 12, or it may be coupled to the conduits coupling reactant reservoir 14 and reagent reservoir 16 to reactor 12. According to exemplary embodiments, all reactant and reservoir conduits coupled to Reactor 12 may be coupled to one another prior to coupling to reactor 12. The oxidizing reagent can include 0 and/or Cl in the form of 02 and/or CI2, respectively. The oxidizing reagent can be fed to reactor 12 as a mole percentage of the reactants and reagents. For example the mole percentage of the oxidizing reagent can be at least about 0.1% of the combined total of the oxidizing reagent, the reagent, and the reactant provided to reactor 12. As another example, the mole percentage of the oxidizing reagent can be from about 0.1 % to about 0.3%.
The oxidizing reagent may be provided during activation and/or preparation of catalyst composition 20, and/or provided after the activation of catalyst composition 20 in combination with the reactant.
As shown in the exemplary Figure, catalyst composition 20 is contained within reactor 12. In the shown embodiment, catalyst composition 20 resides within the volume of reactor 12. However, catalyst composition 20 may also reside along the walls of reactor 12 or within the center of reactor 12, for example. According to exemplary embodiments, reactor 12 may be formed of stainless steel and may take a tubular form such as a pipe. According to other exemplary implementations, reactor 12 may be formed of inconel , monel , carbon steel, and/or nickel. At the lower portion of reactor 12 a mesh screen (not shown) may be provided.
Composition 20 may be provided to within reactor 12 over this mesh screen, for example.
Catalyst composition 20 can include chromium and at least one alkali metal. Catalyst composition 20 may also include a substrate. The substrate can include the interior walls of reactor 12 as well as carbon and/or other substrates known to those of ordinary skill in the art.
According to exemplary embodiments, the substrate can include activated carbon. In particular embodiments, for example, the substrate of catalyst composition 20 can include Takeda Brand activated carbon (Takeda Chemical Industries, LTD., 12-10, Nihonbashi 2-chome Chuo-ku, Tokyo 103-8868, Japan) and/or Calgon Brand carbon (Calgon Carbon Corpoation, 400 Calgon Carbon Drive Pittsburgh, PA. 15205). The alkali metal can include potassium, for example, as well as other alkali metals of Group I of the periodic table of elements. In exemplary embodiments, a mole ratio of the chromium to the one alkali metal of the catalyst composition can be at least about 50:1.
Catalyst composition 20 may be produced by preparing a first solution including an acid composition. According to exemplary embodiments, the acid composition can be chromic acid, and may provide the majority of the chromium in the catalyst composition. The first solution can also include a solvent such as water.
A second solution including an alkali metal composition may be prepared separately and then combined with the first solution or together with the first solution of the acid composition to form a second solution, for example. According to an exemplary implementation, the second solution can include a solvent such as water. It is contemplated that other solvents for the first and second solutions may be utilized as well.
The alkali metal composition can include potassium, as well as, chromium and/or oxygen. The alkali metal composition can be a salt of an alkali metal, including alkali metal salts of chromic acids, such as potassium dichromate or K2Cr2O7. Alkali metal salts of other acids may be comprised by the alkali metal composition. The alkali metal composition of the alkali metal solution can be at least about 4% (wt./wt.), for example.
Upon preparing the first and second solutions, the solutions may be combined, if necessary, to form a third solution that includes the solvent, the acid composition, and the alkali metal composition. This third solution can be referred to as chromium-alkali metal solution. These solutions can be prepared by agitating the compositions with the solvents to form a solution of the composition according to exemplary implementations. Vessels appropriate for such mixing include plastic and/or glass vessels, and the mixing can be accomplished using a magnetic stir-bar, for example.
The chromium-alkali metal solution can be combined with a substrate to form a catalyst solution. As described above, the substrate can include carbon and/or activated carbon such as Takeda and/or Calgon carbon. According to exemplary implementations, the substrate can be provided to a tumbler apparatus in substantially dry form. The chromium-alkali metal solution can be combined with the substrate in the apparatus and mixed utilizing the apparatus to form the catalyst solution.
A second solution including an alkali metal composition may be prepared separately and then combined with the first solution or together with the first solution of the acid composition to form a second solution, for example. According to an exemplary implementation, the second solution can include a solvent such as water. It is contemplated that other solvents for the first and second solutions may be utilized as well.
The alkali metal composition can include potassium, as well as, chromium and/or oxygen. The alkali metal composition can be a salt of an alkali metal, including alkali metal salts of chromic acids, such as potassium dichromate or K2Cr2O7. Alkali metal salts of other acids may be comprised by the alkali metal composition. The alkali metal composition of the alkali metal solution can be at least about 4% (wt./wt.), for example.
Upon preparing the first and second solutions, the solutions may be combined, if necessary, to form a third solution that includes the solvent, the acid composition, and the alkali metal composition. This third solution can be referred to as chromium-alkali metal solution. These solutions can be prepared by agitating the compositions with the solvents to form a solution of the composition according to exemplary implementations. Vessels appropriate for such mixing include plastic and/or glass vessels, and the mixing can be accomplished using a magnetic stir-bar, for example.
The chromium-alkali metal solution can be combined with a substrate to form a catalyst solution. As described above, the substrate can include carbon and/or activated carbon such as Takeda and/or Calgon carbon. According to exemplary implementations, the substrate can be provided to a tumbler apparatus in substantially dry form. The chromium-alkali metal solution can be combined with the substrate in the apparatus and mixed utilizing the apparatus to form the catalyst solution.
The catalyst solution may include a weight ratio of Cr03/K2CrO7/activated carbon/water of about 10.8/0.6/30/23, for example. According to exemplary embodiments, combining the substrate with the chromium-alkali solution may result in an exotherm. The resulting exotherm may be sufficient to separate significant amounts of, solvent from the catalyst solution. According to exemplary implementations, the combination of mixing the catalyst solution and the exotherm can separate a majority of the solvent from the catalyst solution, and in other implementations, can remove all but trace amounts of solvent leaving a catalyst composition that includes ppm quantities of the solvent.
In exemplary embodiments, the amount of alkali metal composition used to create the catalyst can vary depending on the amount of catalyst desired, for example. For example and by way of example only, about 45.4 kgs of chromic acid can be combined with about 1.81 kgs of potassium dichromate to form a chromium-alkali solution than can be mixed with about 100g activated carbon.
The following four examples are exemplary of the preparation of the catalyst composition.
Example 1 An acid composition solution A can be prepared by dissolving 3000g of Cr03 (chromium (VI) oxide) in 2222g of DI water. The acid composition solution can be mixed in a Nalgene container equipped with spigot and magnetic stirring. An alkali metal composition solution B can be prepared by adding '166.7g of K2CrO7 (potassium dichromate) to 4167g of DI water. The alkali-metal solution can be placed in a second Nalgene container equipped with spigot and magnetic stirring for mixing.
To ensure that all compositions were dissolved in the solvent aliquots of the solvent can be analyzed form metals such as chromium and/or potassium. Solution A can then be added to solution B and mixed further if deemed appropriate to form the chromium-alkali solution. A tumbler apparatus substantially lined with a fluoropolymer such as Kynar (Arkema, 4-8= cours Michelet, Ia Defense 10, F92091 Paris Ia Defense Cedex) having polypropylene port and plug, as well as, a stainless steel gauge and valve fittings can be loaded with 8333g of activated carbon (Takeda, coconut, pelletized). The tumbler apparatus can be sealed by bolting the flange in place and tightening. The solution (A+B) can be poured from the spigot of the Nalgene container through the port.
U'pon addition of the chromium-alkali solution to the carbon to form the catalyst solution, water vapor can be observed emanating from the solution. After adding the entirety of the chromium-alkali solution to the carbon, the tumbler apparatus can be plugged and the vapor pressure can be relieved via a valve to maintain the pressure within the tumbler apparatus between about 136 kPa to about 143 kPa. The catalyst solution can be mixed within the tumbler apparatus for about 5 minutes which can generate significant vapor production. Upon completion of mixing, the catalyst composition can be observed to emanate vapor, but it can be essentially dry.
Example 2 The process of Example 1 can be repeated utilizing Calgon (coconut, flake) carbon. The vapor produced can have an orange tint.
Example 3 An acid composition solution A can be prepared by dissolving 72g of Cr03 (chromium (VI) oxide) in 53.3g of DI water. The acid composition solution can be mixed in a Nalgene container equipped with spigot and magnetic stirring. An alkali metal composition solution B can be prepared by adding 4g of K2CrO7 (potassium dichromate) to 100g of DI water. The alkali-metal solution can be placed in a second Nalgene container equipped with spigot and magnetic stirring for mixing. To ensure that all compositions were dissolved in the solvent, aliquots of the solvent can be analyzed for metals such as chromium and/or potassium. Solution A can then be added to solution B and mixed further if deemed appropriate to form the chromium-alkali solution.
A tumbler apparatus substantially lined with a fluoropolymer such as Kynar having polypropylene port and plug, as well as a stainless steel gauge and valve fittings, can be loaded with 200g of activated carbon (Takeda, coconut, pelletized). The tumbler apparatus can be sealed by bolting the flange in place and tightening. The solution (A+B) can be poured from the spigot of the Nalgene container through the port.
Upon addition of the chromium-alkali solution to the carbon to form the catalyst solution, water vapor can be observed emanating from the solution. After adding the entirety of the chromium-alkali solution to the carbon, the tumbler apparatus can be plugged and the vapor pressure can be relieved via a Whitney valve to maintain the pressure within the tumbler apparatus between about 136 kPa to about 143 kPa. The catalyst solution can be mixed within the tumbler apparatus for about 4 minutes which can generate significant vapor production. Upon completion of mixing the catalyst composition can be observed to emanate vapor, but it can be essentially dry.
Example 4 A chromium-alkali solution can be prepared by dissolving 360g of Cr03 (chromium (VI) oxide) and 20.Og of K2CrO7 in 650g of DI water in a 1 liter plastic container.
The chromium-alkali solution can then be added to a vessel containing 1000g of Takeda activated carbon to form the catalyst solution.
The catalyst solution can be mixed, and the solvent removed using the exotherm in combination with the mixing. After about 2 hours of mixing, little if any heat can be observed emanating from the vessel, and the vessel contains the catalyst composition essentially free of solvent.
Referring again to system 10, catalyst composition 20 can be loaded into reactor 12 to form a solid matrix contained within reactor 12.
Prior to being used to catalyze the reaction of reactants of reactant reservoir 14 and reagents of reagent reservoir 16, catalyst composition 20 can be prepared and/or activated. For example, and by way of example only, reactor 12 can be heated to approximately 250 C and a flow of inert gas such as nitrogen at approximately 5 liters/minute can be fed through reactor 12. After passing through reactor 12, the nitrogen can be monitored for water content, and when water content is sufficiently low, for example, no more than ppm levels, the catalyst can be viewed as sufficiently dry and allowed to be useful for reaction.
According to exemplary implementations, catalyst composition 20 can be activated and prepared for use with specific reagents. For example, catalyst composition 20 can be provided to within reactor 12.
According to exemplary implementations, composition 20 may completely fill the interior of reactor 12. Reactor 12 may be heated to provide heat to composition 12 and a drying composition, such as an inert gas, may be provided to reactor 12. According to exemplary implementations, N in the form of N2 may be provided to the reactor 12 having heated composition 20 therein. Upon providing the drying composition to reactor 12, an effluent from reactor 12 may be monitored for water. Upon reaching a predetermined level of water within the effluent, the supply of drying composition may be stopped and a supply of activating composition to reactor 12 may be started. The activating composition may include a halogenating reagent such as HF described herein, but can also include other halogenating reagents such as HBr and/or HCI depending on the desired product.
According to exemplary implementations, an activating composition such as HF can be provided to a catalyst composition comprising Cr and 0, such as a catalyst composition prepared from a Cr03 solution described herein. Upon providing the activating composition to the catalyst composition, the effluent from reactor 12 may be monitored for water. Upon reaching a predetermined level of water and/or HF within the effluent, the supply of activating composition may be stopped and the catalyst composition considered activated and/or prepared.
As another example of catalyst composition 20 activation and/or preparation, where the reagent of reagent reservoir 16 includes a halogenation reagent. such as hydrofluoric acid, for example, a combination of hydrogen fluoride, inert gas, and in certain embodiments, an oxidizing reagent from oxidizing reagent reservoir 22, such as oxygen, can be provided to the catalyst composition through the reactor to prepare the catalyst composition for use and/or activate the catalyst composition. For example and by way of example only, the reactor can be heated to approximately 380 C and approximately 0.6 grams/minute of HF, 0.9 grams/minute of N2 and 0.1 grams/minute of 02 can be fed through the catalyst composition for a period of about 12 hours. Prior to exposing the catalyst composition to a reactant, the reactor can be cooled to the temperature to be utilized for the reaction. Examples 5 and 6 below are exemplary of catalyst composition activation.
Example 5 About 2400g of catalyst composition can be charged to a reactor (tube having a volume = 2832cc). The catalyst composition can be dried under nitrogen and then heated to 100 C and allowed to equilibrate holding the temperature at about 100 C for 30 minutes and increasing to about 150 C, about 175 C, about 200 C, and about 250 C holding the temperature for 30 minutes after equilibration. The total drying time can range from about 3 to about 8 hours. Once the catalyst is dry (no water vapor detected leaving the reactor), an HF flow can be started and the reactor temperature can be brought up to about 300 C. HF can be run through the reactor until HF breakthrough is detected. HF can be fed at 5g/min. to give a 14.5 second contact time involving 900g of HF being fed which is about 0.375g HF/g of catalyst.
Example 6 About 69.5g of catalyst composition can be charged to an industrial hot oil reactor. A nitrogen purge of 150cc/min nitrogen can be provided to the reactor for drying the catalyst bed. The reactor can be maintained at 100 C and the increased from 100 C to 343 C over 7 hours until no more water vapor was detected leaving the reactor. HF can then be provided to the reactor at a flow rate of 383.4cc/min for I hour before starting the reactants.
According to exemplary embodiments, a compound and/or reactant from reactant reservoir 14 can be exposed to a reagent from reagent reservoir 16 in the presence of catalyst composition 20. According to exemplary embodiments, the reactant of reactant reservoir 14 can be a C-3 compound, and in exemplary embodiments, this C-3 compound can include at least one halogen. The one halogen can be one or more of F, CI, Br, and I, for example. The C-3 compound can also include H, for example. According to exemplary embodiments, the C-3 compound is 1,1,1,3-tetrachloropropane (tetrachloropropane, TCP). Other C-3 compounds can be reacted utilizing the catalyst composition, however, the C-3 compounds that contain halogens at both terminal ends without a halogen at the geminal carbon have been shown to exchange halogens, as well as, eliminate halogens, thereby forming halogenated olefins such as the reaction of HF and tetrachloropropane to form 3,3,3-trifluoroprop-1 -ene (trifluoropropene, TFP) in the presence of catalyst composition 20.
Referring to the reagent of reagent reservoir 16, the reagent can include at least one halogen, and the halogen can include one or more of F, Cl, Br, and I. The reagent can also include a hydrogen, for example.
Exemplary reagents can be referred to as halogenating reagents and/or can include HX, with X being one of F, Cl, Br, and I. According to exemplary embodiments, catalyst composition 20 can include at least one alkali metal when exposed to the C-3 compound and the reagent of reagent reservoir 16. The exposing of the C-3 compound to the reagent of reagent reservoir 16 can occur within reactor 12 configured to maintain the temperature of the catalyst composition within the reaction chamber to at least about 250 C, according to exemplary embodiments. According to other embodiments, the temperature of the catalyst composition within the reaction chamber can be maintained at less than about 350 C, and still other embodiments the temperature of the catalyst composition within the reaction chamber during exposure of the C-3 compound to the reagent can be maintained at from about 300 C to about 330 C.
Exemplary depicted System 10 can include an oxidizing reagent reservoir 22. According to exemplary embodiments, the oxidizing reagent can be provided to the reaction chamber during the exposure of a compound, including the reactant, to the reagent of reagent reservoir 16.
This oxidizing reagent can include oxygen in the form of 02, for example.
According to exemplary implementations, reagent reservoir 16 can include the reagent HF. The reactant reservoir 14 can include the reactant compound tetrachloropropane, and the oxidizing reagent reservoir 22 can include the oxidizing reagent oxygen. The oxygen can be at least about 0.1 to about 0.3% of the molar amount of both the C-3 compound and the reagent when being provided to reactor 12. The tetrachloropropane can be provided from a telomerization reaction such the telomerization of carbon tetrachloride and ethylene. According to exemplary implementations, the HF can be fed through a 836L reactor at approximately 10.6 kgs/minute. The tetrachloropropane can be fed through thereactor at approximately 5.37 kgs/minute, and the oxygen can be fed through the reactor at approximately 0.03 kgs/minute. According to exemplary embodiments, the exposure of these reactants and reagents to catalyst composition 20 can result in the formation of trifluoropropene or particularly, 1,1,1-trifluoropropene. This trifluoropropene, along with reactants, reagents, and/or by-products can be provided to product reservoir 18. Product reservoir 18 can be coupled to exemplary product purification apparatuses such as distillation, scrubbing, and/or drying apparatuses known to those of ordinary skill in the art.
According to another exemplary embodiment, the reactant of reactant reservoir 14 can include a C-1 compound that can include at least one halogen, and the halogen can be F, Cl, Br, and I, for example.
The C-1 compound of reactant reservoir 14 can also comprise an H, for example. In exemplary embodiments, the C-1 compound can be dichloromethane. The reagent of reagent reservoir 16 can be HF, for example. According to exemplary embodiments, the dichloromethane from reactant reservoir 14 can be exposed to the catalyst composition in the presence of the reagent of reagent reservoir 16. In exemplary embodiments, the reagent of reagent reservoir 16 can be HF, for example. The dichloromethane may be provided at about10.8kgs/minute and the HF may be provided at about 40.8kgs/minute to a reactor having an internal volume of about 2158L. The exposure of the dichloromethane to the HF can be performed in the presence of the oxidizing reagent and the oxidizing reagent can be less than about 0.3% mole percent of the reactants. The exposure of dichloromethane to HF can be performed while maintaining the catalyst composition at a temperature of at least about 316 C in an exemplary embodiment. In other embodiments, the catalyst composition within the reaction chamber when exposing the dichloromethane to HF can be maintained at less than about 343 C and in still other embodiments, the catalyst composition can be maintained to from about 316 C to about 341 C.
According to exemplary embodiments, the exposure of dichloromethane to the reagent HF can result in the production of difluoromethane. The difluoromethane can be efficiently produced from the dichloromethane, thereby resulting in very few intermediate products, such as fluorochloromethane and/or unreacted products, such as dichloromethane. The difluoromethane can be provided to product reservoir 18, and product reservoir 18 can either take the form of and/or be configured to be coupled to purification apparatuses such as distillation, scrubbing, and/or drying apparatuses, for example.
Upon use of catalyst composition 20 for extended periods of time, the catalyst composition may be reactivated. For example, without providing reactants to reactor 12, the oxidizing reagent may be provided to the catalyst composition. According to exemplary implementations, the catalyst composition may be heated to a predetermined temperature and the oxidizing reagent provided to the composition for a predetermined amount of time. Upon completion of this time, catalyst composition 20 may be exposed to the halogenating reagent, for example as described herein, until specificed compounds are determined to be in the effluent at pretermined levels.
As another example, without providing reactant compounds, the reagent may be provided to the catalyst composition in the presence of an inert gas such as nitrogen and the oxidizing reagent. In exemplary embodiments, while heating the reactor to' a predetermined temperature about 3.6 kgs/minute of HF, 2.9 kgs/minute of N2 and about 0.12 kgs/minute of 02 can be provided to a 836L reactor.
Production systems that include catalyst composition 20 and as configured as exemplarily described herein can be relied upon to produce product for extended periods of time. For example and by way of example only, the production of TFP can be continuously relied upon 24 hours a day, 7 days a week to produce TFP from TCP and HF in the presence of catalyst composition 20 for weeks at a time without reactivation and/or replacement of catalyst composition 20. Upon reactivation of catalyst composition 20, TFP may be produced for months at a time, and even up to 6 months at time running 24 hours a day, 7 days a week.
As another example and by way of example only, the production of difluoromethane from the reaction of dichloromethane and HF in the presence of catalyst composition 20 can be continuously relied upon 24 hours a day, 7 days a week for months at a time and even an entire year without reactivation and/or replacement of catalyst composition 20. As an example about 600,000 kgs of difluoromethane can be produced using only 136 kgs of catalyst composition 20.
In exemplary embodiments, the amount of alkali metal composition used to create the catalyst can vary depending on the amount of catalyst desired, for example. For example and by way of example only, about 45.4 kgs of chromic acid can be combined with about 1.81 kgs of potassium dichromate to form a chromium-alkali solution than can be mixed with about 100g activated carbon.
The following four examples are exemplary of the preparation of the catalyst composition.
Example 1 An acid composition solution A can be prepared by dissolving 3000g of Cr03 (chromium (VI) oxide) in 2222g of DI water. The acid composition solution can be mixed in a Nalgene container equipped with spigot and magnetic stirring. An alkali metal composition solution B can be prepared by adding '166.7g of K2CrO7 (potassium dichromate) to 4167g of DI water. The alkali-metal solution can be placed in a second Nalgene container equipped with spigot and magnetic stirring for mixing.
To ensure that all compositions were dissolved in the solvent aliquots of the solvent can be analyzed form metals such as chromium and/or potassium. Solution A can then be added to solution B and mixed further if deemed appropriate to form the chromium-alkali solution. A tumbler apparatus substantially lined with a fluoropolymer such as Kynar (Arkema, 4-8= cours Michelet, Ia Defense 10, F92091 Paris Ia Defense Cedex) having polypropylene port and plug, as well as, a stainless steel gauge and valve fittings can be loaded with 8333g of activated carbon (Takeda, coconut, pelletized). The tumbler apparatus can be sealed by bolting the flange in place and tightening. The solution (A+B) can be poured from the spigot of the Nalgene container through the port.
U'pon addition of the chromium-alkali solution to the carbon to form the catalyst solution, water vapor can be observed emanating from the solution. After adding the entirety of the chromium-alkali solution to the carbon, the tumbler apparatus can be plugged and the vapor pressure can be relieved via a valve to maintain the pressure within the tumbler apparatus between about 136 kPa to about 143 kPa. The catalyst solution can be mixed within the tumbler apparatus for about 5 minutes which can generate significant vapor production. Upon completion of mixing, the catalyst composition can be observed to emanate vapor, but it can be essentially dry.
Example 2 The process of Example 1 can be repeated utilizing Calgon (coconut, flake) carbon. The vapor produced can have an orange tint.
Example 3 An acid composition solution A can be prepared by dissolving 72g of Cr03 (chromium (VI) oxide) in 53.3g of DI water. The acid composition solution can be mixed in a Nalgene container equipped with spigot and magnetic stirring. An alkali metal composition solution B can be prepared by adding 4g of K2CrO7 (potassium dichromate) to 100g of DI water. The alkali-metal solution can be placed in a second Nalgene container equipped with spigot and magnetic stirring for mixing. To ensure that all compositions were dissolved in the solvent, aliquots of the solvent can be analyzed for metals such as chromium and/or potassium. Solution A can then be added to solution B and mixed further if deemed appropriate to form the chromium-alkali solution.
A tumbler apparatus substantially lined with a fluoropolymer such as Kynar having polypropylene port and plug, as well as a stainless steel gauge and valve fittings, can be loaded with 200g of activated carbon (Takeda, coconut, pelletized). The tumbler apparatus can be sealed by bolting the flange in place and tightening. The solution (A+B) can be poured from the spigot of the Nalgene container through the port.
Upon addition of the chromium-alkali solution to the carbon to form the catalyst solution, water vapor can be observed emanating from the solution. After adding the entirety of the chromium-alkali solution to the carbon, the tumbler apparatus can be plugged and the vapor pressure can be relieved via a Whitney valve to maintain the pressure within the tumbler apparatus between about 136 kPa to about 143 kPa. The catalyst solution can be mixed within the tumbler apparatus for about 4 minutes which can generate significant vapor production. Upon completion of mixing the catalyst composition can be observed to emanate vapor, but it can be essentially dry.
Example 4 A chromium-alkali solution can be prepared by dissolving 360g of Cr03 (chromium (VI) oxide) and 20.Og of K2CrO7 in 650g of DI water in a 1 liter plastic container.
The chromium-alkali solution can then be added to a vessel containing 1000g of Takeda activated carbon to form the catalyst solution.
The catalyst solution can be mixed, and the solvent removed using the exotherm in combination with the mixing. After about 2 hours of mixing, little if any heat can be observed emanating from the vessel, and the vessel contains the catalyst composition essentially free of solvent.
Referring again to system 10, catalyst composition 20 can be loaded into reactor 12 to form a solid matrix contained within reactor 12.
Prior to being used to catalyze the reaction of reactants of reactant reservoir 14 and reagents of reagent reservoir 16, catalyst composition 20 can be prepared and/or activated. For example, and by way of example only, reactor 12 can be heated to approximately 250 C and a flow of inert gas such as nitrogen at approximately 5 liters/minute can be fed through reactor 12. After passing through reactor 12, the nitrogen can be monitored for water content, and when water content is sufficiently low, for example, no more than ppm levels, the catalyst can be viewed as sufficiently dry and allowed to be useful for reaction.
According to exemplary implementations, catalyst composition 20 can be activated and prepared for use with specific reagents. For example, catalyst composition 20 can be provided to within reactor 12.
According to exemplary implementations, composition 20 may completely fill the interior of reactor 12. Reactor 12 may be heated to provide heat to composition 12 and a drying composition, such as an inert gas, may be provided to reactor 12. According to exemplary implementations, N in the form of N2 may be provided to the reactor 12 having heated composition 20 therein. Upon providing the drying composition to reactor 12, an effluent from reactor 12 may be monitored for water. Upon reaching a predetermined level of water within the effluent, the supply of drying composition may be stopped and a supply of activating composition to reactor 12 may be started. The activating composition may include a halogenating reagent such as HF described herein, but can also include other halogenating reagents such as HBr and/or HCI depending on the desired product.
According to exemplary implementations, an activating composition such as HF can be provided to a catalyst composition comprising Cr and 0, such as a catalyst composition prepared from a Cr03 solution described herein. Upon providing the activating composition to the catalyst composition, the effluent from reactor 12 may be monitored for water. Upon reaching a predetermined level of water and/or HF within the effluent, the supply of activating composition may be stopped and the catalyst composition considered activated and/or prepared.
As another example of catalyst composition 20 activation and/or preparation, where the reagent of reagent reservoir 16 includes a halogenation reagent. such as hydrofluoric acid, for example, a combination of hydrogen fluoride, inert gas, and in certain embodiments, an oxidizing reagent from oxidizing reagent reservoir 22, such as oxygen, can be provided to the catalyst composition through the reactor to prepare the catalyst composition for use and/or activate the catalyst composition. For example and by way of example only, the reactor can be heated to approximately 380 C and approximately 0.6 grams/minute of HF, 0.9 grams/minute of N2 and 0.1 grams/minute of 02 can be fed through the catalyst composition for a period of about 12 hours. Prior to exposing the catalyst composition to a reactant, the reactor can be cooled to the temperature to be utilized for the reaction. Examples 5 and 6 below are exemplary of catalyst composition activation.
Example 5 About 2400g of catalyst composition can be charged to a reactor (tube having a volume = 2832cc). The catalyst composition can be dried under nitrogen and then heated to 100 C and allowed to equilibrate holding the temperature at about 100 C for 30 minutes and increasing to about 150 C, about 175 C, about 200 C, and about 250 C holding the temperature for 30 minutes after equilibration. The total drying time can range from about 3 to about 8 hours. Once the catalyst is dry (no water vapor detected leaving the reactor), an HF flow can be started and the reactor temperature can be brought up to about 300 C. HF can be run through the reactor until HF breakthrough is detected. HF can be fed at 5g/min. to give a 14.5 second contact time involving 900g of HF being fed which is about 0.375g HF/g of catalyst.
Example 6 About 69.5g of catalyst composition can be charged to an industrial hot oil reactor. A nitrogen purge of 150cc/min nitrogen can be provided to the reactor for drying the catalyst bed. The reactor can be maintained at 100 C and the increased from 100 C to 343 C over 7 hours until no more water vapor was detected leaving the reactor. HF can then be provided to the reactor at a flow rate of 383.4cc/min for I hour before starting the reactants.
According to exemplary embodiments, a compound and/or reactant from reactant reservoir 14 can be exposed to a reagent from reagent reservoir 16 in the presence of catalyst composition 20. According to exemplary embodiments, the reactant of reactant reservoir 14 can be a C-3 compound, and in exemplary embodiments, this C-3 compound can include at least one halogen. The one halogen can be one or more of F, CI, Br, and I, for example. The C-3 compound can also include H, for example. According to exemplary embodiments, the C-3 compound is 1,1,1,3-tetrachloropropane (tetrachloropropane, TCP). Other C-3 compounds can be reacted utilizing the catalyst composition, however, the C-3 compounds that contain halogens at both terminal ends without a halogen at the geminal carbon have been shown to exchange halogens, as well as, eliminate halogens, thereby forming halogenated olefins such as the reaction of HF and tetrachloropropane to form 3,3,3-trifluoroprop-1 -ene (trifluoropropene, TFP) in the presence of catalyst composition 20.
Referring to the reagent of reagent reservoir 16, the reagent can include at least one halogen, and the halogen can include one or more of F, Cl, Br, and I. The reagent can also include a hydrogen, for example.
Exemplary reagents can be referred to as halogenating reagents and/or can include HX, with X being one of F, Cl, Br, and I. According to exemplary embodiments, catalyst composition 20 can include at least one alkali metal when exposed to the C-3 compound and the reagent of reagent reservoir 16. The exposing of the C-3 compound to the reagent of reagent reservoir 16 can occur within reactor 12 configured to maintain the temperature of the catalyst composition within the reaction chamber to at least about 250 C, according to exemplary embodiments. According to other embodiments, the temperature of the catalyst composition within the reaction chamber can be maintained at less than about 350 C, and still other embodiments the temperature of the catalyst composition within the reaction chamber during exposure of the C-3 compound to the reagent can be maintained at from about 300 C to about 330 C.
Exemplary depicted System 10 can include an oxidizing reagent reservoir 22. According to exemplary embodiments, the oxidizing reagent can be provided to the reaction chamber during the exposure of a compound, including the reactant, to the reagent of reagent reservoir 16.
This oxidizing reagent can include oxygen in the form of 02, for example.
According to exemplary implementations, reagent reservoir 16 can include the reagent HF. The reactant reservoir 14 can include the reactant compound tetrachloropropane, and the oxidizing reagent reservoir 22 can include the oxidizing reagent oxygen. The oxygen can be at least about 0.1 to about 0.3% of the molar amount of both the C-3 compound and the reagent when being provided to reactor 12. The tetrachloropropane can be provided from a telomerization reaction such the telomerization of carbon tetrachloride and ethylene. According to exemplary implementations, the HF can be fed through a 836L reactor at approximately 10.6 kgs/minute. The tetrachloropropane can be fed through thereactor at approximately 5.37 kgs/minute, and the oxygen can be fed through the reactor at approximately 0.03 kgs/minute. According to exemplary embodiments, the exposure of these reactants and reagents to catalyst composition 20 can result in the formation of trifluoropropene or particularly, 1,1,1-trifluoropropene. This trifluoropropene, along with reactants, reagents, and/or by-products can be provided to product reservoir 18. Product reservoir 18 can be coupled to exemplary product purification apparatuses such as distillation, scrubbing, and/or drying apparatuses known to those of ordinary skill in the art.
According to another exemplary embodiment, the reactant of reactant reservoir 14 can include a C-1 compound that can include at least one halogen, and the halogen can be F, Cl, Br, and I, for example.
The C-1 compound of reactant reservoir 14 can also comprise an H, for example. In exemplary embodiments, the C-1 compound can be dichloromethane. The reagent of reagent reservoir 16 can be HF, for example. According to exemplary embodiments, the dichloromethane from reactant reservoir 14 can be exposed to the catalyst composition in the presence of the reagent of reagent reservoir 16. In exemplary embodiments, the reagent of reagent reservoir 16 can be HF, for example. The dichloromethane may be provided at about10.8kgs/minute and the HF may be provided at about 40.8kgs/minute to a reactor having an internal volume of about 2158L. The exposure of the dichloromethane to the HF can be performed in the presence of the oxidizing reagent and the oxidizing reagent can be less than about 0.3% mole percent of the reactants. The exposure of dichloromethane to HF can be performed while maintaining the catalyst composition at a temperature of at least about 316 C in an exemplary embodiment. In other embodiments, the catalyst composition within the reaction chamber when exposing the dichloromethane to HF can be maintained at less than about 343 C and in still other embodiments, the catalyst composition can be maintained to from about 316 C to about 341 C.
According to exemplary embodiments, the exposure of dichloromethane to the reagent HF can result in the production of difluoromethane. The difluoromethane can be efficiently produced from the dichloromethane, thereby resulting in very few intermediate products, such as fluorochloromethane and/or unreacted products, such as dichloromethane. The difluoromethane can be provided to product reservoir 18, and product reservoir 18 can either take the form of and/or be configured to be coupled to purification apparatuses such as distillation, scrubbing, and/or drying apparatuses, for example.
Upon use of catalyst composition 20 for extended periods of time, the catalyst composition may be reactivated. For example, without providing reactants to reactor 12, the oxidizing reagent may be provided to the catalyst composition. According to exemplary implementations, the catalyst composition may be heated to a predetermined temperature and the oxidizing reagent provided to the composition for a predetermined amount of time. Upon completion of this time, catalyst composition 20 may be exposed to the halogenating reagent, for example as described herein, until specificed compounds are determined to be in the effluent at pretermined levels.
As another example, without providing reactant compounds, the reagent may be provided to the catalyst composition in the presence of an inert gas such as nitrogen and the oxidizing reagent. In exemplary embodiments, while heating the reactor to' a predetermined temperature about 3.6 kgs/minute of HF, 2.9 kgs/minute of N2 and about 0.12 kgs/minute of 02 can be provided to a 836L reactor.
Production systems that include catalyst composition 20 and as configured as exemplarily described herein can be relied upon to produce product for extended periods of time. For example and by way of example only, the production of TFP can be continuously relied upon 24 hours a day, 7 days a week to produce TFP from TCP and HF in the presence of catalyst composition 20 for weeks at a time without reactivation and/or replacement of catalyst composition 20. Upon reactivation of catalyst composition 20, TFP may be produced for months at a time, and even up to 6 months at time running 24 hours a day, 7 days a week.
As another example and by way of example only, the production of difluoromethane from the reaction of dichloromethane and HF in the presence of catalyst composition 20 can be continuously relied upon 24 hours a day, 7 days a week for months at a time and even an entire year without reactivation and/or replacement of catalyst composition 20. As an example about 600,000 kgs of difluoromethane can be produced using only 136 kgs of catalyst composition 20.
Claims (55)
1. A catalyst composition comprising:
a substrate;
at least about 13 %(wt/wt) chromium; and at least one alkali metal.
a substrate;
at least about 13 %(wt/wt) chromium; and at least one alkali metal.
2. The catalyst composition of claim 1 wherein the substrate comprises activated carbon.
3. The catalyst composition of claim 1 wherein the one alkali metal comprises potassium.
4. The catalyst composition of claim 1 wherein:
the substrate comprises activated carbon; and the one alkali metal is potassium.
the substrate comprises activated carbon; and the one alkali metal is potassium.
5. The catalyst composition of claim 1 wherein the mole ratio of the chromium to the one alkali metal of the catalyst composition is at least about 50:1.
6. A production process comprising:
preparing a first solution comprising an alkali metal composition comprising K2CrO7;
exposing the first solution to a substrate to form a second solution, the second solution comprising the substrate and the alkali metal composition; and removing a catalyst composition from the second solution, the catalyst composition comprising the alkali metal composition and the substrate.
preparing a first solution comprising an alkali metal composition comprising K2CrO7;
exposing the first solution to a substrate to form a second solution, the second solution comprising the substrate and the alkali metal composition; and removing a catalyst composition from the second solution, the catalyst composition comprising the alkali metal composition and the substrate.
7. (cancelled).
8. (cancelled).
9. (cancelled).
10. The production process of claim 6 wherein the first solution comprises water.
11. (cancelled).
12. (cancelled).
13. The production process of claim 6 wherein the substrate comprises activated carbon.
14. (cancelled).
15. The production process of claim 6 wherein the second solution further comprises water, and the removing a catalyst composition from the second solution comprises separating at least a portion of the water of the second solution from the alkali metal composition and the substrate.
16. The production process of claim 15 wherein the portion of the water comprises a majority of the water.
17. The production process of claim 16 wherein the portion of the water comprises all but trace amounts of the water.
18. A production process comprising exposing a an at least partially halogenated compound to a reagent in the presence of a catalyst composition, the catalyst composition comprising a substrate, chromium, and at least one alkali metal.
19. The production process of claim 18 wherein the exposing the compound to the reagent in the presence of the catalyst composition comprises:
providing a reaction chamber containing the catalyst composition, and configured to receive both the compound and the reagent; and further comprises providing oxygen to the reaction chamber during the exposing.
providing a reaction chamber containing the catalyst composition, and configured to receive both the compound and the reagent; and further comprises providing oxygen to the reaction chamber during the exposing.
20. The production process of claim 19 wherein the oxygen is provided to the chamber in an amount that is at least about 0.1 % of the molar amount of both the compound and the reagent.
21. The production process of claim 18 wherein the compound is a C-3 compound.
22. (cancelled).
23. The production process of claim 21 wherein a halogen of the C-3 compound is one of F, Cl, Br, and I.
24. The production process of claim 23 wherein the C-3 compound comprises H.
25. The production process of claim 24 wherein the C-3 compound is 1,1,1,3-tetrachloropropane.
26. The production process of claim 18 wherein the compound is a C-1 compound.
27. The production process of claim 26 wherein the exposing the compound to the reagent in the presence of the catalyst composition comprises:
providing a reaction chamber containing the catalyst composition, and configured to receive both the compound and the reagent; and further comprises providing oxygen to the reaction chamber during the exposing.
providing a reaction chamber containing the catalyst composition, and configured to receive both the compound and the reagent; and further comprises providing oxygen to the reaction chamber during the exposing.
28. The production process of claim 27 wherein the oxygen is provided to the chamber in an amount that is at least about 0.1 % of the molar amount of both the compound and the reagent.
29. (cancelled).
30. The production process of claim 27 wherein a halogen of the C-1 compound is one of F, Cl, Br, and I.
31. The production process of claim 30 wherein the C-1 compound comprises H.
32. The production process of claim 31 wherein the C-1 compound is dichloromethane.
33. The production process of claim 32 wherein the exposing the C-1 compound to the reagent in the presence of the catalyst composition comprises:
providing a reaction chamber containing the catalyst composition, and configured to receive both the C-1 compound and the reagent;
maintaining the temperature of the catalyst within the reaction chamber to at least about 316°C; and providing both the C-1 compound and the reagent to within the reaction chamber.
providing a reaction chamber containing the catalyst composition, and configured to receive both the C-1 compound and the reagent;
maintaining the temperature of the catalyst within the reaction chamber to at least about 316°C; and providing both the C-1 compound and the reagent to within the reaction chamber.
34. The production process of claim 32 wherein the exposing the C-1 compound to the reagent in the presence of the catalyst composition comprises:
providing a reaction chamber containing the catalyst composition, and configured to receive both the C-1 compound and the reagent;
maintaining the temperature of the catalyst within the reaction chamber to less than about 343°C; and providing both the C-1 compound and the reagent to within the reaction chamber.
providing a reaction chamber containing the catalyst composition, and configured to receive both the C-1 compound and the reagent;
maintaining the temperature of the catalyst within the reaction chamber to less than about 343°C; and providing both the C-1 compound and the reagent to within the reaction chamber.
35. The production process of claim 32 wherein the exposing the C-1 compound to the reagent in the presence of the catalyst composition comprises:
providing a reaction chamber containing the catalyst composition, and configured to receive both the C-1 compound and the reagent;
maintaining the temperature of the catalyst within the reaction chamber to from about 316°C to about 341°C; and providing both the C-1 compound and the reagent to within the reaction chamber.
providing a reaction chamber containing the catalyst composition, and configured to receive both the C-1 compound and the reagent;
maintaining the temperature of the catalyst within the reaction chamber to from about 316°C to about 341°C; and providing both the C-1 compound and the reagent to within the reaction chamber.
36. The production process of claim 18 wherein the reagent comprises at least one halogen.
37. The production process of claim 36 wherein the one halogen is one of F, Cl, Br, and I.
38. The production process of claim 37 wherein the reagent comprises H.
39. The production process of claim 38 wherein the reagent comprises HX, X
being one of F, Cl, Br, and I.
being one of F, Cl, Br, and I.
40. The production process of claim 18 wherein the substrate comprises activated carbon.
41. The production process of claim 18 wherein the one alkali metal is potassium.
42. The production process of claim 18 wherein the mole ratio of the chromium to the one alkali metal of the catalyst composition comprises at least about 50:1.
43. A production process comprising exposing an at least partially halogenated compound to a reagent in the presence of a catalyst composition, the catalyst composition comprising at least one alkali metal.
44. The production process of claim 43 wherein the exposing the C-3 compound to the reagent in the presence of the catalyst composition comprises:
providing a reaction chamber containing the catalyst composition, and configured to receive both the C-3 compound and the reagent;
maintaining the temperature of the catalyst composition within the reaction chamber to at least about 300°C; and providing both the C-3 compound and the reagent to within the reaction chamber.
providing a reaction chamber containing the catalyst composition, and configured to receive both the C-3 compound and the reagent;
maintaining the temperature of the catalyst composition within the reaction chamber to at least about 300°C; and providing both the C-3 compound and the reagent to within the reaction chamber.
45. The production process of claim 43 wherein the exposing the C-3 compound to the reagent in the presence of the catalyst composition comprises:
providing a reaction chamber containing the catalyst composition, and configured to receive both the C-3 compound and the reagent;
maintaining the temperature of the catalyst composition within the reaction chamber to less than about 350°C; and providing both the C-3 compound and the reagent to within the reaction chamber.
providing a reaction chamber containing the catalyst composition, and configured to receive both the C-3 compound and the reagent;
maintaining the temperature of the catalyst composition within the reaction chamber to less than about 350°C; and providing both the C-3 compound and the reagent to within the reaction chamber.
46. The production process of claim 43 wherein the exposing the C-3 compound to the reagent in the presence of the catalyst composition comprises:
providing a reaction chamber containing the catalyst composition, and configured to receive both the C-3 compound and the reagent;
maintaining the temperature of the catalyst composition within the reaction chamber to from about 300°C to about 330°C; and providing both the C-3 compound and the reagent to within the reaction chamber.
providing a reaction chamber containing the catalyst composition, and configured to receive both the C-3 compound and the reagent;
maintaining the temperature of the catalyst composition within the reaction chamber to from about 300°C to about 330°C; and providing both the C-3 compound and the reagent to within the reaction chamber.
47. The production process of claim 43 wherein the exposing the C-3 compound to the reagent in the presence of the catalyst composition comprises:
providing a reaction chamber containing the catalyst composition, and configured to receive both the C-3 compound and the reagent; and further comprises providing oxygen to the reaction chamber during the exposing.
providing a reaction chamber containing the catalyst composition, and configured to receive both the C-3 compound and the reagent; and further comprises providing oxygen to the reaction chamber during the exposing.
48. The production process of claim 47 wherein the oxygen is provided to the chamber in an amount that is at least about 0.1 % of the molar amount of both the C-3 compound and the reagent.
49. A production system comprising a reactor coupled to both a reactant reservoir and a reagent reservoir, the reactor containing a catalyst composition comprising at least about 13% (wt/wt) chromium and at least one alkali metal.
50. (cancelled).
51. The production system of claim 49 wherein the catalyst composition further comprises a substrate.
52. The production system of claim 50 wherein the substrate comprises activated carbon.
53. The production system of claim 52 wherein the one alkali metal is potassium.
54. The production system of claim 49 wherein the reactor is also coupled to an oxidizing reagent reservoir.
55. The production system of claim 49 wherein the one alkali metal is potassium.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US65660005P | 2005-02-25 | 2005-02-25 | |
| US60/656,600 | 2005-02-25 | ||
| PCT/US2006/006501 WO2006091758A1 (en) | 2005-02-25 | 2006-02-24 | Production processes, production systems, and catalyst compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2601929A1 true CA2601929A1 (en) | 2006-08-31 |
Family
ID=36927760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002601929A Abandoned CA2601929A1 (en) | 2005-02-25 | 2006-02-24 | Production processes, production systems, and catalyst compositions |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP1855798A1 (en) |
| JP (1) | JP2008531261A (en) |
| KR (1) | KR20070110387A (en) |
| CN (1) | CN101132857A (en) |
| CA (1) | CA2601929A1 (en) |
| MX (1) | MX2007010376A (en) |
| RU (1) | RU2007135352A (en) |
| WO (1) | WO2006091758A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10968153B2 (en) * | 2019-08-14 | 2021-04-06 | Eagle Us 2 Llc | Method of converting a brominated hydrocarbon to a chlorinated hydrocarbon |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2861106A (en) * | 1954-02-26 | 1958-11-18 | Knapsack Ag | Process of preparing aldehydes or ketones by dehydrogenation of alcohols |
| US3632834A (en) * | 1968-10-23 | 1972-01-04 | Du Pont | Process for preparing trichlorotrifluoroethane and dichlorotetrafluoroethane |
| US3981794A (en) * | 1973-09-16 | 1976-09-21 | Exxon Research And Engineering Company | Aromatization process and catalysts |
| US4220608A (en) * | 1979-06-06 | 1980-09-02 | E. I. Du Pont De Nemours And Company | Preparation of 3,3,3-trifluoropropene-1 |
| US4798818A (en) * | 1987-11-27 | 1989-01-17 | Dow Corning Corporation | Catalyst composition and process for its preparation |
| EP0641598B1 (en) * | 1993-09-07 | 1999-01-07 | Showa Denko Kabushiki Kaisha | Chromium-based fluorination catalyst, process for producing the catalyst, and fluorination process using the catalyst |
| GB0214383D0 (en) * | 2002-06-21 | 2002-07-31 | Isis Innovation | Catalyst |
-
2006
- 2006-02-24 JP JP2007557172A patent/JP2008531261A/en active Pending
- 2006-02-24 KR KR1020077021955A patent/KR20070110387A/en not_active Application Discontinuation
- 2006-02-24 MX MX2007010376A patent/MX2007010376A/en unknown
- 2006-02-24 WO PCT/US2006/006501 patent/WO2006091758A1/en active Search and Examination
- 2006-02-24 EP EP06735957A patent/EP1855798A1/en not_active Withdrawn
- 2006-02-24 CN CNA2006800060824A patent/CN101132857A/en active Pending
- 2006-02-24 RU RU2007135352/04A patent/RU2007135352A/en not_active Application Discontinuation
- 2006-02-24 CA CA002601929A patent/CA2601929A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| WO2006091758A1 (en) | 2006-08-31 |
| WO2006091758B1 (en) | 2006-11-23 |
| JP2008531261A (en) | 2008-08-14 |
| CN101132857A (en) | 2008-02-27 |
| KR20070110387A (en) | 2007-11-16 |
| MX2007010376A (en) | 2007-09-25 |
| RU2007135352A (en) | 2009-03-27 |
| EP1855798A1 (en) | 2007-11-21 |
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| EEER | Examination request | ||
| FZDE | Discontinued |