阅读说明：本技术 用于由氢气和碘制造碘化氢的整合方法和催化剂 (Integrated process and catalyst for the production of hydrogen iodide from hydrogen and iodine ) 是由 特里斯·杨 王海友 邱永 R·威尔考克斯 克里斯蒂安·郑工 哈洛克·科普卡利 于 2020-04-16 设计创作，主要内容包括：本发明提供了一种用于产生碘化氢的方法。所述方法包括提供包含氢气和碘的气相反应物流,以及使所述反应物流在催化剂的存在下反应以产生包含碘化氢的产物流。所述催化剂包含选自镍、钴、铁、氧化镍、氧化钴和氧化铁的组中的至少一种。所述催化剂负载在载体上。(The present invention provides a process for producing hydrogen iodide. The process includes providing a vapor phase reactant stream comprising hydrogen and iodine, and reacting the reactant stream in the presence of a catalyst to produce a product stream comprising hydrogen iodide. The catalyst comprises at least one selected from the group of nickel, cobalt, iron, nickel oxide, cobalt oxide and iron oxide. The catalyst is supported on a carrier.)

1. A process for producing hydrogen iodide, the process comprising:

providing a gas phase reactant stream comprising hydrogen and iodine; and

reacting the reactant stream in the presence of a catalyst to produce a product stream comprising hydrogen iodide, wherein the catalyst comprises at least one selected from the group of nickel, cobalt, iron, nickel oxide, cobalt oxide, and iron oxide, and wherein the catalyst is supported on a support.

2. The method of claim 1, wherein in the providing step, the hydrogen gas comprises less than about 500ppm by weight water and less than about 500ppm by weight oxygen.

3. The method of claim 1, wherein in the providing step, the iodine comprises less than about 500ppm water by weight.

4. The method of claim 1, wherein in the providing step, the molar ratio of the hydrogen to the iodine in the reactant stream is from about 1: 1 to about 10: 1.

5. The process of claim 1, wherein the support is selected from the group of activated carbon, silica gel, zeolite, silicon carbide, metal oxide, or combinations thereof.

6. The process of claim 5, wherein the support is a metal oxide support comprising alumina, magnesia, titania, zinc oxide, zirconia, chromia, and combinations thereof.

7. The process of claim 6, wherein the catalyst comprises nickel and the support is alumina.

8. The process of claim 1, wherein the product stream further comprises unreacted iodine, and the process further comprises the additional steps of:

separating the unreacted iodine from the product stream as solid iodine;

heating the solid iodine to produce liquid iodine; and

returning the liquid iodine to the reactant stream.

9. The process of claim 8, wherein the product stream further comprises unreacted hydrogen, and the process further comprises the additional steps of:

separating the hydrogen from the product stream; and

returning the separated hydrogen to the reactant stream.

10. The method of claim 9, wherein separating the hydrogen from the product stream comprises:

compressing the product stream; and

subjecting the compressed product stream to flash cooling.

Technical Field

The present disclosure relates to a process for producing hydrogen iodide. In particular, the present disclosure relates to a process for producing anhydrous hydrogen iodide from hydrogen and iodine in the presence of a catalyst.

Background

Hydrogen iodide is an important industrial chemical used as a reducing agent and in the preparation of hydroiodic acid, organic and inorganic iodides, and alkyl iodides. 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. In addition, 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 usually prepared locally for immediate use.

Various methods for preparing hydrogen iodide have been reported. See, e.g., n.n. greenwood et al, Chemistry of Elements (The Chemistry of The Elements), 2 nd edition, Oxford: Butterworth-Heineman Press, page 809-815, 1997, in which hydrogen iodide is prepared from the reaction of elemental iodine with hydrazine according to equation 1 below:

equation 1: 2I₂+N₂H₄→4HI+N₂。

In another example, in a Textbook of Practical Organic Chemistry (Textbook of Practical Organic Chemistry), 3 rd edition, a.i. vogel, a hydrogen iodide may be prepared by reacting a hydrogen sulfide stream with iodine according to equation 2 below:

equation 2: h₂S+I₂→2HI+S。

Each of the above examples uses expensive starting materials such as hydrogen sulfide or hydrazine, which limits their use to large-scale, economical production of hydrogen iodide. In addition, the preparation of hydrogen iodide using hydrazine results in the formation of nitrogen as a by-product. Separation of nitrogen from hydrogen iodide to purify hydrogen iodide is difficult and expensive, thus increasing the manufacturing cost. Similarly, the use of hydrogen sulfide results in the formation of sulfur, which is difficult to separate from unreacted iodine, again increasing manufacturing costs. Sulfur can diminish the effect of any catalyst used, further increasing manufacturing costs.

In some other examples, hydrogen iodide is prepared from elemental iodine and hydrogen gas according to equation 3 below:

equation 3: h₂+I₂→2HI。

Such examples can more easily produce high purity hydrogen iodide because no nitrogen or sulfur is produced. For example, JP4713895B2 shows the production of hydrogen iodide in the gas phase using hydrogen and iodine vapor catalyzed by a noble metal-based catalyst. In particular, the disclosed reaction may be catalyzed by platinum, rhodium, palladium, and ruthenium supported on a metal oxide selected from the group consisting of magnesia, titania, silica, alumina, and zirconia. However, since the cost of the noble metal is generally high, the use of a noble metal-based catalyst to prepare hydrogen iodide further increases the manufacturing cost. Therefore, there is a need for alternative metal catalysts that do not contain noble metals for catalyzing the reaction of hydrogen and iodine to produce hydrogen iodide.

Disclosure of Invention

The present disclosure provides a method for generating hydrogen (H)₂) And elemental iodine (I)₂) An integrated process for the manufacture of Hydrogen Iodide (HI), the process comprising the use ofA catalyst comprising at least one selected from the group consisting of nickel, cobalt, iron, nickel oxide, cobalt oxide and iron oxide supported on a carrier.

In one embodiment, the present invention provides a process for producing hydrogen iodide. The process includes providing a vapor phase reactant stream comprising hydrogen and iodine, and reacting the reactant stream in the presence of a catalyst to produce a product stream comprising hydrogen iodide. The catalyst comprises at least one selected from the group of nickel, cobalt, iron, nickel oxide, cobalt oxide and iron oxide. The catalyst is supported on a carrier.

In another embodiment, the present invention provides a process for producing hydrogen iodide. The method comprises the following steps: reacting hydrogen and iodine in the gas phase in the presence of a catalyst to produce a product stream comprising hydrogen iodide and unreacted iodine, removing at least some of the unreacted iodine from the product stream by the cooling of the product stream to form solid iodine, producing liquid iodine from the solid iodine, and recycling liquefied iodine to the reacting step. The solid iodine may be formed in the first iodine removal vessel or the second iodine removal vessel. Producing the liquid iodine from the solid iodine by: heating the first iodine removal vessel to liquefy the solid iodine while the product stream is cooled by the second iodine removal vessel; or heating the second iodine removal vessel to liquefy the solid iodine while the product stream is cooled by the first iodine removal vessel. The catalyst comprises at least one selected from the group of nickel, cobalt, iron, nickel oxide, cobalt oxide and iron oxide. The catalyst is supported on a carrier.

Drawings

Fig. 1 is a process flow diagram illustrating an integrated process for producing anhydrous hydrogen iodide.

Fig. 2 is a process flow diagram illustrating another integrated process for producing anhydrous hydrogen iodide.

Detailed Description

The present disclosure provides a method for generating hydrogen (H)₂) And elemental iodine (I)₂) Integrated process for the manufacture of anhydrous Hydrogen Iodide (HI), processThe process comprises using a nickel, cobalt, iron, nickel oxide, cobalt oxide and/or iron oxide catalyst supported on a carrier. It has been found that the use of such catalysts can be effective for the production of hydrogen iodide on a commercial scale. The production efficiency of hydrogen iodide is further enhanced by recycling the reactants. The recycling of elemental iodine is particularly important because it is an expensive raw material with a wholesale price of $20 to $100 per kilogram. However, recycling iodine presents challenges because it is a solid below 113.7 ℃. The present disclosure also provides an integrated process for the manufacture of hydrogen iodide comprising recycling iodine in an efficient and continuous manner.

As disclosed herein, anhydrous hydrogen iodide consists of hydrogen (H) gas₂) And iodine (I)₂) The reactant stream of (a). The reactant stream may consist essentially of hydrogen, iodine and recycled hydrogen iodide. The reactant stream may consist of hydrogen, iodine and hydrogen iodide.

The term "anhydrous hydrogen iodide" means hydrogen iodide that is substantially free of water. That is, the amount of any water in the anhydrous hydrogen iodide is less than about 500ppm, about 300ppm, about 200ppm, about 100ppm, about 50ppm, about 30ppm, about 20ppm, about 10ppm, about 5ppm, about 3ppm, about 2ppm, or about 1ppm, or less than any value defined between any two of the foregoing values, by weight. Preferably, anhydrous hydrogen iodide contains less than about 100ppm by weight water. More preferably, anhydrous hydrogen iodide contains less than about 10ppm by weight water. Most preferably, anhydrous hydrogen iodide contains less than about 1ppm by weight water.

It is preferred that as little water as possible be present in the reactant stream because the presence of moisture results in the formation of hydriodic acid, which is corrosive and may be harmful to downstream equipment and production lines. In addition, recovery of hydrogen iodide from hydroiodic acid increases manufacturing costs.

The hydrogen is substantially free of water, including any water less than about 500ppm, about 300ppm, about 200ppm, about 100ppm, about 50ppm, about 30ppm, about 20ppm, 10ppm, or about 5ppm, or less than any value defined between any two of the foregoing values, by weight. Preferably, the hydrogen gas comprises less than about 50ppm by weight of any water. More preferably, the hydrogen gas comprises less than about 10ppm by weight of any water. Most preferably, the hydrogen gas comprises less than about 5ppm by weight of any water.

The hydrogen gas is substantially free of oxygen. That is, the amount of any oxygen in the reactant stream is less than about 500 parts per million, about 300ppm, about 200ppm, about 100ppm, about 50ppm, about 30ppm, about 20ppm, about 10ppm, about 5ppm, about 3ppm, about 2ppm, or about 1ppm, or less than any value defined between any two of the foregoing values, by weight. Preferably, the amount of oxygen in the hydrogen gas is less than about 100ppm by weight. More preferably, the amount of oxygen in the hydrogen gas is less than about 10ppm by weight. Most preferably, the amount of oxygen in the hydrogen gas is less than about 1ppm by weight. It is preferred that as little oxygen as possible be present in the hydrogen gas, as oxygen can react with hydrogen to form water.

Iodine is also substantially free of water, including any water less than about 500ppm, about 300ppm, about 200ppm, about 100ppm, about 50ppm, about 30ppm, about 20ppm, or about 10ppm, or less than any value defined between any two of the foregoing values, by weight. Preferably, the iodine comprises less than about 100ppm by weight of any water. More preferably, the iodine comprises less than about 30ppm by weight of any water. Most preferably, the iodine comprises less than about 10ppm by weight of any water.

Elemental iodine in solid form is commercially available from, for example, SQM corporation (SQM, Santiago, Chile) in san diego, Chile, or Kanto Natural Gas Development co. Hydrogen in the form of a compressed gas is commercially available from, for example, Air Chemicals (Airgas, Radnor, PA) in ladono, pennsylvania or Air Products and Chemicals, inc.

The molar ratio of hydrogen to iodine in the reactant stream can 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 any range defined between any two of the foregoing values, such as, for example, from about 1: 1 to about 10: 1, from about 2: 1 to about 8: 1, from about 3: 1 to about 6: 1, from about 2: 1 to about 5: 1, from about 2: 1 to about 3: 1, from about 2.5: 1 to about 3: 1, from about 2.7: 1 to about 3.0: 1. Preferably, the molar ratio of hydrogen to iodine is from about 2: 1 to about 5: 1. More preferably, the molar ratio of hydrogen to iodine is from about 2: 1 to about 3: 1. Most preferably, the molar ratio of hydrogen to iodine is from about 2.5: 1 to 3: 1.

The reactant stream is reacted in the presence of a catalyst contained within the reactor to produce a product stream comprising anhydrous hydrogen iodide according to equation 3 above. The reactor may be a heated tube reactor, such as a fixed bed tube reactor, including tubes containing catalyst. The tube may be made of metal, such as stainless steel, nickel and/or nickel alloys (such as nickel-chromium alloy, nickel-molybdenum alloy, nickel-chromium-molybdenum alloy, nickel-iron-chromium alloy, or nickel-copper alloy). The tube reactor is heated and therefore also the catalyst. Alternatively, the reactor may be any type of packed reactor, such as a multi-tubular reactor (e.g., a shell-and-tube reactor), in which the catalyst is packed into the tubes and the heat transfer medium is brought into contact with, for example, the outside of the tubes. The reactor may be operated isothermally or adiabatically.

As noted above, the catalyst is a supported nickel, cobalt, iron, nickel oxide, cobalt oxide and/or iron oxide catalyst. Thus, the catalyst comprises at least one selected from the group of nickel, cobalt, iron, nickel oxide, cobalt oxide and iron oxide, wherein the catalyst is supported on a carrier. The support 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 aluminum oxide, magnesium oxide, titanium oxide, zinc oxide, zirconium oxide, chromium oxide, and combinations thereof.

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.

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 magnesia support. The catalyst may comprise nickel on a titania 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 magnesia support. The catalyst may consist essentially of nickel on a titania 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 magnesia support. The catalyst may consist of nickel on a titania support. The catalyst may consist of nickel on a zinc oxide support. The catalyst may consist of nickel on a zirconia support. The catalyst may consist of nickel on a chromia support.

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.

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 titania 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 titania 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 of nickel oxide on an alumina support. The catalyst may consist of nickel oxide on a magnesium oxide support. The catalyst may consist of nickel oxide on a titania support. The catalyst may consist of nickel oxide on a zinc oxide support. The catalyst may consist of nickel oxide on a zirconia support. The catalyst may consist of nickel oxide on a chromia support.

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.

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 titania 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 titania 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 consist of nickel and nickel oxide on an alumina support. The catalyst may consist of nickel and nickel oxide on a magnesium oxide support. The catalyst may consist of nickel and nickel oxide on a titania support. The catalyst may consist of nickel and nickel oxide on a zinc oxide support. The catalyst may consist of nickel and nickel oxide on a zirconia support. The catalyst may consist of nickel and nickel oxide on a chromia support.

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.

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 magnesia support. The catalyst may comprise cobalt on a titania 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 magnesia support. The catalyst may consist essentially of cobalt on a titania 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 of cobalt on an alumina support. The catalyst may consist of cobalt on a magnesia support. The catalyst may consist of cobalt on a titania support. The catalyst may consist of cobalt on a zinc oxide support. The catalyst may consist of cobalt on a zirconia support. The catalyst may consist of cobalt on a chromia support.

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.

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 titania 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 titania 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 consist of cobalt oxide on an alumina support. The catalyst may consist of cobalt oxide on a magnesium oxide support. The catalyst may consist of cobalt oxide on a titania support. The catalyst may consist of cobalt oxide on a zinc oxide support. The catalyst may consist of cobalt oxide on a zirconia support. The catalyst may consist of cobalt oxide on a chromia support.

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.

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 magnesia support. The catalyst may comprise cobalt and cobalt oxide on a titania 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 magnesia support. The catalyst may consist essentially of cobalt and cobalt oxide on a titania 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 titania support. The catalyst may consist of cobalt and cobalt oxide on a zinc oxide support. The catalyst may consist of cobalt on a zirconia support and cobalt oxide. The catalyst may consist of cobalt and cobalt oxide on a chromia support.

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.

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 magnesia support. The catalyst may comprise iron on a titania 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 magnesia support. The catalyst may consist essentially of iron on a titania 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 magnesia support. The catalyst may consist of iron on a titania support. The catalyst may consist of iron on a zinc oxide support. The catalyst may consist of iron on a zirconia support. The catalyst may consist of iron on a chromia support.

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.

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 titania 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 titania 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 consist of iron oxide on a titania support. The catalyst may consist of iron oxide on a zinc oxide support. The catalyst may consist of iron oxide on a zirconia support. The catalyst may consist of iron oxide on a chromia support.

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.

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 titania 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 titania 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 consist of iron and iron oxide on an alumina support. The catalyst may consist of iron and iron oxide on a magnesium oxide support. The catalyst may consist of iron and iron oxide on a titania support. The catalyst may consist of iron and iron oxide on a zinc oxide support. The catalyst may consist of iron and iron oxide on a zirconia support. The catalyst may consist of iron and iron oxide on a chromia support.

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.

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 magnesia support. The catalyst may comprise nickel and cobalt on a titania 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 magnesia support. The catalyst may consist essentially of nickel and cobalt on a titania 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 magnesia support. The catalyst may consist of nickel and cobalt on a titania 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.

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.

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 titania 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 titania 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 titania 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.

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.

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 magnesia support. The catalyst may comprise nickel and iron on a titania 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 magnesia support. The catalyst may consist essentially of nickel and iron on a titania 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 of nickel and iron on an alumina support. The catalyst may consist of nickel and iron on a magnesia support. The catalyst may consist of nickel and iron on a titania support. The catalyst may consist of nickel and iron on a zinc oxide support. The catalyst may consist of nickel and iron on a zirconia support. The catalyst may consist of nickel and iron on a chromia support.

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.

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 titania 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 titania 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 titania support. The catalyst may consist of 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.

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.

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 magnesia support. The catalyst may comprise cobalt and iron on a titania 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 magnesia support. The catalyst may consist essentially of cobalt and iron on a titania 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 magnesia support. The catalyst may consist of cobalt and iron on a titania 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.

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.

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 titania 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 titania 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 titania 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.

The catalyst may be in the form of beads, pellets, extrudates, powders, spheres or mats. Preferably, the catalyst comprises nickel on an alumina support. More preferably, the catalyst comprises nickel in the form of pellets on an alumina support. Most preferably, the catalyst comprises nickel in the form of pellets having a diameter in the range of from about 1mm to about 7mm on an alumina support.

The catalyst is commercially available. Various loadings (weight percent) of nickel metal supported on alumina are available, for example, from Honeywell oil products, Des Plaines, IL, USA, or from january santheu, London, UK, of delbrun.

The weight percent of the catalyst (as a percentage of the total weight of the catalyst and support) can be as low as about 0.1 weight percent (wt%), about 1 wt%, about 3 wt%, about 5 wt%, about 10 wt%, about 15 wt%, or about 20 wt%, or up to about 35 wt%, about 40 wt%, about 45 wt%, or about 50 wt%, or within any range defined between any two of the foregoing values, such as, for example, from about 0.1 wt% to about 50 wt%, from about 3 wt% to about 45 wt%, from about 10 wt% to about 40 wt%, from about 15 wt% to about 35 wt%, or from about 3 wt% to about 25 wt%. Preferably, the weight percent of catalyst is from about 5 weight percent to about 45 weight percent. More preferably, the weight percent of the catalyst is from about 10 weight percent to about 40 weight percent. Most preferably, the weight percent of the catalyst is from about 15 weight percent to about 35 weight percent.

The catalyst may have the following surface area: down to about 1 square meter per gram (m)²Per g), about 5m²G, about 10m²A,/g, about 25m²A,/g, about 40m²G, about 60m²In the range of/g or about 80m²Per g, or up to about 100m²G, about 120m²G, about 150m²G, about 200m²G, about 250m²G, about 300m²A/g or about 1,000m²G, or within any range defined between any two of the preceding values, such as, for example, about 1m²A/g to about 1,00m²G, about 5m²G to about 300m²G, about 10m²G to about 250m²A,/g, about 25m²G to about 200m²A,/g, about 40m²G to about 150m²G, about 60m²G to about 120m²In the range of/g or about 80m²G to about 120m²(ii) in terms of/g. According to ISO 9277: 2010, the surface area of the catalyst was measured by the BET method.

The reactant stream may be contacted with the catalyst for the following contact times: 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, about 200 seconds, or about 1,800 seconds, or within any range defined between any two of the foregoing values, such as, for example, about 0.1 seconds to about 1,800 seconds, about 2 seconds to about 120 seconds, about 4 seconds to about 100 seconds, about 6 seconds to about 80 seconds, about 8 seconds to about 70 seconds, about 10 seconds to about 60 seconds, about 15 seconds to about 50 seconds, about 20 seconds to about 40 seconds, about 20 seconds to about 30 seconds, about 10 seconds to about 20 seconds, or about 100 seconds to about 120 seconds. Preferably, the reactant stream is contacted with the catalyst for a contact time of from about 2 seconds to about 200 seconds. More preferably, the reactant stream is contacted with the catalyst for a contact time of from about 40 seconds to about 100 seconds. Most preferably, the reactant stream is contacted with the catalyst for a contact time of from about 60 seconds to about 80 seconds.

The reactant stream and catalyst may be preheated to the reaction temperature. The reaction temperature may be as low as about 150 ℃, about 200 ℃, about 250 ℃, about 280 ℃, about 290 ℃, about 300 ℃, about 310 ℃, or about 320 ℃, or the reaction temperature is as high as about 330 ℃, about 340 ℃, about 350 ℃, about 360 ℃, about 380 ℃, about 400 ℃, about 450 ℃, about 500 ℃, about 550 ℃, or about 600 ℃, or any range defined between any two of the foregoing values, such as, for example, about 150 ℃ to about 600 ℃, about 200 ℃ to about 550 ℃, about 250 ℃ to about 500 ℃, about 280 ℃ to about 450 ℃, about 290 ℃ to about 400 ℃, about 300 ℃ to about 380 ℃, about 310 ℃ to about 360 ℃, about 320 ℃ to about 350 ℃, or about 320 ℃ to about 340 ℃. Preferably, the reaction temperature is from about 200 ℃ to about 500 ℃. More preferably, the reaction temperature is from about 300 ℃ to about 400 ℃. Most preferably, the reaction temperature is from about 300 ℃ to about 350 ℃.

Hydrogen in the flow of reactants to the reactor reduces the catalyst comprising nickel oxide, cobalt oxide and/or iron oxide to the corresponding metal. Preferably, such catalysts are reduced by a hydrogen stream flowing through the reactor prior to the reaction to reduce the catalyst to the corresponding metal.

The operating pressure of the reactor can be as low as about 10kPag (kilopascals gauge), about 50kPag, about 100kPag, about 200kPag, about 300kPag, about 400kPag, or about 600kPag, or as high as about 800kPag, about 1,000kPag, about 1,500kPag, about 2,000kPag, about 2,500kPag, about 3,000kPag, or about 4,000kPag, or any range defined between any two of the foregoing values, such as, for example, about 10kPag to about 4,000kPag, about 50kPag to about 3,000kPag, about 100kPag to about 2,500kPag, about 200kPag to about 2,000kPag, about 300kPag to about 1,500kPag, about 400kPag to about 1,000kPag, about 600kPag to about 10kPag, or about 800 kPag. Preferably, the operating pressure of the reactor is from about 10kPag to about 800 kPag. More preferably, the operating pressure of the reactor is from about 10kPag to about 400 kPag. Most preferably, the operating pressure of the reactor is from about 10kPag to about 200 kPag.

Iodine is supplied to the reactor from solid iodine that is continuously or intermittently added to the heated iodine liquefier to maintain a level of liquid iodine in the liquefier. A positive pressure is maintained in the liquefier to deliver liquid iodine to the iodine vaporizer. For example, the flow rate of liquid iodine can be provided by monitoring the weight loss of a container providing iodine, by calculation based on the stroke volume of a pump (if a pump is used), and/or by passing liquid iodine through a flow meter. The temperature of the iodine in the iodine liquefier is maintained such that the temperature is high enough to melt the iodine, but low enough to avoid evaporating the iodine. The liquid iodine is vaporized in the vaporizer to form an iodine vapor. The iodine vapor exiting the vaporizer can be mixed with hydrogen from a hydrogen supply to form a reactant stream. Alternatively or additionally, hydrogen from a hydrogen supply source may be provided to the iodine vaporizer to assist in the vaporization of iodine, thereby reducing the vaporization temperature. In either case, the hydrogen gas may also include recycled hydrogen gas and hydrogen iodide. The reactant stream is preheated to reaction temperature and fed to the reactor preloaded with any of the catalysts described above. The production lines between the liquefier and the evaporator are thermally traced to ensure that the iodine remains as a liquid in these lines. The process line carrying the iodine vapor and hydrogen/iodine vapor mixture is thermally traced to ensure that the gas phase is maintained. Alternatively, solid iodine may be provided to a container that liquefies the iodine and evaporates the iodine to produce an iodine vapor.

A product stream comprising hydrogen iodide, unreacted hydrogen and unreacted iodine is directed from the reactor to one or more iodine removal vessels where the product stream is cooled to allow condensation of the unreacted iodine to remove at least some of the iodine from the product stream for recycle as a reactant. Optionally, the product stream is directed to a cooler to remove some heat from the product stream, and then unreacted iodine is condensed in one or more iodine removal vessels. In one or more iodine removal vessels, the product stream may be cooled to a temperature below the boiling point of iodine but above the melting point of iodine to recover iodine in liquid form. Alternatively or additionally, the product stream exiting the reactor may be cooled to a temperature below the melting point of iodine to recover iodine in solid form. The product stream may travel from one or more iodine removal vessels to one or more additional iodine removal vessels to remove additional unreacted iodine for recycle.

The substantially iodine-free product stream can be directed from the one or more iodine removal vessels to a compressor to increase the product stream pressure to a separation pressure sufficient to effectively recover unreacted hydrogen. The separation pressure is greater than the operating pressure of the reactor. The separation pressure can be as low as about 800kPag, about 850kPag, about 900kPag, about 950kPag, or about 1,000kPag, or as high as about 1,100kPag, about 1,200kPag, about 1,300kPag, about 1,400kPag, or about 1,500kPag, or any range defined between any two of the foregoing values, such as, for example, from 800kPag to about 1,500kPag, from about 850kPag to about 1,400kPag, from about 900kPag to about 1,300kPag, from about 950kPag to about 1,200kPag, from about 1,000kPag to about 1,100kPag, or from about 900kPag to about 1,100 kPag. Preferably, the separation pressure is from about 10kPag to about 2,000 kPag. More preferably, the separation pressure is from about 300kPag to about 1,500 kPag. Most preferably, the separation pressure is from about 600kPag to about 1,000 kPag.

The compressed product stream is subjected to a first stage of quench cooling or distillation to recover a liquid stream and a vapor stream. The vapor stream comprises hydrogen and small amounts of hydrogen iodide. The liquid stream is substantially free of hydrogen and includes hydrogen iodide, residual iodine and other higher boiling materials, such as any water. The vapor stream can be recycled to the reactor. The liquid stream is directed to a distillation column to separate liquid hydrogen iodide in the overhead stream from residual iodine and other higher boiling materials (including any residual water) in the bottoms stream. Higher boiling materials are directed from the bottoms stream of the distillation column for further processing, including iodine recovery and recycle. The vapor effluent from the top of the distillation column may be used as a purge to remove any non-condensable gases, such as hydrogen.

Alternatively, the product stream may be directed from the one or more iodine removal vessels to a heavy ends distillation column to separate higher boiling point materials (such as hydrogen iodide and any residual iodine) from lower boiling point materials (such as unreacted hydrogen). The higher boiling point materials are directed from the bottoms stream of the heavies distillation column to an iodine recycle distillation column to separate hydrogen iodide from residual iodine. The overhead stream of the heavies column, including hydrogen and any residual hydrogen iodide, is directed to a product distillation column. The bottoms stream of the iodine recycle distillation column, including residual iodine, is recycled back to the iodine liquefier. The overhead stream of the iodine recycle column including hydrogen iodide is directed to a product distillation column to separate the hydrogen iodide from the hydrogen and other non-condensable gases from the heavies column and the iodine recycle column. The overhead stream of the product column comprising hydrogen and residual hydrogen iodide may be recycled back to the reactor. The bottom stream of the product column comprises purified hydrogen iodide.

In any of the above processes, an additional product column may be added to increase the purity of the hydrogen iodide. The purified hydrogen iodide may be passed through a suitable drying agent to remove any residual moisture prior to use in subsequent processes, such as, for example, any of the methods described above. The purified hydrogen iodide may be directly supplied to the subsequent process. Alternatively or in addition, the purified hydrogen iodide may be collected in a storage tank for short-term storage before being used in subsequent processes. The recycling of iodine and hydrogen results in an efficient process for the production of hydrogen iodide.

Hydrogen (H) according to the present disclosure₂) And elemental iodine (I)₂) The process for making Hydrogen Iodide (HI), including the use of a nickel, cobalt, iron, nickel oxide, cobalt oxide and/or iron oxide catalyst supported on a support, may be a batch process or may be a continuous process, as described below.

Fig. 1 is a process flow diagram illustrating an integrated process for producing anhydrous hydrogen iodide. As shown in fig. 1, the integrated process 10 includes a material stream of solid iodine 12 and hydrogen 14. Solid iodine 12 may be added continuously or intermittently to the solid storage tank 16. A stream of solid iodine 18 is transferred from the solid storage tank 16 to the iodine liquefier 20 by a solids transfer system (not shown) or by gravity, wherein the solid iodine is heated above its melting point but below its boiling point to maintain the level of liquid iodine in the iodine liquefier 20. Although only one liquefier 20 is shown, it should be understood that multiple liquefiers 20 may be used in a parallel arrangement. Liquid iodine 22 flows from the iodine liquefier 20 to an iodine vaporizer 24. Iodine liquefier 20 may be pressurized with an inert gas to drive the flow of liquid iodine 22. The inert gas may include, for example, nitrogen, argon or helium or mixtures thereof. Alternatively or additionally, the flow of liquid iodine 22 may be driven by a pump (not shown). The flow of liquid iodine 22 may be controlled by a liquid flow controller 26. In the iodine vaporizer 24, the iodine is heated above its boiling point to form a stream of iodine vapor 28.

The flow rate of the hydrogen gas 14 may be controlled by a gas flow controller 30. The iodine vapor stream 28 and hydrogen stream 14 are provided to superheater 36 and heated to a reaction temperature to form a reactant stream 38. The reactant stream 38 is provided to a reactor 40.

The reactant stream 38 reacts in the presence of a catalyst 42 contained within a reactor 40 to produce a product stream 44. Catalyst 42 may be any of the catalysts described herein. Product stream 44 can include hydrogen iodide, unreacted iodine, unreacted hydrogen, and trace amounts of water, as well as other high boiling impurities.

Product stream 44 may be provided to upstream valve 46. Upstream valve 46 may direct product stream 44 to an iodine removal step. Alternatively, product stream 44 may pass through a cooler (not shown) to remove some of the heat before being directed to the iodine removal step. In the iodine removing step, the first iodine removing system 48a may include a first iodine removing container 50a and a second iodine removing container 50 b. Product stream 44 can be cooled in first iodine removal vessel 50a to a temperature below the boiling point of iodine to condense or lose the sublimation mechanism of at least some of the iodine, thereby separating it from product stream 44. Product stream 44 can be further cooled in first iodine removal vessel 50a to a temperature below the melting point of iodine to separate even more iodine from product stream 44, thereby depositing at least some of the iodine within first iodine removal vessel 50a as a solid and producing reduced iodine product stream 52. Reduced iodine product stream 52 can be provided to second iodine removal vessel 50b and cooled to separate at least some of the iodine from reduced iodine product stream 52, thereby producing additional crude hydrogen iodide product stream 54.

While the first iodine removal train 48a consists of two iodine removal vessels operating in a series configuration, it should be understood that the first iodine removal train 48a may include two or more iodine removal vessels operating in a parallel configuration, more than two iodine removal vessels operating in a series configuration, or any combination thereof. It should also be understood that the first iodine removal train 48a may consist of a single iodine removal vessel. It should also be understood that any iodine removal container may include or be in the form of a heat exchanger. It should also be understood that successive containers may be combined into a single container having multiple cooling stations.

The iodine collected in the first iodine removal vessel 50a can form a first iodine recycle stream 56 a. Similarly, iodine collected in second iodine removal vessel 50b can form second iodine recycle stream 56 b. Each of first iodine recycle stream 56a and second iodine recycle stream 56b may be provided continuously or intermittently to iodine liquefier 20 and/or iodine vaporizer 24 as shown.

To provide continuous operation while collecting iodine in solid form, upstream valve 46 may be configured to selectively direct product stream 44 to second iodine removal train 48 b. The second iodine removal system 48b may be substantially similar to the first iodine removal system 48a, as described above. Once the first iodine removal vessel 50a or the second iodine removal vessel 50b of the first iodine removal train 48a accumulates sufficient solid iodine to facilitate removal of the solid iodine, the upstream valve 46 may be selected to direct the product stream 44 from the first iodine removal train 48a to the second iodine removal train 48 b. At about the same time, downstream valve 58, which is configured to selectively direct crude hydrogen iodide product stream 54 from first iodine removal system 48a or second iodine removal system 48b, can be selected to direct crude hydrogen iodide product stream 54 from second iodine removal system 48b such that the process of removing iodine from product stream 44 to produce crude hydrogen iodide product stream 54 can continue uninterrupted. Once product stream 44 is no longer directed to first iodine removal train 48a, first and second iodine removal vessels 50a, 50b of first iodine removal train 48a may be heated above the melting point of iodine, thereby liquefying solid iodine so that it may flow through first and second iodine recycle streams 56a, 56b of first iodine removal train 48a to iodine liquefier 20.

As the process continues and either of first iodine removal vessel 50a or second iodine removal vessel 50b of second iodine removal system 48b accumulates sufficient solid iodine to facilitate removal of the solid iodine, upstream valve 46 may be selected to direct product stream 44 from second iodine removal system 48b back to first iodine removal system 48a, and downstream valve 58 may be selected to direct crude hydrogen iodide product stream 54 from first iodine removal system 48a, such that the process of removing iodine from product stream 44 to produce crude hydrogen iodide product stream 54 may continue uninterrupted. Once product stream 44 is no longer directed to second iodine removal train 48b, first and second iodine removal vessels 50a, 50b of second iodine removal train 48b may be heated above the melting point of iodine, thereby liquefying solid iodine so that it may flow through first and second iodine recycle streams 56a, 56b of second iodine removal train 48b to iodine liquefier 20. By continuing to switch between the first and second iodine removal systems 48a, 48b, unreacted iodine in the product stream 44 can be efficiently and continuously removed and recycled.

As described above, liquid iodine may flow through first and second iodine recycle streams 56a and 56b of first and second iodine removal trains 48a and 48b to iodine liquefier 20. Alternatively, liquid iodine may flow through first and second iodine recycle streams 56a and 56b of first and second iodine removal trains 48a and 48b to iodine evaporator 24, thereby bypassing iodine liquefier 20 and liquid flow controller 26.

In the integrated process shown in fig. 1, crude hydrogen iodide product stream 54 is provided to a heavies distillation column 60. Heavy distillation column 60 may be configured to separate higher boiling point materials, such as hydrogen iodide and residual unreacted iodine, from lower boiling point materials, such as unreacted hydrogen. A bottoms stream 62 from the mass distillation column 60 comprising hydrogen iodide and residual unreacted iodine may be provided to an iodine recycle column 64. The iodine recycle column 64 may be configured to separate residual unreacted iodine from hydrogen iodide. The bottoms stream 66 of iodine recycle column 64, including unreacted iodine, may be recycled back to iodine liquefier 20. Alternatively, the bottoms stream 66 of iodine recycle column 64, including unreacted iodine, can be recycled back to iodine vaporizer 24. An overhead stream 68 of iodine recycle column 64 comprising hydrogen iodide may be provided to product distillation column 70.

An overhead stream 72 from the mass distillation column 60 comprising hydrogen and residual hydrogen iodide may also be provided to the product distillation column 70. The product distillation column 70 may be configured to separate unreacted hydrogen from hydrogen iodide. The overhead stream 74 of the product column 70, including unreacted hydrogen and residual hydrogen iodide, may be recycled back to the reactor 40. The resulting purified hydrogen iodide product may be collected from the bottoms stream 76 of the product column 70.

Fig. 2 is a process flow diagram illustrating another integrated process for producing anhydrous hydrogen iodide. The integrated process 78 shown in fig. 2 is the same as the integrated process 10 described above with reference to fig. 1 until a crude hydrogen iodide product stream 54 is produced. In the integrated process 78 of fig. 2, the crude hydrogen iodide product stream 54 is provided to a compressor 80 to increase the pressure of the crude hydrogen iodide product stream 54 to facilitate recovery of hydrogen and hydrogen iodide. Compressor 80 increases the pressure of crude hydrogen iodide product stream 54 to a separation pressure greater than the operating pressure of reactor 42 to produce a compressed product stream 82. The compressed product stream 82 is directed to a dephlegmator 84 where it is subjected to a first stage of rapid cooling for separating higher boiling point materials such as hydrogen iodide and trace amounts of residual unreacted iodine from lower boiling point materials such as unreacted hydrogen. The overhead stream 86 from partial condenser 84, including hydrogen and residual hydrogen iodide, may be recycled back to reactor 40. A bottoms stream 88 from partial condenser 84 comprising hydrogen iodide, trace amounts of residual unreacted iodine, and trace amounts of water may be provided to product column 90. Product column 90 may be configured to separate residual unreacted iodine, water, and other higher boiling compounds from hydrogen iodide. The bottoms stream 92 of the product column 90, including unreacted iodine, may be recycled back to the iodine liquefier 20. Alternatively, bottoms stream 92 of product column 90, including unreacted iodine, can be recycled back to iodine vaporizer 24. The resulting purified hydrogen iodide product may be collected from the overhead stream 94 of the product column 90. A purge stream 96 may be withdrawn from the product column 90 to control the accumulation of low boiling impurities. A portion of the purge stream 96 may be recycled back into the reactor 40, while another portion may be discarded.

While this invention has been described with respect to an exemplary design, the present invention may be further modified within the spirit and scope of this disclosure. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains.

As used herein, the phrase "within any range defined between any two of the preceding values" literally means that any range can be selected from any two values listed before such phrase, whether such values are in the lower portion of the list or in the upper 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

Example 1: preparation of hydrogen iodide from hydrogen and iodine catalyzed by nickel catalyst

In example 1, the determination of hydrogen (H) from hydrogen according to equation 3 above was confirmed under a range of reaction conditions using an alumina-supported nickel catalyst₂) And elemental iodine (I)₂) Preparation of Hydrogen Iodide (HI). The catalyst in the fixed bed tubular reactor was activated prior to introducing the mixture of hydrogen and iodine vapor into the reactor. The catalyst was activated by purging the catalyst with nitrogen, then introducing hydrogen, heating the reactor to 120 ℃, holding for two hours, then raising the reactor temperature to 230 ℃ and holding for an additional hour. The reactor temperature was then adjusted to the desired reaction temperature. A predetermined fixed flow rate of hydrogen gas is bubbled into the iodine evaporator, which is initially filled with a predetermined amount of solid elemental iodine. The iodine evaporator temperature is controlled between 150 ℃ and 170 ℃, which produces iodine vapor. The evaporator temperature and hydrogen flow rate are adjusted accordingly to achieve the desired hydrogen to iodine molar ratio. A mixture of hydrogen and iodine vapor is fed to a reactor to react in the presence of a catalyst to form hydrogen iodide. The reactor effluent was then passed through a two-stage iodine collector to collect any unreacted iodine in solid form. The iodine collector effluent stream containing the crude hydrogen iodide product was then collected in a dry ice trap. The effluent stream from the dry ice trap was bubbled through a scrubber containing deionized water to capture residual hydrogen iodide from the unreacted hydrogen stream. After a predetermined period of time, the system is shut down and the iodine evaporator weight loss and iodine collector weight gain are measured to calculate an average H₂/I₂Feed molar ratio. The residence time was calculated based on the combined feed rate of hydrogen and iodine, and the conversion was calculated based on the amount of hydrogen iodide collected and iodine fed to the reactor.

All reactions were carried out in the range of 0psig to 5 psig. Using a 21 wt% nickel catalyst (Ni/Al) on an alumina support₂O₃) Each having a 24-hour runAnd (3) removing the solvent. 20 wt% Ni/Al was used₂O₃Or 5 wt% Ni/Al₂O₃The catalyst was run with 72 hours of run time per run. Other reaction conditions are shown in table 1.

The results of each run are shown in table 1. As shown in table 1, with 21 wt% nickel catalyst on alumina support, the average conversion was greater than 90% when the contact time was greater than 7 seconds, and the average productivity was about 351b./h/ft for reaction temperatures of about 320 ℃ to about 360 ℃³. While the 20 wt% nickel on alumina support catalyst showed slightly better performance than the 21 wt% nickel on alumina support catalyst under comparable reaction conditions, the 5 wt% nickel on alumina support catalyst showed much lower activity.

TABLE 1

_{2 2}Example 2: effect of H/I molar ratio in the preparation of Hydrogen iodide from Hydrogen and iodine catalyzed by Nickel catalyst gas

In example 2, 21 wt% Ni/Al was used₂O₃The catalyst was confirmed to be H under a series of reaction conditions₂/I₂Effect of molar ratio on HI collection rate. The same experimental setup and experimental procedure as described in example 1 was used in example 2, with a 24 hour run time per run. The HI collection rate is defined as the percentage of HI collected in the dry ice trap relative to the total HI produced. As shown in Table 2, when H₂/I₂At a molar ratio of 2.7 (below 3), the HI collection rate was above 90%, however, with H₂/I₂The HI collection rate decreased significantly with increasing molar ratio. Without wishing to be bound by any theory, this indicates that the condensation of HI becomes more difficult in the presence of excess hydrogen.

TABLE 2

Aspect(s)

Aspect 1 is a process for producing hydrogen iodide. The process includes providing a vapor phase reactant stream comprising hydrogen and iodine, and reacting the reactant stream in the presence of a catalyst to produce a product stream comprising hydrogen iodide. The catalyst comprises at least one selected from the group of nickel, cobalt, iron, nickel oxide, cobalt oxide and iron oxide. The catalyst is supported on a carrier.

Aspect 2 is the method of aspect 1, wherein in the providing step, the hydrogen gas comprises less than about 500ppm by weight water and less than about 500ppm by weight oxygen.

Aspect 3 is the method of any one of aspects 1 or 2, wherein in the providing step, the iodine comprises less than about 500ppm water by weight.

Aspect 4 is the method of any one of aspects 1 to 3, wherein in the providing step, the molar ratio of the hydrogen to the iodine in the reactant stream is from about 1: 1 to about 10: 1.

Aspect 5 is the method of aspect 4, wherein the molar ratio of the hydrogen to the iodine in the reactant stream is from about 2.5: 1 to about 3: 1.

Aspect 6 is the method of any one of aspects 1 to 5, wherein the support is selected from the group of activated carbon, silica gel, zeolite, silicon carbide, metal oxide, or a combination thereof.

Aspect 7 is the method of aspect 6, wherein the support is a metal oxide support comprising alumina, magnesia, titania, zinc oxide, zirconia, chromia, and combinations thereof.

Aspect 8 is the method of aspect 7, wherein the catalyst comprises nickel and the support is alumina.

Aspect 9 is the method of any one of aspects 1 to 8, wherein the catalyst is about 0.1 wt% to about 50 wt% of the total weight of the catalyst and the support.

Aspect 10 is the method of any one of aspects 1 to 9, wherein in the reacting step, the reactant stream is in contact with the catalyst for a time of about 0.1 seconds to about 1,800 seconds.

Aspect 11 is the method of any one of aspects 1 to 10, further comprising heating the reactant stream to a reaction temperature of about 150 ℃ to about 600 ℃ prior to the reacting step.

Aspect 12 is the method of any one of aspects 1 to 11, wherein the product stream further comprises unreacted iodine, and the method further comprises the additional steps of: separating the unreacted iodine from the product stream as solid iodine, heating the solid iodine to produce liquid iodine, and returning the liquid iodine to the reactant stream.

Aspect 13 is the method of any one of aspects 1 to 12, wherein the method is a continuous method.

Aspect 14 is the method of any one of aspects 1 to 13, wherein the product stream further comprises unreacted hydrogen, and the method further comprises the additional steps of: separating the hydrogen from the product stream and returning the separated hydrogen to the reactant stream.

Aspect 15 is the method of aspect 14, wherein separating the hydrogen from the product stream comprises: compressing the product stream; and subjecting the compressed product stream to flash cooling.

Aspect 16 is a method for producing hydrogen iodide. The process includes providing a vapor phase reactant stream comprising hydrogen gas and iodine in a molar ratio of hydrogen to the iodine of from about 1: 1 to about 10: 1, heating the reactant stream to a reaction temperature of from about 150 ℃ to about 600 ℃, and reacting the reactant stream in the presence of a catalyst to produce a product stream comprising hydrogen iodide. The catalyst comprises at least one selected from the group of nickel, cobalt, iron, nickel oxide, cobalt oxide and iron oxide. The catalyst is supported on a carrier. The catalyst is about 0.1 wt% to about 50 wt% of the total weight of the catalyst and the support. The contact time of the reactant stream with the catalyst is from about 0.1 seconds to about 1,800 seconds.

Aspect 17 is a method for producing hydrogen iodide. The process includes providing a vapor phase reactant stream comprising hydrogen gas and iodine in a molar ratio of hydrogen to the iodine of about 2: 1 to about 5: 1, heating the reactant stream to a reaction temperature of about 200 ℃ to about 500 ℃, and reacting the reactant stream in the presence of a catalyst to produce a product stream comprising hydrogen iodide. The catalyst comprises at least one selected from the group of nickel, cobalt and iron. The catalyst is supported on a carrier. The catalyst is about 5 wt% to about 45 wt% of the total weight of the catalyst and the support. The contact time of the reactant stream with the catalyst is from about 2 seconds to about 100 seconds.

Aspect 18 is a method for producing hydrogen iodide. The process includes providing a vapor phase reactant stream comprising hydrogen gas and iodine in a molar ratio of hydrogen to the iodine of about 2: 1 to about 3: 1, heating the reactant stream to a reaction temperature of about 300 ℃ to about 400 ℃, and reacting the reactant stream in the presence of a catalyst to produce a product stream comprising hydrogen iodide. The catalyst comprises nickel. The catalyst is supported on a carrier. The catalyst is about 10 wt% to about 40 wt% of the total weight of the catalyst and the support. The contact time of the reactant stream with the catalyst is from about 2 seconds to about 60 seconds.

Aspect 19 is a method for producing hydrogen iodide. The process includes providing a gas phase reactant stream comprising hydrogen and iodine in a molar ratio of hydrogen to iodine of about 2.5: 1 to about 3: 1, heating the reactant stream to a reaction temperature of about 300 ℃ to about 350 ℃, and reacting the reactant stream in the presence of a catalyst to produce a product stream comprising hydrogen iodide. The catalyst comprises nickel. The catalyst is supported on an alumina support. The catalyst is about 15 wt% to about 35 wt% of the total weight of the catalyst and the support. The contact time of the reactant stream with the catalyst is from about 2 seconds to about 40 seconds.

Aspect 20 is the method of any one of aspects 16-19, wherein in the providing step, the hydrogen gas comprises less than about 500ppm by weight of oxygen hydrated at less than 500ppm by weight, and the iodine comprises less than about 500ppm by weight of water.

Aspect 21 is the method of any one of aspects 16 to 19, wherein in the providing step, the hydrogen gas comprises less than about 50ppm by weight water and less than about 100ppm by weight oxygen, and the iodine comprises less than about 100ppm water.

Aspect 22 is the method of any one of aspects 16 to 19, wherein in the providing step, the hydrogen gas comprises less than about 10ppm by weight water and less than about 10ppm by weight oxygen, and the iodine comprises less than about 30ppm water.

Aspect 23 is the method of any one of aspects 16 to 19, wherein in the providing step, the hydrogen gas comprises less than about 5ppm by weight water and less than about 1ppm by weight oxygen, and the iodine comprises less than about 10ppm water.

Aspect 24 is the method of any one of aspects 16 to 23, wherein the product stream further comprises unreacted iodine and unreacted hydrogen, and the method further comprises the additional steps of: separating the unreacted iodine from the product stream as solid iodine, heating the solid iodine to produce liquid iodine, returning the liquid iodine to the reactant stream, separating the hydrogen from the product stream by compressing the product stream and subjecting the compressed product stream to rapid cooling, and returning the separated hydrogen to the reactant stream, wherein the process is a continuous process.

Aspect 25 is the method of any one of aspects 16 to 23, wherein the product stream further comprises unreacted iodine and unreacted hydrogen, and the method further comprises the additional steps of: separating the unreacted iodine from the product stream as solid iodine, heating the solid iodine to produce liquid iodine, returning the liquid iodine to the reactant stream, separating the hydrogen from the product stream by compressing the product stream and subjecting the compressed product stream to rapid cooling, and returning the separated hydrogen to the reactant stream, wherein the process is a batch process.

Aspect 26 is a method for producing hydrogen iodide. The method comprises the following steps: reacting hydrogen and iodine in the gas phase in the presence of a catalyst to produce a product stream comprising hydrogen iodide and unreacted iodine, wherein the catalyst comprises at least one of nickel, cobalt, iron, nickel oxide, cobalt oxide, and iron oxide, and wherein the catalyst is supported on a support; removing at least some of the unreacted iodine from the product stream by cooling the product stream to form solid iodine, the solid iodine being formed in one of: a first iodine removal container or a second iodine removal container; producing liquid iodine from the solid iodine by: heating the first iodine removal vessel to liquefy the solid iodine while the product stream is cooled by the second iodine removal vessel; or heating the second iodine removal vessel to liquefy the solid iodine while the product stream is cooled by the first iodine removal vessel; and recycling the liquefied iodine to the reaction step.

Aspect 27 is the method of aspect 26, wherein the product stream further comprises unreacted hydrogen, and the method further comprises the additional steps of: separating the hydrogen from the product stream and recycling the separated hydrogen to the reacting step.

Aspect 28 is the method of aspect 27, wherein separating the hydrogen from the product stream comprises: compressing the product stream; and subjecting the compressed product stream to flash cooling.

Aspect 29 is the method of any one of aspects 26 to 28, wherein the method is a continuous method.

Aspect 30 is the method of any one of aspects 26 to 28, wherein the method is a batch process.

Aspect 31 is the method of any one of aspects 26 to 30, wherein the support is selected from the group of activated carbon, silica gel, zeolite, silicon carbide, metal oxide, or a combination thereof.

Aspect 32 is the method of aspect 31, wherein the support is a metal oxide support comprising alumina, magnesia, titania, zinc oxide, zirconia, chromia, or a combination thereof.

Aspect 33 is the method of aspect 32, wherein the catalyst comprises nickel on an alumina support.

Aspect 34 is the method of any one of aspects 26 to 33, wherein reacting hydrogen and iodine in the gas phase in the presence of a catalyst is carried out at a reaction temperature of about 150 ℃ to about 600 ℃.

Aspect 35 is a method for producing hydrogen iodide. The method comprises the following steps: reacting hydrogen and iodine in the vapor phase at a molar ratio of the hydrogen to the iodine of from about 1: 1 to about 10: 1 in the presence of a catalyst at a reaction temperature of from about 150 ℃ to about 600 ℃ and a contact time of from about 0.1 second to about 1,800 seconds to produce a product stream comprising hydrogen iodide and unreacted iodine, wherein the catalyst comprises at least one of nickel, cobalt, iron, nickel oxide, cobalt oxide, and iron oxide, the catalyst is supported on a support, and the catalyst is from about 0.1 wt% to about 50 wt% of the total weight of the catalyst and the support; removing at least some of the unreacted iodine from the product stream by cooling the product stream to form solid iodine, the solid iodine being formed in one of: a first iodine removal container or a second iodine removal container; producing liquid iodine from the solid iodine by: heating the first iodine removal vessel to liquefy the solid iodine while the product stream is cooled by the second iodine removal vessel; or heating the second iodine removal vessel to liquefy the solid iodine while the product stream is cooled by the first iodine removal vessel; and recycling the liquefied iodine to the reaction step.

Aspect 36 is a method for producing hydrogen iodide. The method comprises the following steps: reacting hydrogen and iodine in the vapor phase at a molar ratio of the hydrogen to the iodine of from about 2: 1 to about 5: 1 in the presence of a catalyst at a reaction temperature of from about 200 ℃ to about 500 ℃ and a contact time of from about 2 seconds to about 100 seconds to produce a product stream comprising hydrogen iodide and unreacted iodine, wherein the catalyst comprises at least one of nickel, cobalt, and iron, the catalyst is supported on a support, and the catalyst is from about 5 wt% to about 45 wt% of the total weight of the catalyst and the support; removing at least some of the unreacted iodine from the product stream by cooling the product stream to form solid iodine, the solid iodine being formed in one of: a first iodine removal container or a second iodine removal container; producing liquid iodine from the solid iodine by: heating the first iodine removal vessel to liquefy the solid iodine while the product stream is cooled by the second iodine removal vessel; or heating the second iodine removal vessel to liquefy the solid iodine while the product stream is cooled by the first iodine removal vessel; and recycling the liquefied iodine to the reaction step.

Aspect 37 is a method for producing hydrogen iodide. The method comprises the following steps: reacting hydrogen and iodine in the vapor phase at a molar ratio of the hydrogen to the iodine of from about 2: 1 to about 3: 1 in the presence of a catalyst at a reaction temperature of from about 300 ℃ to about 400 ℃ and a contact time of from about 2 seconds to about 60 seconds to produce a product stream comprising hydrogen iodide and unreacted iodine, wherein the catalyst comprises nickel, the catalyst is supported on a support, and the catalyst is from about 10 wt.% to about 40 wt.% of the total weight of the catalyst and the support; removing at least some of the unreacted iodine from the product stream by cooling the product stream to form solid iodine, the solid iodine being formed in one of: a first iodine removal container or a second iodine removal container; producing liquid iodine from the solid iodine by: heating the first iodine removal vessel to liquefy the solid iodine while the product stream is cooled by the second iodine removal vessel; or heating the second iodine removal vessel to liquefy the solid iodine while the product stream is cooled by the first iodine removal vessel; and recycling the liquefied iodine to the reaction step.

Aspect 38 is a method for producing hydrogen iodide. The method comprises the following steps: reacting hydrogen and iodine in the vapor phase at a molar ratio of the hydrogen to the iodine of from about 2.5: 1 to about 3: 1 in the presence of a catalyst at a reaction temperature of from about 300 ℃ to about 350 ℃ and a contact time of from about 2 seconds to about 40 seconds to produce a product stream comprising hydrogen iodide and unreacted iodine, wherein the catalyst comprises nickel on an alumina support and the catalyst is from about 15 wt% to about 35 wt% of the total weight of the catalyst and the support; removing at least some of the unreacted iodine from the product stream by cooling the product stream to form solid iodine, the solid iodine being formed in one of: a first iodine removal container or a second iodine removal container; producing liquid iodine from the solid iodine by: heating the first iodine removal vessel to liquefy the solid iodine while the product stream is cooled by the second iodine removal vessel; or heating the second iodine removal vessel to liquefy the solid iodine while the product stream is cooled by the first iodine removal vessel; and recycling the liquefied iodine to the reaction step.

Aspect 39 is the method of any one of aspects 35 to 38, wherein the product stream further comprises unreacted hydrogen, and the method further comprises the additional steps of: separating the hydrogen from the product stream by compressing the product stream and subjecting the compressed product stream to flash cooling, and recycling the separated hydrogen to the reacting step; and the process is a continuous process.

Aspect 40 is the method of any one of aspects 35 to 39, wherein the product stream further comprises unreacted hydrogen, and the method further comprises the additional steps of: separating the hydrogen from the product stream by compressing the product stream and subjecting the compressed product stream to flash cooling, and recycling the separated hydrogen to the reacting step; and the process is a batch process.

Aspect 41 is the method of any one of aspects 35 to 40, wherein the hydrogen gas comprises less than about 500ppm by weight water and less than about 500ppm by weight oxygen, and the iodine comprises less than about 500ppm water.

Aspect 42 is the method of any one of aspects 35 to 41, wherein the hydrogen gas comprises less than about 50ppm by weight water and less than about 100ppm by weight oxygen, and the iodine comprises less than about 100ppm water.

Aspect 43 is the method of any one of aspects 35 to 42, wherein the hydrogen gas comprises less than about 10ppm by weight water and less than about 10ppm by weight oxygen, and the iodine comprises less than about 30ppm water.

Aspect 44 is the method of any one of aspects 35 to 43, wherein the hydrogen gas comprises less than about 5ppm by weight water and less than about 1ppm by weight oxygen, and the iodine comprises less than about 10ppm water.