JPH02141402A - Method for reforming methanol - Google Patents

Abstract

PURPOSE:To increase the rate of heat transfer and to increase the reforming reaction rate for methanol, etc., by depositing an Ni-contg. metal on an Al-contg. metallic member to form a catalyst on the surface, and supplying methanol, etc., onto the catalyst on the surface. CONSTITUTION:The Ni-contg. metal is deposited on the metallic member, into which Al is incorporated to increase the heat conductivity, to form a catalyst on the surface. Methanol or a mixture of methanol and water is supplied to the catalytic surface, and a hydrogen-contg. gas is produced from the mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for reforming methanol, and particularly to a method for reforming methanol or a mixture of methanol and water into a hydrogen-containing gas.

[Conventional technology]

Currently, crude oil and petroleum products refined from it are used to produce liquid fuel, gaseous fuel, and reducing gas used in power generation boilers, internal combustion engines, etc., but due to the recent rise in crude oil prices, fuels are diversifying. methanol, which can be synthesized from fossil fuels other than crude oil, is attracting attention. Furthermore, since methanol is decomposed into hydrogen-containing gas at a much lower temperature than naphtha, it has the advantage that waste heat can be used as a heat source for methanol decomposition reactions and steam reforming reactions. The methano-decomposition reaction is as follows (1), 12
This is one type of Toshi.

CHBOH-+CO+2H1”25°C=21.7kc
aA/n+ot...(1) CH10H+nH2O→(2+n)Hl + (1-n
)CO+nCO where 0 (n (1) The methanol steam reforming reaction is expressed by the following equation (3).

CHIIOH+H2O→co,+! lH2d25°C
=11.8kC1lA/mO4... (3) The gas produced in the above reaction has the advantage that the calorific value of the produced gas increases by the amount equivalent to the endothermic amount (d) of the reaction, and furthermore, this produced gas has a high octane number and high output. When applied to designed internal combustion engines, it has the advantages of increasing the compression ratio to improve thermal efficiency, and eliminating emissions of aldehydes and other substances during methanol combustion, resulting in clean combustion.It is a non-polluting fuel for automobiles and even power generation. It can be used as

Furthermore, the gas produced by the above reactions (1) to (3)) separates hydrogen, and this hydrogen can be used as fuel for fuel cell power generation, and as a hydrogen source for hydrogenation reactions of various organic compounds in oil refining and chemical industries. It can also be used as reaction (1)
(2) Carbon monoxide can be separated from the generated gas and used as a carbon monoxide source.

[Problem to be solved by the invention]

Conventionally, when decomposition or steam reforming reactions are carried out using methanol or a mixture of methanol and water as a raw material using the sensible heat of exhaust gas from engines, gas turbines, etc. as a heat source, the exhaust gas temperature is well-known to be <200°C. From 700
'Q, so it can be reformed over a wide temperature range with a small amount of catalyst that can be mounted on an internal combustion engine, and the reforming performance will not deteriorate even if it is exposed to high temperatures of about 700 °C as mentioned above. Reforming methods and stable catalysts are needed.

As a conventional catalyst for reforming methanol, alumina (
Catalysts have been proposed in which platinum metal elements such as platinum or base metal elements such as copper, nickel, chromium, and zinc and their oxides are supported on a carrier such as A/403 (hereinafter referred to as A/403). Currently, many problems remain, such as poor activity and easy thermal deterioration.

In addition to the above-mentioned catalyst preparation method using the metal support method, there is also a preparation method using the precipitation method.A typical example of a catalyst prepared using this method is the synthesis of methanol containing zinc, chromium, and even copper. There is a catalyst for this. Although this catalyst for methanol synthesis is generally known to be effective in the reaction of reforming methanol into a gas containing hydrogen and carbon monoxide, it is susceptible to thermal deterioration.

In addition, the reactor is a shell μ-and-tube heat exchanger type, and the tube is filled with a catalyst, allowing the catalytic reaction between the methanol vapor as the raw material or the mixed vapor of methanol and water with the catalyst. y) is reformed into hydrogen-containing gas.

This reforming reaction is a large endothermic reaction, and the necessary reaction heat is supplied from the heat medium on the shell side, but the heat transfer rate is not very high, so the temperature inside the catalyst layer is low due to the reaction heat. , there is a problem that it is difficult to increase the reaction rate.

[Means to solve the problem]

Therefore, in order to increase the heat transfer rate of the reactor, the present inventors developed a methanol reforming reactor by using a heat transfer tube carrying a catalyst, thereby achieving both heat transfer and catalytic functions at the same time. The present invention was completed based on this finding.

That is, the present invention provides a method for producing a hydrogen-containing gas from methanol or a mixture of methanol and water, in which a metal member containing aluminum is supported with a metal containing nickel to catalyze the surface, and the catalyzed surface is This is a methanol reforming method characterized by supplying methanol or a mixture of methanol and water so that they are in contact with each other.

The present invention will be explained in detail below.

The hydrogen-containing gas in the present invention is a gas containing 50% or more hydrogen, 35% or less carbon oxide, and 25% or less carbon dioxide.

In addition, the metal containing aluminum as used in the present invention refers to a metal containing 99.00% or more of an aluminum component or a metal whose surface is treated with aluminum, that is, a metal containing 99.00% or more of aluminum, or a metal whose surface is treated with aluminum.
1080F to A1200P and 7y minized steel can be used.

Further, the metal containing nickel in the present invention is a metal containing 50% or more of nickel, and a metal containing copper or zinc as a component other than nickel.

Next, regarding a method of supporting a metal containing nickel μ, a plating method can be suitably used.

There are two plating methods: electrolytic method or electroless plating method using chemical reduction, but the latter method is preferable for supporting nickel-containing metal on the aluminum-containing metal used in the reaction tube for methanol reforming. Alternatively, nickel-phosphorous plating or nickel-boron plating, which is commonly practiced as an electroless plating method for nickel, or chemical plating, which uses ionization tendency to perform plating, can be used.

The present invention will be specifically explained below using examples.

[Example 1] A pre-degreased and washed 5 m x 50 x 2 t aluminum plate (Al050 F) was pickled by immersing it in a 1N hydrochloric acid solution at 20°C to 30°C for about 10 minutes, washed with water, and then chlorinated. Shinitsuke μ was supported by electroless plating in a nickel solution, washed with water, immersed in a sodium hydroxide solution for alkali treatment, washed with water and dried.
was prepared.

This catalyst was packed into a quartz glass reactor, and the activity of the catalyst was evaluated under the conditions shown in Table 1.

The results are shown in Table 2.

As is clear from Table 2, hydrogen and carbon monoxide were obtained in approximately stoichiometric amounts, indicating good selectivity.

Table 1 Table 2 The following reformed gas compositions are expressed excluding H, O, and CH3OH [Example 2] Preliminary degreased and washed aluminized steel of 5 sieves x 50 m x 2 t was used. Also, instead of the nickel chloride V aqueous solution, a mixed aqueous solution of a nickel chloride aqueous solution and a nitric acid aqueous solution was used to electroless plating the nickel nickel μ and copper (
A catalyst was prepared in the same manner as in Example 1, except that the atomic ratio of Ni and Cu (atomic ratio of Ni to Cu = 70:30) was supported, and the activity was evaluated in the same manner as in Example 1. The conditions are shown in Table 3, and the results are shown in Table 4.

Table 3 Table 4 [Effects of the Invention] By the present invention, which uses a catalyst that has both heat transfer function and catalytic function, a purposeful methanol reforming reaction can be carried out.

Claims (1)

[Claims] In a method for producing hydrogen-containing gas from methanol or a mixture of methanol and water, a metal containing nickel is supported on a metal member containing aluminum to catalyze the surface, and methanol or methanol is placed in contact with the catalyzed surface. A method for reforming methanol, comprising supplying a mixture of water and water.