The synthesis-gas steam reforming using catalyzed equipment

 

This invention is directed to the production of synthesis gas by steam reforming of hydrocarbons by contact with catalyzed equipment. A method of obtaining a gas enriched in hydrogen and carbon monoxide by catalytic reforming of hydrocarbon raw materials, includes the operation and transmission process gas containing hydrocarbon raw material, through a tubular reactor with a steam reforming catalyst heated by burning fuel. Moreover, the steam reforming catalyst deposited on a metal sheet having the same shape as the wall of the reactor, and is in close thermal communication with the inner pipe wall of the tubular reactor. The method further includes an operation bandwidth before surgery (a) of hydrocarbons through the first reactor catalyst for steam reforming. The reforming catalyst in the reactor in operation (a) used in combination with granules of catalyst reforming process. The reforming catalyst comprises Nickel and/or noble metals. This invention allows to increase service life of reactors and leads to better use of raw materials. 3 C.p. f-crystals, 1 Il., table 1.

the contact with the catalyzed equipment.

The term "catalyzed the equipment used for the catalytic system, where the catalyst layer is fixed on the surface of another material, such as metallic surfaces. This other material is used as a catalyst carrier, giving the system strength. This allows you to create catalysts such configurations, the mechanical strength of which by itself would be insufficient.

Synthesis gas is produced from hydrocarbons by steam reforming in accordance with the following reactions (1)-(3): CnHm+nH2O _nCO+(n+m/2)H2(H°298<0) (1) CO+H2OCO2+H2(H°298= 41 kJ/mol) (2) CH4+H2OCO+3H2(H°298= -206 kJ/mol) (3) At the present level of technology in the technology of the steam reforming process using the catalyst of the reforming process in the form of granules of various sizes and shapes. Granules of the catalyst placed in the reactor with fixed bed (pipe reforming process-setup). The reaction of reforming endothermic. In the reforming-installations of conventional type, the necessary heat is supplied from the ing-installation. Heat is transferred through the pipe wall on the inner surface of the pipe by conduction and is transferred to the gas phase by convection. Finally, heat is transferred from the gas phase to the catalyst granules by means of convection. The temperature of the catalyst can be more than 100oC lower than the temperature of the inner wall of the tube at the same axial position of the pipe reforming installation.

It was found that the heat transfer is more effective when used in a process catalyzed steam reforming equipment. The transfer of heat to the catalyst occurs from the inner wall of the pipe by conduction. This transfer mechanism is much more efficient than transfer by convection through the gas phase. The result is that the temperature of the inner wall of the pipe and catalyst are almost identical (the difference is less than 5oC). Moreover, it is possible to reduce the thickness of the pipe, which reduces the temperature difference between the inner and outer sides of the tubes of the reformer installation. Consequently, it is possible to have both a higher temperature of the catalyst and lower the temperature of the pipe, when the pipe replacement reforming-install conventional type of pipe katalizirovannogo low, as this prolongs the service life of the pipe. The high temperature of the catalyst has advantages, since the reaction rate increases with temperature, and since the equilibrium of reaction (3) is moved to the right, which leads to better use of raw materials.

The pressure drop in the catalyzed pipe reformer installation is much lower than in the normal case, for the same pipe diameter. This allows the use of a pipe reactor with a smaller diameter and nevertheless support an acceptable pressure drop. When using a smaller diameter pipe, the service life of the pipe increases, the pipe is resistant to higher temperatures, reduced material consumption.

Finally, the amount of the catalyst when using catalyzed equipment pipe reformer installation is reduced compared to the reforming-installations of conventional type with a fixed catalyst bed reformer.

The drawing shows the front part of the installation for the production of synthesis gas.

Raw material 2 is heated, disulfiram in unit 4, is mixed with process steam 6 and further heated before serving in the adiabatic pre-reforming-installation 8. Flow arising from pre-reforming is in a tubular steam reforming process-setting 14, where the conversion of methane to hydrogen, carbon monoxide and carbon dioxide. Processing resulting from the reforming process is the installation of the gas flow depends on the use of the product.

Catalyzed equipment can be used in both blocks shown in the drawing: in the heating coil 10 to heat resulting from the pre-reforming process is the installation of the gas stream prior to its entrance into the tubular reformer installation 14; in the tubular reformer installation 14.

The catalytic coating of metal surfaces (thin layer) is a well - known process (its description can be found, for example, Cybulski, A. , Moulijn, J. A. , Structured catalysts and reactors, Marcel Dekker, Inc. , New York, 1998, Chapter 3 and references therein). A thin layer of a slurry containing a ceramic precursor, is applied to the surface, for example by spraying, painting or dipping. After coating the slurry is dried and calcined usually at a temperature in the range from 350 to 1000oC. Finally, the ceramic layer is impregnated with a catalytically active material. Alternatively, you can apply a catalytically active material simultaneously with the ceramic precursor.

Unfortunately, the reactor catalyzed equipment is , if he's going to lose their activity with time or as a result of poisoning of the catalyst layer can be applied only on certain materials. And pipes of the reactor must be made of this type of material, and it may be more expensive than the usual material for pipes. The reaction of the steam reforming process flow at high pressure, and the pipe has a large thickness, therefore, the cost of the material significantly affects the price; moreover, the production of long tubes catalyzed reactor equipment can be difficult. The length of the pipe reactor can reach 10 m or more. It would be difficult to obtain a layer of the catalyst for reforming a uniform thickness along the entire length of such pipe, and means for obtaining a uniform layer, which can be used on a small scale, such as centrifugation tubes, it is more difficult to apply for a pipe of this size. Moreover, the corresponding heat treatment of pipes of this size is difficult.

These disadvantages can be overcome if the manufacturing catalyzed equipment separately from the reactor, as described below.

The metal substrate is cut into pieces of suitable size. On sheet a thin layer as described above. After n is th form before applying a thin layer. Metal substrate give essentially the same form that has a reactor wall, and positioned so that she was directly in thermally conductive communication with the reactor wall.

You can replace the catalyst bed, if he will not have sufficient catalytic activity. Expensive steel, used for connection of the catalyst metal surface will constitute only a small share in the total consumption of the metal. Catalyzed equipment can be made in smaller sections that are easier to manufacture and handle.

Accordingly, this invention provides a method of obtaining a gas enriched in hydrogen and carbon monoxide by catalytic steam reforming of hydrocarbons, including operation:
(a) passing the process gas containing hydrocarbon raw material, through a tubular reactor with a steam reforming catalyst heated by burning fuel, and the steam reforming catalyst deposited on a metal substrate, having essentially the same shape as the wall of the reactor, and is in close heat-conducting relation with the inner wall of the pipe t (a) of hydrocarbons through the first reactor catalyst for steam reforming, heated hot gas stream, and a steam reforming catalyst deposited on a metal substrate, having essentially the same shape as the wall of the reactor, and is in close heat-conducting relation with the inner wall of the pipe reactor.

In a specific embodiment of this invention, the reforming catalyst in the reactor in operation (a) deposited on a metal substrate, used in combination with the catalyst granules reformer.

The steam reforming catalyst used in the proposed method may include Nickel and/or noble metals.

Example
System reactor with heating coil for conversion of hydrocarbons consists of 16 pipe length 20 m Pipes have an internal diameter of 100 mm and an outer diameter of 120 mm, an Inner wall of each tube is designed to cover a thin layer of catalyst reforming process.

The mechanical strength of each pipe is satisfactory when using steel 18Cr/8Ni containing Cr, Ni and Fe in the ratio of 18:8:74. However, the material of the catalyst has no adhesion to this type of steel. He has adhesion to high-alloy Nickel steel, such as Inconel 600, which contains CR, Ni and Fe in sootnosheniem steel that would be extremely expensive, as can be seen from the above table. In addition, it would be difficult for the entire length of each pipe (20 m) to obtain a uniform coating thickness of the catalyst.

According to the proposed method, using a reactor in which each pipe is made of cheaper steel 18Cr/8Ni, and the pipe is a sheet of foil alloyed Nickel steel, coated with catalyst. This plate is made by cutting the foil into sheets with dimensions corresponding to the internal dimensions of the tube, with the subsequent implementation of the covering foil from the liquid phase reforming catalyst and forming it into a tubular form corresponding to each pipe. Then it is introduced into the pipe and is placed in close thermal communication with the inner pipe wall.

Characteristics of the reactor containing tubes of high-alloy Nickel steel reactor containing steel pipe 18Cr/8Ni and foil alloyed Nickel steel, are identical. However, the price of the reactor tubes containing foil, approximately 50% lower, as can be seen from the table.


Claims

1. A method of obtaining a gas enriched in hydrogen and carbon monoxide by catalytic R is the hydrocarbon feedstock, through a tubular reactor with a steam reforming catalyst heated by burning fuel, and the steam reforming catalyst deposited on a metal sheet having the same shape as the wall of the reactor, and is in close thermal communication with the inner pipe wall of the tubular reactor.

2. The method according to p. 1, further comprising an operation bandwidth before surgery (a) of hydrocarbons through the first reactor with the steam reforming catalyst heated by a hot gas stream, and a steam reforming catalyst deposited on a metal sheet having the same shape as the wall of the reactor, and is in close heat-conducting relation with the inner wall of the pipe reactor.

3. The method according to p. 1 or 2, in which the reforming catalyst in the reactor in operation (a) used in combination with the catalyst granules reformer.

4. The method according to any of paragraphs.1-3, in which the steam reforming catalyst comprises Nickel and/or noble metals.

 

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