The reaction of hydrogen (H2) with iodine (I2) dissolved in a solvent to produce hydrogen iodide (HI)

Abstract

A process for producing hydrogen iodide (HI) from hydrogen (H) and elemental iodine (I) dissolved in a suitable solvent by the use of at least one catalyst selected from the group consisting of platinum, palladium, nickel, cobalt, iron, nickel oxide, cobalt oxide, and iron oxide.

Description

[Technical field]

[0001] Disclosed is a process for making hydrogen iodide (HI) using iodine and hydrogen. Specifically, the disclosure relates to a process for producing hydrogen iodide from hydrogen and dissolved iodine in the presence of a catalyst. [Background technology]

[0002] Hydrogen iodide is an important industrial chemical used as a reducing agent and in the preparation of hydroiodic acid, organic and inorganic iodides, and iodoalkane blends. However, hydrogen iodide is very difficult to handle due to its instability and reactivity. For example, hydrogen iodide decomposes in the presence of heat or light to form hydrogen and iodine. Furthermore, in the presence of moisture, hydrogen iodide forms hydroiodic acid, which can corrode most metals. The instability and reactivity of hydrogen iodide makes it difficult to store and transport. Therefore, anhydrous hydrogen iodide is often prepared locally for immediate use.

[0003] Various methods for making hydrogen iodide have been reported, see, for example, NN Greenwood et al., The Chemistry of the Elements, 2nd edition, Oxford: Butterworth-Heineman. p 809-815, 1997, which prepares hydrogen iodide from the reaction of elemental iodine with hydrazine according to the following equation 1: Equation 1: 2I2+N2H4→4HI+N2

[0004] In another embodiment, the method includes the steps of: rd In this edition, AI Vogel teaches that hydrogen iodide can be prepared by reacting a stream of hydrogen sulfide with iodine according to the following equation 2: Equation 2: H2S+I2→2HI+S

[0005] Each of the above examples uses expensive starting materials such as hydrogen sulfide or hydrazine, which limits their application for large-scale economical preparation of hydrogen iodide. Furthermore, the use of hydrazine for the preparation of hydrogen iodide results in the formation of nitrogen gas as a by-product. Separation of nitrogen gas from hydrogen iodide to purify hydrogen iodide is difficult and expensive, thus adding to production costs. Similarly, the use of hydrogen sulfide results in the formation of sulfur, which is difficult to separate from unreacted iodine, again adding to production costs. Sulfur is poisonous to any catalyst used, further adding to production costs.

[0006] In some other embodiments, gaseous hydrogen iodide is prepared from elemental iodine and hydrogen gas according to Equation 3 below. Equation 3: H2+I2→2HI

[0007] For example, U.S. Patent No. 3,154,382 describes the use of an iodide melt or aqueous iodide solution together with hydrogen gas to prepare hydrogen iodide. U.S. Patent No. 8,268,284(B2) also discloses the use of elemental iodine to prepare hydrogen iodide, where solid iodine is first melted and then vaporized to allow for gas-phase reaction with hydrogen.

[0008] As exemplified by the aforementioned references, solid iodine can present difficulties in its use because it is difficult to generate a gas feed stream to the reactor from the solid iodine and causes further difficulties with clogging of reactor parts as the evaporated iodine recondenses. Summary of the Invention

[0009] The present disclosure provides a process for producing hydrogen iodide (HI) from hydrogen (H2) and elemental iodine (I2) dissolved in a suitable solvent by the use of at least one catalyst selected from the group consisting of platinum, palladium, nickel, cobalt, iron, nickel oxide, cobalt oxide, and iron oxide.

[0010] The present disclosure provides a process for producing hydrogen iodide comprising providing a reactant stream comprising hydrogen (H2) and iodine (I2) (wherein iodine can be dissolved in a suitable solvent and conveniently fed into the reactor by a liquid pump, reducing the inherent difficulties involved in adding solid / gaseous iodine to the reactor), and reacting the reactant stream in the presence of a catalyst to produce a product stream comprising hydrogen iodide.

[0011] The solvent may comprise at least one solvent selected from the group consisting of ethers such as diethyl ether and diglyme; nitriles such as benzonitrile and acetonitrile; formamides such as dimethylformamide; ionic liquids such as 1-ethyl-3-methylimidazolium acetate; sulfolane; carbon disulfide; toluene; naphthalene; xylene; 2,2-dimethylbutane; cyclohexane; acetone; ethanol; perfluoroheptane, and mesitylene.

[0012] The catalyst may comprise at least one catalyst selected from the group consisting of platinum, palladium, nickel, cobalt, iron, nickel oxide, cobalt oxide, and iron oxide. [Brief description of the drawings]

[0013] [Figure 1] FIG. 1 is a process flow diagram showing a process for producing hydrogen iodide (HI). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The present disclosure provides a process for producing hydrogen iodide (HI) from hydrogen (H2) and elemental iodine (I2) dissolved in a suitable solvent in the presence of at least one catalyst, such as platinum, palladium, nickel, cobalt, iron, nickel oxide, cobalt oxide, and iron oxide.

[0015] As disclosed herein, hydrogen iodide is produced from a reactant stream comprising hydrogen (H2), iodine (I2), and a suitable solvent.

[0016] The solvent is used to dissolve the iodine to facilitate its handling as a reactant and to facilitate reliable delivery of the iodine to the reactor for reaction with hydrogen. The dissolved iodine may be blended with the hydrogen upstream of the reactor or the dissolved iodine may be delivered directly to the reactor for reactive contact with the hydrogen in the reactor.

[0017] Suitable solvents for iodine, which may also be solvents for the reaction of iodine with hydrogen, may have boiling points greater than 100° C., greater than 125° C., or greater than 150° C., e.g., are stable under the high temperature reaction conditions and are non-reactive when exposed to the reagents, products, and catalysts present in the reaction.

[0018] The solvent may be capable of dissolving at least about 5 weight percent (wt%), at least about 10 wt%, at least about 15 wt%, at least about 20 wt%, or at least about 25 wt% iodine (I2). The weight percent measurement is defined as the ratio of the mass of the solute to the total mass of the solute / solvent mixture. For example, in a 20 wt% iodine (I2) solution, 100 grams of the solution contains 20 grams of iodine (I2).

[0019] The solvent may be selected from ethers such as diethyl ether and diglyme; nitriles such as benzonitrile and acetonitrile; formamides such as dimethylformamide; ketones such as acetone; ionic liquids such as 1-ethyl-3-methylimidazolium acetate; sulfolane; carbon disulfide; toluene; naphthalene; xylene; 2,2-dimethylbutane; cyclohexane; ethanol; perfluoroheptane; mesitylene; carbon tetrachloride; 1,1-dichloroethene; and alkanes. Iodine (I2) is provided to the reactor dissolved in a solvent. The dissolved iodine may be blended with hydrogen upstream of the reactor and co-fed to the reactor. Alternatively, the dissolved iodine may be conveyed directly to the reactor for reactive contact with the hydrogen in the reactor.

[0020] The solvent in which iodine (I2) is dissolved is selected from at least one of ethers, such as diethyl ether and diglyme; nitriles, such as benzonitrile and acetonitrile; formamides, such as dimethylformamide; ionic liquids, such as 1-ethyl-3-methylimidazolium acetate; sulfolane; carbon disulfide; toluene; naphthalene; xylene; 2,2-dimethylbutane; cyclohexane; ethanol; perfluoroheptane, and mesitylene.

[0021] The following table shows the approximate solubility of iodine in some of the solvents. Different solvents were tested - ethers such as diethyl ether and diglyme; nitriles such as benzonitrile and acetonitrile; formamides such as dimethylformamide; ionic liquids such as 1-ethyl-3-methylimidazolium acetate; sulfolane; carbon disulfide; toluene; naphthalene; xylene; 2,2-dimethylbutane; cyclohexane; ethanol; perfluoroheptane; and mesitylene. Thermally stable solvents (steam decomposition temperature >500°C) such as toluene, benzonitrile, and naphthalene may also be used and can be reused. [Table 1]

[0022] The hydrogen, iodine, and solvents may be anhydrous. It is preferred that there is as little water as possible in the reactant streams, since the presence of moisture results in hydroiodic acid that is corrosive and can be harmful to downstream equipment and process lines. In addition, recovery of hydrogen iodide from hydroiodic acid increases production costs.

[0023] The hydrogen may be substantially free of water, containing any water in an amount of less than about 500 ppm by weight, less than about 300 ppm by weight, less than about 200 ppm by weight, less than about 100 ppm by weight, less than about 50 ppm by weight, less than about 30 ppm by weight, less than about 20 ppm by weight, less than about 10 ppm by weight, or less than about 5 ppm by weight, or any value defined between any two of the preceding values. Preferably, the hydrogen contains any water in an amount of less than about 50 ppm by weight. More preferably, the hydrogen contains any water in an amount of less than about 10 ppm by weight. Most preferably, the hydrogen contains any water in an amount of less than about 5 ppm by weight.

[0024] The iodine may also be substantially free of water, with any water content being less than about 500 ppm by weight, less than about 300 ppm, less than about 200 ppm, less than about 100 ppm, less than about 50 ppm, less than about 30 ppm, less than about 20 ppm, or less than about 10 ppm, or any value defined between any two of the preceding values. More preferably, the iodine contains any water in an amount of less than about 30 ppm by weight. Most preferably, the iodine contains any water in an amount of less than about 30 ppm by weight. contains any water in an amount less than about 10 ppm by weight.

[0025] The solvent may also be substantially free of water, containing any water in an amount of less than about 500 ppm by weight, less than about 300 ppm by weight, less than about 200 ppm by weight, less than about 100 ppm by weight, less than about 50 ppm by weight, less than about 30 ppm by weight, less than about 20 ppm by weight, less than about 10 ppm by weight, or less than about 5 ppm by weight, or any value defined between any two of the preceding values. Preferably, the solvent contains any water in an amount of less than about 50 ppm by weight. More preferably, the solvent contains any water in an amount of less than about 10 ppm by weight. Most preferably, the solvent contains any water in an amount of less than about 5 ppm by weight.

[0026] Elemental iodine in solid form is commercially available, for example, from SQM, Santiago, Chile, or Kanto Natural Gas Development Co., Ltd, Chiba, Japan. Hydrogen in compressed gas form is commercially available, for example, from Airgas, Radnor, PA.

[0027] In the reactants, the molar ratio of hydrogen to iodine may be as low as about 1:1, about 1.5:1, about 2:1, about 2.5:1, about 2.7:1, or about 3:1, or as high as about 4:1, about 5:1, about 6:1, about 7:1, about 8:1, about 9:1, or about 10:1, or may be within any range defined between any two of the aforementioned values, such as, for example, about 1:1 to about 10:1, about 2:1 to about 8:1, about 3:1 to about 6:1, about 2:1 to about 5:1, about 2:1 to about 3:1, about 2.5:1 to about 3:1, or about 2.7:1 to about 3.0:1. Preferably, the molar ratio of hydrogen to iodine is about 2:1 to about 5:1. More preferably, the molar ratio of hydrogen to iodine is about 2:1 to about 3:1. Most preferably, the molar ratio of hydrogen to iodine is about 2.5:1 to 3:1.

[0028] A reactant stream comprising iodine dissolved in a solvent and hydrogen reacts in the presence of a catalyst contained within a reactor to produce a product stream comprising hydrogen iodide according to equation 3 above. The reactor may be a heated tube reactor, such as a fixed-bed tubular reactor, including a tube containing the catalyst. The tube may be made of metal, such as stainless steel, nickel, nickel alloy, e.g., nickel-chromium alloy, nickel-molybdenum alloy, nickel-chromium-molybdenum alloy, nickel-iron-chromium alloy, or nickel-copper alloy. Heating the tube reactor also heats the catalyst. Alternatively, the reactor may be any type of packed reactor.

[0029] As mentioned above, the catalyst is a platinum, palladium, nickel, cobalt, iron, nickel oxide, cobalt oxide, and iron oxide catalyst. The catalyst may be supported on a carrier. Thus, the catalyst includes at least one selected from the group of platinum, palladium, nickel, cobalt, iron, nickel oxide, cobalt oxide, and iron oxide, and the catalyst is supported on a carrier. The carrier may be selected from the group of activated carbon, silica gel, zeolite, silicon carbide, metal oxide, and combinations thereof. Non-exclusive examples of metal oxides include alumina, magnesium oxide, titanium oxide, zinc oxide, zirconia, chromia, and combinations thereof.

[0030] The catalyst may comprise platinum on a metal oxide support. The catalyst may consist essentially of platinum on a metal oxide support. The catalyst may consist of platinum on a metal oxide support. The catalyst may comprise platinum on an alumina support. The catalyst may comprise platinum on an activated carbon support. The catalyst may consist essentially of platinum on an activated carbon support. The catalyst may consist of platinum on an activated carbon support.

[0031] The catalyst may comprise palladium on a metal oxide support. The catalyst may consist essentially of palladium on a metal oxide support. The catalyst may consist of palladium on a metal oxide support. The catalyst may comprise palladium on an alumina support. The catalyst may comprise palladium on an activated carbon support. The catalyst may consist essentially of palladium on an activated carbon support. The catalyst may consist of palladium on an activated carbon support.

[0032] The catalyst may comprise nickel on a silica gel support. The catalyst may comprise nickel on a zeolite support. The catalyst may comprise nickel on an activated carbon support. The catalyst may comprise nickel on a silicon carbide support. The catalyst may consist essentially of nickel on a silica gel support. The catalyst may consist essentially of nickel on a zeolite support. The catalyst may consist essentially of nickel on an activated carbon support. The catalyst may consist essentially of nickel on a silicon carbide support. The catalyst may consist of nickel on a silica gel support. The catalyst may consist of nickel on a zeolite support. The catalyst may consist of nickel on an activated carbon support. The catalyst may consist of nickel on a silicon carbide support.

[0033] The catalyst may comprise nickel on a metal oxide support. The catalyst may consist essentially of nickel on a metal oxide support. The catalyst may consist of nickel on a metal oxide support. The catalyst may comprise nickel on an alumina support. The catalyst may comprise nickel on a magnesium oxide support. The catalyst may comprise nickel on a titanium oxide support. The catalyst may comprise nickel on a zinc oxide support. The catalyst may comprise nickel on a zirconia support. The catalyst may comprise nickel on a chromia support. The catalyst may consist essentially of nickel on an alumina support. The catalyst may consist essentially of nickel on a magnesium oxide support. The catalyst may consist essentially of nickel on a titanium oxide support. The catalyst may consist essentially of nickel on a zinc oxide support. The catalyst may consist essentially of nickel on a zirconia support. The catalyst may consist essentially of nickel on a chromia support. The catalyst may consist of nickel on an alumina support. The catalyst may consist of nickel on a magnesium oxide support. The catalyst may consist of nickel on a titanium oxide support. The catalyst may be comprised of nickel on a zinc oxide support.The catalyst may be comprised of nickel on a zirconia support.The catalyst may be comprised of nickel on a chromia support.

[0034] The catalyst may comprise nickel oxide on a silica gel support. The catalyst may comprise nickel oxide on a zeolite support. The catalyst may comprise nickel oxide on an activated carbon support. The catalyst may comprise nickel oxide on a silicon carbide support. The catalyst may consist essentially of nickel oxide on a silica gel support. The catalyst may consist essentially of nickel oxide on a zeolite support. The catalyst may consist essentially of nickel oxide on an activated carbon support. The catalyst may consist essentially of nickel oxide on a silicon carbide support. The catalyst may consist of nickel oxide on a silica gel support. The catalyst may consist of nickel oxide on a zeolite support. The catalyst may consist of nickel oxide on an activated carbon support. The catalyst may consist of nickel oxide on a silicon carbide support.

[0035] The catalyst may comprise nickel oxide on a metal oxide support. The catalyst may consist essentially of nickel oxide on a metal oxide support. The catalyst may consist of nickel oxide on a metal oxide support. The catalyst may comprise nickel oxide on an alumina support. The catalyst may comprise nickel oxide on a magnesium oxide support. The catalyst may comprise nickel oxide on a titanium oxide support. The catalyst may comprise nickel oxide on a zinc oxide support. The catalyst may comprise nickel oxide on a zirconia support. The catalyst may comprise nickel oxide on a chromia support. The catalyst may consist essentially of nickel oxide on an alumina support. The catalyst may consist essentially of nickel oxide on a magnesium oxide support. The catalyst may consist essentially of nickel oxide on a titanium oxide support. The catalyst may consist essentially of nickel oxide on a zinc oxide support. The catalyst may consist essentially of nickel oxide on a zirconia support. The catalyst may consist essentially of nickel oxide on a chromia support. The catalyst may consist essentially of nickel oxide on an alumina support. The catalyst may consist of nickel oxide on a magnesium oxide support. The catalyst may be comprised of nickel oxide on a titanium oxide support. The catalyst may be comprised of nickel oxide on a zinc oxide support. The catalyst may be comprised of nickel oxide on a zirconia support. The catalyst may be comprised of nickel oxide on a chromia support.

[0036] The catalyst may comprise nickel and nickel oxide on a silica gel support. The catalyst may comprise nickel and nickel oxide on a zeolite support. The catalyst may comprise nickel and nickel oxide on an activated carbon support. The catalyst may comprise nickel and nickel oxide on a silicon carbide support. The catalyst may consist essentially of nickel and nickel oxide on a silica gel support. The catalyst may consist essentially of nickel and nickel oxide on a zeolite support. The catalyst may consist essentially of nickel and nickel oxide on an activated carbon support. The catalyst may consist essentially of nickel and nickel oxide on a silicon carbide support. The catalyst may consist of nickel and nickel oxide on a silica gel support. The catalyst may consist of nickel and nickel oxide on a zeolite support. The catalyst may consist of nickel and nickel oxide on an activated carbon support. The catalyst may consist of nickel and nickel oxide on a silicon carbide support.

[0037] The catalyst may comprise nickel and nickel oxide on a metal oxide support. The catalyst may consist essentially of nickel and nickel oxide on a metal oxide support. The catalyst may consist of nickel and nickel oxide on a metal oxide support. The catalyst may comprise nickel and nickel oxide on an alumina support. The catalyst may comprise nickel and nickel oxide on a magnesium oxide support. The catalyst may comprise nickel and nickel oxide on a titanium oxide support. The catalyst may comprise nickel and nickel oxide on a zinc oxide support. The catalyst may comprise nickel and nickel oxide on a zirconia support. The catalyst may comprise nickel and nickel oxide on a chromia support. The catalyst may consist essentially of nickel and nickel oxide on an alumina support. The catalyst may consist essentially of nickel and nickel oxide on a magnesium oxide support. The catalyst may consist essentially of nickel and nickel oxide on a titanium oxide support. The catalyst may consist essentially of nickel and nickel oxide on a zinc oxide support. The catalyst may consist essentially of nickel and nickel oxide on a zirconia support. The catalyst may consist essentially of nickel and nickel oxide on a chromia support. The catalyst may be comprised of nickel and nickel oxide on an alumina support. The catalyst may be comprised of nickel and nickel oxide on a magnesium oxide support. The catalyst may be comprised of nickel and nickel oxide on a titanium oxide support. The catalyst may be comprised of nickel and nickel oxide on a zinc oxide support. The catalyst may be comprised of nickel and nickel oxide on a zirconia support. The catalyst may be comprised of nickel and nickel oxide on a chromia support.

[0038] The catalyst may comprise cobalt on a silica gel support. The catalyst may comprise cobalt on a zeolite support. The catalyst may comprise cobalt on an activated carbon support. The catalyst may comprise cobalt on a silicon carbide support. The catalyst may consist essentially of cobalt on a silica gel support. The catalyst may consist essentially of cobalt on a zeolite support. The catalyst may consist essentially of cobalt on an activated carbon support. The catalyst may consist essentially of cobalt on a silicon carbide support. The catalyst may consist of cobalt on a silica gel support. The catalyst may consist of cobalt on a zeolite support. The catalyst may consist of cobalt on an activated carbon support. The catalyst may consist of cobalt on a silicon carbide support.

[0039] The catalyst may comprise cobalt on a metal oxide support. The catalyst may consist essentially of cobalt on a metal oxide support. The catalyst may consist of cobalt on a metal oxide support. The catalyst may comprise cobalt on an alumina support. The catalyst may comprise cobalt on a magnesium oxide support. The catalyst may comprise cobalt on a titanium oxide support. The catalyst may comprise cobalt on a zinc oxide support. The catalyst may comprise cobalt on a zirconia support. The catalyst may comprise cobalt on a chromia support. The catalyst may consist essentially of cobalt on an alumina support. The catalyst may consist essentially of cobalt on a magnesium oxide support. The catalyst may consist essentially of cobalt on a titanium oxide support. The catalyst may consist essentially of cobalt on a zinc oxide support. The catalyst may consist essentially of cobalt on a zirconia support. The catalyst may consist essentially of cobalt on a chromia support. The catalyst may consist essentially of cobalt on an alumina support. The catalyst may comprise cobalt on a magnesium oxide support. The catalyst may comprise cobalt on a titanium oxide support. The catalyst may comprise cobalt on a zinc oxide support. The catalyst may comprise cobalt on a zirconia support. The catalyst may comprise cobalt on a chromia support.

[0040] The catalyst may comprise cobalt oxide on a silica gel support. The catalyst may comprise cobalt oxide on a zeolite support. The catalyst may comprise cobalt oxide on an activated carbon support. The catalyst may comprise cobalt oxide on a silicon carbide support. The catalyst may consist essentially of cobalt oxide on a silica gel support. The catalyst may consist essentially of cobalt oxide on a zeolite support. The catalyst may consist essentially of cobalt oxide on an activated carbon support. The catalyst may consist essentially of cobalt oxide on a silicon carbide support. The catalyst may consist of cobalt oxide on a silica gel support. The catalyst may consist of cobalt oxide on a zeolite support. The catalyst may consist of cobalt oxide on an activated carbon support. The catalyst may consist of cobalt oxide on a silicon carbide support.

[0041] The catalyst may comprise cobalt oxide on a metal oxide support. The catalyst may consist essentially of cobalt oxide on a metal oxide support. The catalyst may consist of cobalt oxide on a metal oxide support. The catalyst may comprise cobalt oxide on an alumina support. The catalyst may comprise cobalt oxide on a magnesium oxide support. The catalyst may comprise cobalt oxide on a titanium oxide support. The catalyst may comprise cobalt oxide on a zinc oxide support. The catalyst may comprise cobalt oxide on a zirconia support. The catalyst may comprise cobalt oxide on a chromia support. The catalyst may consist essentially of cobalt oxide on an alumina support. The catalyst may consist essentially of cobalt oxide on a magnesium oxide support. The catalyst may consist essentially of cobalt oxide on a titanium oxide support. The catalyst may consist essentially of cobalt oxide on a zinc oxide support. The catalyst may consist essentially of cobalt oxide on a zirconia support. The catalyst may consist essentially of cobalt oxide on a chromia support. The catalyst may be comprised of cobalt oxide on an alumina support. The catalyst may be comprised of cobalt oxide on a magnesium oxide support. The catalyst may be comprised of cobalt oxide on a titanium oxide support. The catalyst may be comprised of cobalt oxide on a zinc oxide support. The catalyst may be comprised of cobalt oxide on a zirconia support. The catalyst may be comprised of cobalt oxide on a chromia support.

[0042] The catalyst may comprise cobalt and cobalt oxide on a silica gel support. The catalyst may comprise cobalt and cobalt oxide on a zeolite support. The catalyst may comprise cobalt and cobalt oxide on an activated carbon support. The catalyst may comprise cobalt and cobalt oxide on a silicon carbide support. The catalyst may consist essentially of cobalt and cobalt oxide on a silica gel support. The catalyst may consist essentially of cobalt and cobalt oxide on a zeolite support. The catalyst may consist essentially of cobalt and cobalt oxide on an activated carbon support. The catalyst may consist essentially of cobalt and cobalt oxide on a silicon carbide support. The catalyst may consist of cobalt and cobalt oxide on a silica gel support. The catalyst may consist of cobalt and cobalt oxide on a zeolite support. The catalyst may consist of cobalt and cobalt oxide on an activated carbon support. The catalyst may consist of cobalt and cobalt oxide on a silicon carbide support.

[0043] The catalyst may comprise cobalt and cobalt oxide on a metal oxide support. The catalyst may consist essentially of cobalt and cobalt oxide on a metal oxide support. The catalyst may consist of cobalt and cobalt oxide on a metal oxide support. The catalyst may comprise cobalt and cobalt oxide on an alumina support. The catalyst may comprise cobalt and cobalt oxide on a magnesium oxide support. The catalyst may comprise cobalt and cobalt oxide on a titanium oxide support. The catalyst may comprise cobalt and cobalt oxide on a zinc oxide support. The catalyst may comprise cobalt and cobalt oxide on a zirconia support. The catalyst may comprise cobalt and cobalt oxide on a chromia support. The catalyst may consist essentially of cobalt and cobalt oxide on an alumina support. The catalyst may consist essentially of cobalt and cobalt oxide on a magnesium oxide support. The catalyst may consist essentially of cobalt and cobalt oxide on a titanium oxide support. The catalyst may consist essentially of cobalt and cobalt oxide on a zinc oxide support. The catalyst may consist essentially of cobalt and cobalt oxide on a zirconia support. The catalyst may consist essentially of cobalt and cobalt oxide on a chromia support. The catalyst may consist of cobalt and cobalt oxide on an alumina support. The catalyst may consist of cobalt and cobalt oxide on a magnesium oxide support. The catalyst may consist of cobalt and cobalt oxide on a titanium oxide support. The catalyst may consist of cobalt and cobalt oxide on a zinc oxide support. The catalyst may consist of cobalt and cobalt oxide on a zirconia support. The catalyst may consist of cobalt and cobalt oxide on a chromia support.

[0044] The catalyst may comprise iron on a silica gel support. The catalyst may comprise iron on a zeolite support. The catalyst may comprise iron on an activated carbon support. The catalyst may comprise iron on a silicon carbide support. The catalyst may consist essentially of iron on a silica gel support. The catalyst may consist essentially of iron on a zeolite support. The catalyst may consist essentially of iron on an activated carbon support. The catalyst may consist essentially of iron on a silicon carbide support. The catalyst may consist of iron on a silica gel support. The catalyst may consist of iron on a zeolite support. The catalyst may consist of iron on an activated carbon support. The catalyst may consist of iron on a silicon carbide support.

[0045] The catalyst may comprise iron on a metal oxide support. The catalyst may consist essentially of iron on a metal oxide support. The catalyst may consist of iron on a metal oxide support. The catalyst may comprise iron on an alumina support. The catalyst may comprise iron on a magnesium oxide support. The catalyst may comprise iron on a titanium oxide support. The catalyst may comprise iron on a zinc oxide support. The catalyst may comprise iron on a zirconia support. The catalyst may comprise iron on a chromia support. The catalyst may consist essentially of iron on an alumina support. The catalyst may consist essentially of iron on a magnesium oxide support. The catalyst may consist essentially of iron on a titanium oxide support. The catalyst may consist essentially of iron on a zinc oxide support. The catalyst may consist essentially of iron on a zirconia support. The catalyst may consist essentially of iron on a chromia support. The catalyst may consist of iron on an alumina support. The catalyst may consist of iron on a magnesium oxide support. The catalyst may consist of iron on a titanium oxide support. The catalyst may comprise iron on a zinc oxide support.The catalyst may comprise iron on a zirconia support.The catalyst may comprise iron on a chromia support.

[0046] The catalyst may comprise iron oxide on a silica gel support. The catalyst may comprise iron oxide on a zeolite support. The catalyst may comprise iron oxide on an activated carbon support. The catalyst may comprise iron oxide on a silicon carbide support. The catalyst may consist essentially of iron oxide on a silica gel support. The catalyst may consist essentially of iron oxide on a zeolite support. The catalyst may consist essentially of iron oxide on an activated carbon support. The catalyst may consist essentially of iron oxide on a silicon carbide support. The catalyst may consist of iron oxide on a silica gel support. The catalyst may consist of iron oxide on a zeolite support. The catalyst may consist of iron oxide on an activated carbon support. The catalyst may consist of iron oxide on a silicon carbide support.

[0047] The catalyst may comprise iron oxide on a metal oxide support. The catalyst may consist essentially of iron oxide on a metal oxide support. The catalyst may consist of iron oxide on a metal oxide support. The catalyst may comprise iron oxide on an alumina support. The catalyst may comprise iron oxide on a magnesium oxide support. The catalyst may comprise iron oxide on a titanium oxide support. The catalyst may comprise iron oxide on a zinc oxide support. The catalyst may comprise iron oxide on a zirconia support. The catalyst may comprise iron oxide on a chromia support. The catalyst may consist essentially of iron oxide on an alumina support. The catalyst may consist essentially of iron oxide on a magnesium oxide support. The catalyst may consist essentially of iron oxide on a titanium oxide support. The catalyst may consist essentially of iron oxide on a zinc oxide support. The catalyst may consist essentially of iron oxide on a zirconia support. The catalyst may consist essentially of iron oxide on a chromia support. The catalyst may consist of iron oxide on an alumina support. The catalyst may consist of iron oxide on a magnesium oxide support. The catalyst may be comprised of iron oxide on a titanium oxide support. The catalyst may be comprised of iron oxide on a zinc oxide support. The catalyst may be comprised of iron oxide on a zirconia support. The catalyst may be comprised of iron oxide on a chromia support.

[0048] The catalyst may comprise iron and iron oxide on a silica gel support. The catalyst may comprise iron and iron oxide on a zeolite support. The catalyst may comprise iron and iron oxide on an activated carbon support. The catalyst may comprise iron and iron oxide on a silicon carbide support. The catalyst may consist essentially of iron and iron oxide on a silica gel support. The catalyst may consist essentially of iron and iron oxide on a zeolite support. The catalyst may consist essentially of iron and iron oxide on an activated carbon support. The catalyst may consist essentially of iron and iron oxide on a silicon carbide support. The catalyst may consist of iron and iron oxide on a silica gel support. The catalyst may consist of iron and iron oxide on a zeolite support. The catalyst may consist of iron and iron oxide on an activated carbon support. The catalyst may consist of iron and iron oxide on a silicon carbide support.

[0049] The catalyst may comprise iron and iron oxide on a metal oxide support. The catalyst may consist essentially of iron and iron oxide on a metal oxide support. The catalyst may consist of iron and iron oxide on a metal oxide support. The catalyst may comprise iron and iron oxide on an alumina support. The catalyst may comprise iron and iron oxide on a magnesium oxide support. The catalyst may comprise iron and iron oxide on a titanium oxide support. The catalyst may comprise iron and iron oxide on a zinc oxide support. The catalyst may comprise iron and iron oxide on a zirconia support. The catalyst may comprise iron and iron oxide on a chromia support. The catalyst may consist essentially of iron and iron oxide on an alumina support. The catalyst may consist essentially of iron and iron oxide on a magnesium oxide support. The catalyst may consist essentially of iron and iron oxide on a titanium oxide support. The catalyst may consist essentially of iron and iron oxide on a zinc oxide support. The catalyst may consist essentially of iron and iron oxide on a zirconia support. The catalyst may consist essentially of iron and iron oxide on a chromia support. The catalyst may be comprised of iron and iron oxide on an alumina support. The catalyst may be comprised of iron and iron oxide on a magnesium oxide support. The catalyst may be comprised of iron and iron oxide on a titanium oxide support. The catalyst may be comprised of iron and iron oxide on a zinc oxide support. The catalyst may be comprised of iron and iron oxide on a zirconia support. The catalyst may be comprised of iron and iron oxide on a chromia support.

[0050] The catalyst may comprise nickel and cobalt on a silica gel support. The catalyst may comprise nickel and cobalt on a zeolite support. The catalyst may comprise nickel and cobalt on an activated carbon support. The catalyst may comprise nickel and cobalt on a silicon carbide support. The catalyst may consist essentially of nickel and cobalt on a silica gel support. The catalyst may consist essentially of nickel and cobalt on a zeolite support. The catalyst may consist essentially of nickel and cobalt on an activated carbon support. The catalyst may consist essentially of nickel and cobalt on a silicon carbide support. The catalyst may consist of nickel and cobalt on a silica gel support. The catalyst may consist of nickel and cobalt on a zeolite support. The catalyst may consist of nickel and cobalt on an activated carbon support. The catalyst may consist of nickel and cobalt on a silicon carbide support.

[0051] The catalyst may comprise nickel and cobalt on a metal oxide support. The catalyst may consist essentially of nickel and cobalt on a metal oxide support. The catalyst may consist of nickel and cobalt on a metal oxide support. The catalyst may comprise nickel and cobalt on an alumina support. The catalyst may comprise nickel and cobalt on a magnesium oxide support. The catalyst may comprise nickel and cobalt on a titanium oxide support. The catalyst may comprise nickel and cobalt on a zinc oxide support. The catalyst may comprise nickel and cobalt on a zirconia support. The catalyst may comprise nickel and cobalt on a chromia support. The catalyst may consist essentially of nickel and cobalt on an alumina support. The catalyst may consist essentially of nickel and cobalt on a magnesium oxide support. The catalyst may consist essentially of nickel and cobalt on a titanium oxide support. The catalyst may consist essentially of nickel and cobalt on a zinc oxide support. The catalyst may consist essentially of nickel and cobalt on a zirconia support. The catalyst may consist essentially of nickel and cobalt on a chromia support. The catalyst may consist of nickel and cobalt on an alumina support. The catalyst may consist of nickel and cobalt on a magnesium oxide support. The catalyst may consist of nickel and cobalt on a titanium oxide support. The catalyst may consist of nickel and cobalt on a zinc oxide support. The catalyst may consist of nickel and cobalt on a zirconia support. The catalyst may consist of nickel and cobalt on a chromia support.

[0052] The catalyst may comprise nickel oxide and cobalt oxide on a silica gel support. The catalyst may comprise nickel oxide and cobalt oxide on a zeolite support. The catalyst may comprise nickel oxide and cobalt oxide on an activated carbon support. The catalyst may comprise nickel oxide and cobalt oxide on a silicon carbide support. The catalyst may consist essentially of nickel oxide and cobalt oxide on a silica gel support. The catalyst may consist essentially of nickel oxide and cobalt oxide on a zeolite support. The catalyst may consist essentially of nickel oxide and cobalt oxide on an activated carbon support. The catalyst may consist essentially of nickel oxide and cobalt oxide on a silicon carbide support. The catalyst may consist of nickel oxide and cobalt oxide on a silica gel support. The catalyst may consist of nickel oxide and cobalt oxide on a zeolite support. The catalyst may consist of nickel oxide and cobalt oxide on an activated carbon support. The catalyst may consist of nickel oxide and cobalt oxide on a silicon carbide support.

[0053] The catalyst may comprise nickel oxide and cobalt oxide on a metal oxide support. The catalyst may consist essentially of nickel oxide and cobalt oxide on a metal oxide support. The catalyst may consist of nickel oxide and cobalt oxide on a metal oxide support. The catalyst may comprise nickel oxide and cobalt oxide on an alumina support. The catalyst may comprise nickel oxide and cobalt oxide on a magnesium oxide support. The catalyst may comprise nickel oxide and cobalt oxide on a titanium oxide support. The catalyst may comprise nickel oxide and cobalt oxide on a zinc oxide support. The catalyst may comprise nickel oxide and cobalt oxide on a zirconia support. The catalyst may comprise nickel oxide and cobalt oxide on a chromia support. The catalyst may consist essentially of nickel oxide and cobalt oxide on an alumina support. The catalyst may consist essentially of nickel oxide and cobalt oxide on a magnesium oxide support. The catalyst may consist essentially of nickel oxide and cobalt oxide on a titanium oxide support. The catalyst may consist essentially of nickel oxide and cobalt oxide on a zinc oxide support. The catalyst may consist essentially of nickel oxide and cobalt oxide on a zirconia support. The catalyst may consist essentially of nickel oxide and cobalt oxide on a chromia support. The catalyst may consist of nickel oxide and cobalt oxide on an alumina support. The catalyst may consist of nickel oxide and cobalt oxide on a magnesium oxide support. The catalyst may consist of nickel oxide and cobalt oxide on a titanium oxide support. The catalyst may consist of nickel oxide and cobalt oxide on a zinc oxide support. The catalyst may consist of nickel oxide and cobalt oxide on a zirconia support. The catalyst may consist of nickel oxide and cobalt oxide on a chromia support.

[0054] The catalyst may comprise nickel and iron on a silica gel support. The catalyst may comprise nickel and iron on a zeolite support. The catalyst may comprise nickel and iron on an activated carbon support. The catalyst may comprise nickel and iron on a silicon carbide support. The catalyst may consist essentially of nickel and iron on a silica gel support. The catalyst may consist essentially of nickel and iron on a zeolite support. The catalyst may consist essentially of nickel and iron on an activated carbon support. The catalyst may consist essentially of nickel and iron on a silicon carbide support. The catalyst may consist of nickel and iron on a silica gel support. The catalyst may consist of nickel and iron on a zeolite support. The catalyst may consist of nickel and iron on an activated carbon support. The catalyst may consist of nickel and iron on a silicon carbide support.

[0055] The catalyst may comprise nickel and iron on a metal oxide support. The catalyst may consist essentially of nickel and iron on a metal oxide support. The catalyst may consist of nickel and iron on a metal oxide support. The catalyst may comprise nickel and iron on an alumina support. The catalyst may comprise nickel and iron on a magnesium oxide support. The catalyst may comprise nickel and iron on a titanium oxide support. The catalyst may comprise nickel and iron on a zinc oxide support. The catalyst may comprise nickel and iron on a zirconia support. The catalyst may comprise nickel and iron on a chromia support. The catalyst may consist essentially of nickel and iron on an alumina support. The catalyst may consist essentially of nickel and iron on a magnesium oxide support. The catalyst may consist essentially of nickel and iron on a titanium oxide support. The catalyst may consist essentially of nickel and iron on a zinc oxide support. The catalyst may consist essentially of nickel and iron on a zirconia support. The catalyst may consist essentially of nickel and iron on a chromia support. The catalyst may consist essentially of nickel and iron on an alumina support. The catalyst may be comprised of nickel and iron on a magnesium oxide support. The catalyst may be comprised of nickel and iron on a titanium oxide support. The catalyst may be comprised of nickel and iron on a zinc oxide support. The catalyst may be comprised of nickel and iron on a zirconia support. The catalyst may be comprised of nickel and iron on a chromia support.

[0056] The catalyst may comprise nickel oxide and iron oxide on a silica gel support. The catalyst may comprise nickel oxide and iron oxide on a zeolite support. The catalyst may comprise nickel oxide and iron oxide on an activated carbon support. The catalyst may comprise nickel oxide and iron oxide on a silicon carbide support. The catalyst may consist essentially of nickel oxide and iron oxide on a silica gel support. The catalyst may consist essentially of nickel oxide and iron oxide on a zeolite support. The catalyst may consist essentially of nickel oxide and iron oxide on an activated carbon support. The catalyst may consist essentially of nickel oxide and iron oxide on a silicon carbide support. The catalyst may consist of nickel oxide and iron oxide on a silica gel support. The catalyst may consist of nickel oxide and iron oxide on a zeolite support. The catalyst may consist of nickel oxide and iron oxide on an activated carbon support. The catalyst may consist of nickel oxide and iron oxide on a silicon carbide support.

[0057] The catalyst may comprise nickel oxide and iron oxide on a metal oxide support. The catalyst may consist essentially of nickel oxide and iron oxide on a metal oxide support. The catalyst may consist of nickel oxide and iron oxide on a metal oxide support. The catalyst may comprise nickel oxide and iron oxide on an alumina support. The catalyst may comprise nickel oxide and iron oxide on a magnesium oxide support. The catalyst may comprise nickel oxide and iron oxide on a titanium oxide support. The catalyst may comprise nickel oxide and iron oxide on a zinc oxide support. The catalyst may comprise nickel oxide and iron oxide on a zirconia support. The catalyst may comprise nickel oxide and iron oxide on a chromia support. The catalyst may consist essentially of nickel oxide and iron oxide on an alumina support. The catalyst may consist essentially of nickel oxide and iron oxide on a magnesium oxide support. The catalyst may consist essentially of nickel oxide and iron oxide on a titanium oxide support. The catalyst may consist essentially of nickel oxide and iron oxide on a zinc oxide support. The catalyst may consist essentially of nickel oxide and iron oxide on a zirconia support. The catalyst may consist essentially of nickel oxide and iron oxide on a chromia support. The catalyst may consist of nickel oxide and iron oxide on an alumina support. The catalyst may consist of nickel oxide and iron oxide on a magnesium oxide support. The catalyst may consist of nickel oxide and iron oxide on a titanium oxide support. The catalyst may include nickel oxide and iron oxide on a zinc oxide support. The catalyst may consist of nickel oxide and iron oxide on a zirconia support. The catalyst may consist of nickel oxide and iron oxide on a chromia support.

[0058] The catalyst may comprise cobalt and iron on a silica gel support. The catalyst may comprise cobalt and iron on a zeolite support. The catalyst may comprise cobalt and iron on an activated carbon support. The catalyst may comprise cobalt and iron on a silicon carbide support. The catalyst may consist essentially of cobalt and iron on a silica gel support. The catalyst may consist essentially of cobalt and iron on a zeolite support. The catalyst may consist essentially of cobalt and iron on an activated carbon support. The catalyst may consist essentially of cobalt and iron on a silicon carbide support. The catalyst may consist of cobalt and iron on a silica gel support. The catalyst may consist of cobalt and iron on a zeolite support. The catalyst may consist of cobalt and iron on an activated carbon support. The catalyst may consist of cobalt and iron on a silicon carbide support.

[0059] The catalyst may comprise cobalt and iron on a metal oxide support. The catalyst may consist essentially of cobalt and iron on a metal oxide support. The catalyst may consist of cobalt and iron on a metal oxide support. The catalyst may comprise cobalt and iron on an alumina support. The catalyst may comprise cobalt and iron on a magnesium oxide support. The catalyst may comprise cobalt and iron on a titanium oxide support. The catalyst may comprise cobalt and iron on a zinc oxide support. The catalyst may comprise cobalt and iron on a zirconia support. The catalyst may comprise cobalt and iron on a chromia support. The catalyst may consist essentially of cobalt and iron on an alumina support. The catalyst may consist essentially of cobalt and iron on a magnesium oxide support. The catalyst may consist essentially of cobalt and iron on a titanium oxide support. The catalyst may consist essentially of cobalt and iron on a zinc oxide support. The catalyst may consist essentially of cobalt and iron on a zirconia support. The catalyst may consist essentially of cobalt and iron on a chromia support. The catalyst may consist of cobalt and iron on an alumina support. The catalyst may consist of cobalt and iron on a magnesium oxide support. The catalyst may consist of cobalt and iron on a titanium oxide support. The catalyst may consist of cobalt and iron on a zinc oxide support. The catalyst may consist of cobalt and iron on a zirconia support. The catalyst may consist of cobalt and iron on a chromia support.

[0060] The catalyst may comprise cobalt oxide and iron oxide on a silica gel support. The catalyst may comprise cobalt oxide and iron oxide on a zeolite support. The catalyst may comprise cobalt oxide and iron oxide on an activated carbon support. The catalyst may comprise cobalt oxide and iron oxide on a silicon carbide support. The catalyst may consist essentially of cobalt oxide and iron oxide on a silica gel support. The catalyst may consist essentially of cobalt oxide and iron oxide on a zeolite support. The catalyst may consist essentially of cobalt oxide and iron oxide on an activated carbon support. The catalyst may consist essentially of cobalt oxide and iron oxide on a silicon carbide support. The catalyst may consist of cobalt oxide and iron oxide on a silica gel support. The catalyst may consist of cobalt oxide and iron oxide on a zeolite support. The catalyst may consist of cobalt oxide and iron oxide on an activated carbon support. The catalyst may consist of cobalt oxide and iron oxide on a silicon carbide support.

[0061] The catalyst may comprise cobalt oxide and iron oxide on a metal oxide support. The catalyst may consist essentially of cobalt oxide and iron oxide on a metal oxide support. The catalyst may consist of cobalt oxide and iron oxide on a metal oxide support. The catalyst may comprise cobalt oxide and iron oxide on an alumina support. The catalyst may comprise cobalt oxide and iron oxide on a magnesium oxide support. The catalyst may comprise cobalt oxide and iron oxide on a titanium oxide support. The catalyst may comprise cobalt oxide and iron oxide on a zinc oxide support. The catalyst may comprise cobalt oxide and iron oxide on a zirconia support. The catalyst may comprise cobalt oxide and iron oxide on a chromia support. The catalyst may consist essentially of cobalt oxide and iron oxide on an alumina support. The catalyst may consist essentially of cobalt oxide and iron oxide on a magnesium oxide support. The catalyst may consist essentially of cobalt oxide and iron oxide on a titanium oxide support. The catalyst may consist essentially of cobalt oxide and iron oxide on a zinc oxide support. The catalyst may consist essentially of cobalt oxide and iron oxide on a zirconia support. The catalyst may consist essentially of cobalt oxide and iron oxide on a chromia support. The catalyst may consist of cobalt oxide and iron oxide on an alumina support. The catalyst may consist of cobalt oxide and iron oxide on a magnesium oxide support. The catalyst may consist of cobalt oxide and iron oxide on a titanium oxide support. The catalyst may consist of cobalt oxide and iron oxide on a zinc oxide support. The catalyst may consist of cobalt oxide and iron oxide on a zirconia support. The catalyst may consist of cobalt oxide and iron oxide on a chromia support.

[0062] The weight percent of the catalyst as a percentage of the total weight of the catalyst and support may be as little as about 0.03 weight percent (wt%), about 0.05 wt%, about 1 wt%, about 5 wt%, about 10 wt%, about 15 wt%, or about 20 wt%, or may be as much as about 35 wt%, about 40 wt%, about 45 wt%, or about 50 wt%, or may be within any range defined between any two of the preceding values, such as, for example, about 0.03 wt% to about 50 wt%, about 0.5 wt% to about 45 wt%, about 10 wt% to about 40 wt%, about 15 wt% to about 35 wt%, or about 3 wt% to about 25 wt%. Preferably, the weight percent of the catalyst is about 0.03 wt% to about 5 wt%. More preferably, the weight percent of the catalyst is about 0.03 wt% to about 2 wt%. Most preferably, the weight percentage of the catalyst is from about 0.05% to about 1% by weight.

[0063] The catalyst may, for example, have a density of about 1 gram per square meter (m 2 / g), about 5m 2 / g, approx. 10m 2 / g, approx. 25m 2 / g, approx. 40m 2 / g, approx. 60m 2 / g, or about 80m 2 / g, or about 100 m 2 / g, approx. 120m 2 / g, approx. 150m 2 / g, approx. 200m 2 / g, approx. 250m 2 / g, approx. 300m 2 / g, or about 1000m 2 / g, or about 1 m 2 / g~about 100m 2 / g, approx. 5m 2 / g~about 300m 2 / g, approx. 10m 2 / g ~ approx. 250m 2 / g, approx. 25m 2 / g~about 200m 2 / g, approx. 40m 2 / g~about 150m 2 / g, approx. 60m 2 / g ~ approx. 120m2 / g, or about 80m 2 / g ~ approx. 120m 2 The surface area of ​​the catalyst may be within any range defined between any two of the preceding values, such as 0.1 to 1.0 μm / g. The surface area of ​​the catalyst is determined by the BET method according to ISO 9277:2010.

[0064] The reactant stream may be in contact with the catalyst for a contact time as short as about 0.1 seconds, about 2 seconds, about 4 seconds, about 6 seconds, about 8 seconds, about 10 seconds, about 15 seconds, about 20 seconds, about 25 seconds, or about 30 seconds, or as long as about 40 seconds, about 50 seconds, about 60 seconds, about 70 seconds, about 80 seconds, about 100 seconds, about 120 seconds, or about 1,800 seconds, or within any range defined between any two of the foregoing values, e.g., from about 0.1 seconds to about 1,800 seconds, from about 2 seconds to about 120 seconds, from about 4 seconds to about 100 seconds, from about 6 seconds to about 80 seconds, from about 8 seconds to about 70 seconds, from about 10 seconds to about 60 seconds, from about 15 seconds to about 50 seconds, from about 20 seconds to about 40 seconds, from about 20 seconds to about 30 seconds, from about 10 seconds to about 20 seconds, or from about 100 seconds to about 120 seconds. Preferably, the reactant stream contacts the catalyst for a contact time of from about 2 seconds to about 100 seconds. More preferably, the reactant stream contacts the catalyst for a contact time of from about 2 seconds to about 60 seconds. Most preferably, the reactant stream contacts the catalyst for a contact time of from about 2 seconds to about 40 seconds.

[0065] Prior to the reaction, hydrogen (H2) and iodine (I2) dissolved in a solvent are fed to a preheater. The preheater may be heated to a reaction temperature as low as about 170°C, about 180°C, about 185°C, about 190°C, or as high as about 195°C, about 200°C, about 210°C, or about 220°C, or to a reaction temperature within any range defined between any two of the aforementioned values, such as about 170°C to about 220°C, about 170°C to about 200°C, about 180°C to about 195°C, about 170°C to about 180°C, or about 200°C to about 210°C. Preferably, the temperature is about 170°C to about 210°C. More preferably, the temperature is 180°C to about 200°C.

[0066] The mixture is then passed through a furnace containing a heated catalyst, which may be used to produce a reaction temperature as low as about 300°C, about 200°C, about 250°C, about 280°C, about 290°C, about 300°C, about 310°C, or about 320°C, or a reaction temperature as high as about 330°C, about 340°C, about 350°C, about 360°C, about 380°C, about 400°C, about 450°C, about 500°C, about 550°C, or about 600°C, or a reaction temperature between 150°C and about 600°C, between about 200°C and about 550°C, between about 250°C and about 500°C, between about 280°C and about The reaction temperature may be heated to any range defined between any two of the aforementioned values, such as 450°C, about 290°C to about 400°C, about 300°C to about 380°C, about 310°C to about 360°C, about 320°C to about 350°C, or about 320°C to about 340°C. Preferably, the reaction temperature is about 200°C to about 550°C. More preferably, the reaction temperature is about 300°C to about 500°C. Most preferably, the reaction temperature is about 350°C to about 450°C.

[0067] Hydrogen in the reactant stream to the reactor reduces catalysts including nickel oxide, cobalt oxide, and iron oxide among the corresponding metals. If desired, such catalysts may also be reduced by flowing hydrogen through the reactor prior to reaction.

[0068] The pressure is not critical, but may be high enough to keep the solvent in liquid form. Convenient operating pressures range from about 10 kPa to about 4,000 kPa, preferably from about 30 kPa to about 300 kPa.

[0069] A product stream containing hydrogen iodide (HI), unreacted hydrogen (H2), and unreacted iodine (I2) dissolved in the solvent is directed from the reactor to at least two cold traps, the first of which is at a higher temperature than the second, and the product stream is cooled to allow collection of at least some of the unreacted iodine (I2) dissolved in the solvent as well as the product HI. Unreacted hydrogen (H2) may also be collected. Unreacted iodine (I2) dissolved in the solvent is collected in the first trap. Crude HI is collected in the second trap. Most of the HI is collected in the second trap, but a small amount may remain dissolved in the solvent in the first trap. The unreacted hydrogen (H2), unreacted iodine (I2) dissolved in the solvent, and any small amount of HI product may be recycled to the reactor.

[0070] The temperature of the first cold trap may be as low as about -30°C, about -25°C, about -20°C, or as high as about -15°C, about -10°C, about -5°C, or about 0°C, or may be within any range defined between any two of the aforementioned values, such as about -30°C to about 0°C, about -20°C to about -10°C, about -25°C to about -20°C, or about -15°C to about -10°C. Preferably, the temperature is about -30°C to about -10°C. More preferably, the temperature is about -25°C to about -15°C. Most preferably, the temperature is -20°C.

[0071] The temperature of the second cold trap may be as low as about -225°C, about -200°C, about -196°C, or as high as about -195°C, about -190°C, or about -180°C, or may be within any range defined between any two of the aforementioned values, such as about -225°C to about -180°C, about -196°C to about -190°C, about -200°C to about -196°C, or about -195°C to about -180°C. Preferably, the temperature is about -225°C to about -190°C. More preferably, the temperature is about -200°C to about -195°C. Most preferably, the temperature is -196°C.

[0072] A process for producing hydrogen iodide (HI) from hydrogen (H2) and elemental iodine (I2) dissolved in a solvent, the solvent being selected from at least one of: ethers, such as diethyl ether and diglyme; nitriles, such as benzonitrile and acetonitrile; formamides, such as dimethylformamide; ionic liquids, such as 1-ethyl-3-methylimidazolium acetate; sulfolane; carbon disulfide; toluene; naphthalene; xylene; 2,2-dimethylbutane; cyclohexane; ethanol; perfluoroheptane; and mesitylene, including the use of platinum, palladium, nickel, cobalt, iron, nickel oxide, cobalt oxide, and iron oxide catalysts, as described below, the catalyst being supported on a support, which may be a batch process or a continuous process according to the present disclosure.

[0073] The figure is a process flow diagram illustrating a process for producing hydrogen iodide (HI). As shown in the figure, the process includes a material flow 10 of iodine (I2) dissolved in a solvent and hydrogen gas 12. The flow rate of the hydrogen gas 12 may be controlled by a flow controller (not shown). The mixture may be fed to a preheater 14, which is maintained above the melting point of iodine (I2). The heated mixture 16 may be fed to a reactor 18, such as a tubular reactor furnace. In the reactor, the mixture contacts a catalyst 20, such as by directing the mixture through a heated catalyst column fed with an inert gas, such as nitrogen.

[0074] The product stream 22 may include hydrogen iodide (HI), unreacted iodine (I2) dissolved in the solvent, unreacted hydrogen (H2), and trace amounts of water. The product stream 22 may be directed to a first cold trap 24 that may cool the product stream 22 to allow collection 32 of the unreacted iodine (I2) dissolved in the solvent. The unreacted iodine dissolved in the solvent 32 may be recycled to the dissolved iodine (I2) feed stream 10.

[0075] The product stream 26 may include unreacted hydrogen (H2), hydrogen iodide (HI), and trace amounts of water. The product stream 26 may then be directed to a second cold trap 28 maintained at a temperature lower than that of the first cold trap, and the product stream may be cooled to allow collection of the hydrogen iodide (HI). The unreacted hydrogen (H2) 30 may be recycled to the hydrogen (H2) gas feed stream 12. The product hydrogen iodide (HI) 34 is collected in an outlet stream.

[0076] While the present disclosure has been described in terms of exemplary designs, the present disclosure may be further modified within the spirit and scope of the present disclosure, and this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which the disclosure pertains.

[0077] As used herein, the phrase "within any range defined between any two of the preceding values" means that any range may be selected from any two of the values ​​listed preceding such phrase, regardless of whether those values ​​are in the lower portion of the list or in the higher portion of the list. For example, a pair of values ​​may be selected from two lower values, two higher values, or a lower value and a higher value. EXAMPLES

[0078] Example 1: Reaction of hydrogen with iodine dissolved in mesitylene Alumina pellets (catalyst volume: approx. 26 cm) equipped with a preheater (190°C to 200°C) 3 A Monel tube reactor (0.5" x 15") filled with 1% platinum on a 13" x 0.5" heating area) was heated to 415°C to 420°C and maintained for approximately 1 hour. After this, hydrogen (67 standard cm 3A 18 wt % solution of iodine in mesitylene (0.5 mL / min, approximately 5.14 g iodine / hr) was introduced into the preheater / reactor via a flow meter and syringe pump, respectively. The ratio of hydrogen (H2) to iodine (I2) was approximately 9:1. The product stream, containing hydrogen iodide (HI), unreacted iodine (I2), mesitylene solvent, and unreacted hydrogen (H2), was passed through two cold traps at -20°C and -196°C, respectively. Under these conditions, 7.1 g of hydrogen iodide (HI) (39% yield based on iodine) and 90 g of mesitylene and unreacted iodine were collected in the cold traps at -196°C and -20°C, respectively, over a 3.5 hour run time. Gas chromatographic (GC) analysis of a 90 g sample showed mesitylene as the only organic compound. The mass balance change for the reaction was within 3%. No significant decomposition of mesitylene was observed under these conditions. Example 2: Reaction of hydrogen with iodine dissolved in p-xylene

[0079] The reaction was carried out in a manner similar to that described in Example 1 using 0.5% palladium on alumina catalyst and 15 wt% iodine (I2) dissolved in p-xylene. The flow rate of hydrogen (H2) was 150 sccm, or about 0.76 g / hr, and a solution of 15 wt% iodine (I2) in p-xylene was delivered at a rate of 0.5 mL / min, about 4.5 g / hr. Under these conditions, 1.9 g of hydrogen iodine (HI) was collected in the second cold trap, giving a conversion of 28% over a run time of 1.5 hours. The temperatures of the first and second cold traps were -20°C and -196°C, respectively. Gas chromatography-mass spectrometry (GC-MS) analysis of the liquid collected in the 0°C trap showed mainly p-xylene. Example 3: Reaction of hydrogen with iodine dissolved in an ionic liquid

[0080] Experiments were carried out as described in Example 1, using a 20 wt % iodine solution dissolved in the ionic liquid 1-ethyl-3-methylimidazolium acetate instead of iodine in mesitylene. Under these conditions, no hydrogen iodide (HI) was obtained, but GC-MS of the gaseous material in the trap at -196 °C showed the presence of CH3I, C2H5I, and C3H7I in reduced amounts. Aspects

[0081] Embodiment 1 is a process for producing hydrogen iodide. The process includes providing a reactant stream comprising hydrogen and iodine, the iodine being dissolved in a solvent, and reacting the reactant stream in the presence of a catalyst to produce a product stream comprising hydrogen iodide.

[0082] Example 2 is the process of example 1, wherein in the providing step, the solvent comprises at least one selected from the group consisting of diethyl ether, diglyme, benzonitrile, acetonitrile, dimethylformamide, 1-ethyl-3-methylimidazolium acetate, sulfolane, carbon disulfide, acetone, toluene, naphthalene, xylene, 2,2-dimethylbutane, cyclohexane, ethanol, perfluoroheptane, and mesitylene.

[0083] Example 3 is the process of example 1, wherein in the providing step, the catalyst comprises at least one of the group of platinum, palladium, nickel, cobalt, iron, nickel oxide, cobalt oxide, and iron oxide, and the catalyst is supported on a support.

[0084] Example 4 is the process of any of Examples 1, 2, or 3, wherein the support is selected from the group of activated carbon, silica gel, zeolite, silicon carbide, metal oxides, or combinations thereof.

[0085] Example 5 is the process of any of Examples 1-4, wherein the support is a metal oxide support, the metal oxide support comprising alumina, magnesium oxide, titanium oxide, zinc oxide, zirconia, chromia, and combinations thereof.

[0086] Example 6 is the process of example 5, wherein the catalyst is selected from platinum on an alumina support or palladium on an alumina support.

[0087] Example 7 is the process of Example 1, wherein the catalyst is about 0.03 wt % to about 50 wt % of the total weight of the catalyst and support.

[0088] Example 8 is the process of example 1, wherein in the providing step, the hydrogen contains less than about 500 ppm by weight of water.

[0089] Example 9 is the process of example 1, wherein in the providing step, the iodine comprises less than about 500 ppm by weight of water.

[0090] Example 10 is the process of example 1, wherein in the providing step, the solvent comprises less than about 500 ppm water by weight.

[0091] Example 11 is the process of any of Examples 1-10, wherein in the providing step, a molar ratio of hydrogen to iodine in the reactant stream is from about 1:1 to about 10:1.

[0092] Example 12 is the process of example 11, wherein the molar ratio of hydrogen to iodine in the reactant stream is from about 2.5:1 to about 3:1.

[0093] Example 13 is the process of Example 1, wherein in the reacting step, the contact time between the reactant stream and the catalyst is from about 0.1 seconds to about 1,800 seconds.

[0094] Example 14 is the process of any of Examples 1-13, further comprising heating the reactant stream to a temperature of about 180° C. to about 210° C. in a preheater prior to the reacting step.

[0095] Example 15 is the process of any of Examples 1-14, further comprising heating the reactant stream to a temperature of about 300° C. to about 600° C. prior to the reacting step.

[0096] Example 16 is the process of any of Examples 1-15, wherein the process is a continuous process.

[0097] Example 17 is the process of any of Examples 1-16, wherein the product stream further comprises unreacted hydrogen, and the process further comprises the additional steps of separating hydrogen from the product stream and returning the separated hydrogen to the reactant stream.

[0098] Embodiment 18 is a process for producing hydrogen iodide, the process comprising reacting hydrogen with iodine, where the iodine dissolves in a solvent, in the presence of a catalyst to produce a product stream including hydrogen iodide, unreacted hydrogen, and dissolved unreacted iodine; removing at least some of the dissolved unreacted iodine from the product stream by cooling the product stream to collect the dissolved unreacted iodine; and recycling the dissolved iodine to the reaction step.

[0099] Example 19 is the process of example 18, wherein the solvent comprises at least one selected from the group of diethyl ether, diglyme, benzonitrile, acetonitrile, dimethylformamide, 1-ethyl-3-methylimidazolium acetate, sulfolane, carbon disulfide, toluene, naphthalene, xylene, 2,2-dimethylbutane, cyclohexane, ethanol, perfluoroheptane, and mesitylene.

[0100] Example 20 is the process of example 18 or example 19, wherein the catalyst comprises at least one of the group of platinum, palladium, nickel, cobalt, iron, nickel oxide, cobalt oxide, and iron oxide, and the catalyst is supported on a support.

[0101] Example 21 is the process of any one of Examples 18 to 20, wherein the catalyst is selected from platinum or palladium.

[0102] Example 22 is the process of any one of Examples 18 to 21, wherein the support is selected from the group of activated carbon, silica gel, zeolite, silicon carbide, metal oxides, or combinations thereof.

[0103] Example 23 is the process of example 22, wherein the support is a metal oxide support, including alumina, magnesium oxide, titanium oxide, zinc oxide, zirconia, chromia, and combinations thereof.

[0104] Example 24 is the process of example 23, wherein the support is alumina.

[0105] Example 25 is the process of any of Examples 18-24, wherein the product stream further comprises unreacted hydrogen, and the process further comprises the additional steps of separating hydrogen from the product stream and recycling the separated hydrogen to the recycle step.

[0106] Example 26 is the process of any of Examples 18-25, wherein the process is a continuous process. The present invention includes the following aspects. [1] 1. A process for producing hydrogen iodide comprising the steps of: providing a reactant stream comprising hydrogen and iodine, the iodine being dissolved in a solvent; reacting said reactant stream in the presence of a catalyst to produce a product stream comprising hydrogen iodide. [2] The process of [1], wherein in the providing step, the solvent comprises at least one selected from the group consisting of diethyl ether, diglyme, benzonitrile, acetonitrile, dimethylformamide, 1-ethyl-3-methylimidazolium acetate, sulfolane, carbon disulfide, toluene, naphthalene, xylene, 2,2-dimethylbutane, cyclohexane, ethanol, perfluoroheptane, and mesitylene. [3] The process of [1], wherein in the providing step, the catalyst comprises at least one of the group consisting of platinum, palladium, nickel, cobalt, iron, nickel oxide, cobalt oxide, and iron oxide, and the catalyst is supported on a support. [4] 2. The process of claim 1, wherein the support is selected from the group consisting of activated carbon, silica gel, zeolite, silicon carbide, metal oxides, or combinations thereof. [5] [4] The process of [4], wherein the support is a metal oxide support, the metal oxide support comprising alumina, magnesium oxide, titanium oxide, zinc oxide, zirconia, chromia, and combinations thereof. [6] In the providing step, at least one of the following is provided: the hydrogen containing less than about 500 ppm by weight of water; the iodine containing less than about 500 ppm by weight of water; The process of [1], wherein the solvent contains less than about 500 ppm by weight of water. [7] The process of [1], wherein in the providing step, a molar ratio of the hydrogen to the iodine in the reactant stream is from about 1:1 to about 10:1. [8] 1. A process for producing hydrogen iodide comprising: reacting hydrogen with iodine, the iodine being dissolved in a solvent, in the presence of a catalyst to produce a product stream comprising hydrogen iodide, unreacted hydrogen, and dissolved unreacted iodine; removing at least some of the dissolved unreacted iodine from the product stream by cooling the product stream and collecting the dissolved unreacted iodine; and recycling said dissolved iodine to said reacting step. [9] the product stream further comprising unreacted hydrogen, the process comprising: the additional step of separating said hydrogen from said product stream; and an additional step of recycling the separated hydrogen to the reaction step.

[10] [8] The process according to [8], wherein the process is a continuous process.

Claims

1. 1. A process for producing hydrogen iodide comprising the steps of: premixing iodine with a solvent; providing a reactant stream comprising hydrogen and iodine dissolved in a solvent; reacting the reactant stream in the presence of a catalyst at a reaction temperature between 200° C. and 550° C. to produce a product stream comprising hydrogen iodide; wherein in said providing, a molar ratio of said hydrogen to said iodine in said reactant stream is from 1:1 to 10:1; The process wherein the catalyst comprises at least one of the group: palladium, nickel, cobalt, iron, nickel oxide, cobalt oxide, and iron oxide.

2. 2. The process of claim 1, wherein the solvent comprises at least one selected from the group of diethyl ether, diglyme, benzonitrile, acetonitrile, dimethylformamide, 1-ethyl-3-methylimidazolium acetate, sulfolane, carbon disulfide, toluene, naphthalene, xylene, 2,2-dimethylbutane, cyclohexane, ethanol, perfluoroheptane, and mesitylene.

3. 10. The process of claim 1, wherein the catalyst is supported on a support, the support being selected from the group of activated carbon, silica gel, zeolites, silicon carbide, metal oxides, or combinations thereof.

4. 4. The process of claim 3, wherein the support is a metal oxide support, the metal oxide support comprising alumina, magnesium oxide, titanium oxide, zinc oxide, zirconia, chromia, and combinations thereof.

5. In the providing, at least one of the following: The hydrogen containing less than 50 ppm by weight of water; said iodine containing less than 500 ppm by weight of water; 2. The process of claim 1, wherein the solvent comprises less than 100 ppm by weight of water.

6. 1. A process for producing hydrogen iodide comprising the steps of: premixing iodine with a solvent; reacting, in a reacting step, hydrogen with iodine dissolved in a solvent in the presence of a catalyst to produce a product stream comprising hydrogen iodide, unreacted hydrogen, and dissolved unreacted iodine; removing at least some of the dissolved unreacted iodine from the product stream by cooling the product stream and collecting the dissolved unreacted iodine; and recycling said dissolved unreacted iodine to said reacting step.

7. the product stream further comprising unreacted hydrogen, the process comprising: the additional step of separating said hydrogen from said product stream; 7. The process of claim 6, further comprising the additional step of recycling said separated hydrogen to said reaction step.

8. The process of claim 6 , wherein the process is a continuous process.

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