JP2002145604A - Method for producing hydrogen - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably produce hydrogen over a long period without depositing carbonaceous material at the time of producing a hydrogen-containing gas by reforming reaction under the optimum condition of a temperature of nearly 900 deg.C, a pressure of nearly 20 kg/cm2 and a steam/carbon ratio of nearly 1. SOLUTION: A reforming catalyst composed of a multiple oxide having a composition expressed by a formula, aM.bCo.cNi.dMg.eCa.fO (M represents manganese, molybdenum, rhodium or the like), and having M, Co and Ni, at least one kind of which is highly dispersed in the multiple oxide, is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hydrogen-containing gas by reacting a hydrocarbon such as methane, natural gas, and naphtha with steam (steam), and can stably produce hydrogen at low cost. It is like that.

[0002]

2. Description of the Related Art Conventionally, methane, natural gas, naphtha,
A hydrocarbon such as petroleum gas, heavy oil, crude oil and steam are sent to a reactor, and 800 to 1000 ° C. in the presence of a reforming catalyst.
At a temperature of (reforming reaction) to produce a reformed gas containing hydrogen and carbon monoxide as main components.
Then, a method of producing hydrogen by separating hydrogen in the reformed gas is known. As the reforming catalyst, nickel / alumina catalyst, nickel / magnesia /
An alumina catalyst or the like is used.

[0003] The hydrogen thus produced is desulfurized,
Used for applications such as hydrorefining, fertilizer production, and reduction iron making.
/ Cm ² (In this specification, all pressures are gauge pressure kg
/ Cm ² G. ) Is preferable, and there is a situation that high-pressure hydrogen is desired by users (purchasers) of hydrogen.

[0004] By the way, in the production of hydrogen by the reforming reaction, it is said that there are optimal reaction conditions in view of energy efficiency and apparatus cost during the reaction. In a normal reforming reaction, a temperature of 600 to 10
00 ° C., the pressure is in the range of 5~30kg / cm ^2, typical reaction temperature of 900 ° C., the pressure is 20 kg / cm
It is performed under about ^two conditions.

[0005] On the other hand, in a hydrogen production plant based on a reforming reaction, a steam / carbon ratio is a factor that greatly affects the operation cost and equipment cost. The steam / carbon ratio is a ratio of the number of moles of steam (water) to 1 mole of carbon in the raw material hydrocarbon. This steam / carbon ratio will preferably simply be around the chemical equivalent of 1.

Therefore, a temperature of 900 ° C. and a pressure of 20 kg
It is most preferable to carry out the reforming reaction under the reaction conditions of about 1 / cm ² and a steam / carbon ratio of about 1. However, if it is attempted to carry out the reaction under the optimum conditions of a temperature of 900 ° C., a pressure of 20 kg / cm ² , and a steam / carbon ratio of about 1, in the conventional reforming catalyst, a large amount of carbonaceous material is precipitated and the reaction is carried out. That was impossible.

FIG. 1 shows the relationship between the reaction pressure at a reaction temperature of 900 ° C. and the steam / carbon ratio in the case where a conventional reforming catalyst is used. The carbonaceous deposition is below the permissible value and is in a practicable range, and the other region indicates that the carbonaceous precipitation exceeds the permissible value and is not practical. From this graph, it can be seen that a reaction cannot be performed practically under the condition that the steam / carbon ratio is close to 1 at a temperature of 900 ° C. and a pressure of 20 kg / cm ² using a conventional reforming catalyst.

For this reason, the conventional method for producing hydrogen by the reforming reaction operates with a steam / carbon ratio of 3 or more, requires excessive steam, increases the production cost, and increases the equipment cost. was there.

[0009]

Accordingly, an object of the present invention is to produce a hydrogen-containing gas under optimum conditions of a temperature of 900 ° C., a pressure of 20 kg / cm ² and a steam / carbon ratio of about 1 by a reforming reaction. Another object of the present invention is to provide a stable and low-cost production for a long period without carbonaceous deposition.

[0010]

This problem can be solved by using the following reforming catalyst. Further, by using this catalyst, the pressure is 5 to 40 kg / cm ² ,
Temperature 750-950 ° C, steam / carbon ratio 1.3-
Even in a wide condition range of 3.0, no carbonaceous material is deposited, and economical production of hydrogen becomes possible. This reforming catalyst is composed of a composite oxide having a composition represented by the following formula, and at least one of M, Co, and Ni is highly dispersed in the composite oxide. aM · bCo · cNi · dMg · eCa · fO (where a, b, c, d, and e are mole fractions and a + b
+ C + d + e = 1, 0 ≦ a ≦ 0.1, 0.001 ≦
(B + c) ≦ 0.3, 0 ≦ b ≦ 0.3, 0 ≦ c ≦ 0.
3,0.6 ≦ (d + e) ≦ 0.999,0 <d ≦ 0.9
99,0 ≦ e ≦ 0.999, f = the number of elements required to maintain charge balance with oxygen, M excluding Group 6A element, Group 7A element, Co and / or Ni 8th
It is at least one kind of group transition element, group 1B element, group 2B element, group 4B element, and lanthanoid element. )

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
First, the reforming catalyst used in the method for producing hydrogen of the present invention will be described. This reforming catalyst is composed of a composite oxide having a composition represented by the following formula, and at least one of M, Co, and Ni is highly dispersed in the composite oxide. aM · bCo · cNi · dMg · eCa · fO (where a, b, c, d, and e are mole fractions and a + b
+ C + d + e = 1, 0 ≦ a ≦ 0.1, 0.001 ≦
(B + c) ≦ 0.3, 0 ≦ b ≦ 0.3, 0 ≦ c ≦ 0.
3,0.6 ≦ (d + e) ≦ 0.999,0 <d ≦ 0.9
99,0 ≦ e ≦ 0.999, f = the number of elements required to maintain charge balance with oxygen, M excluding Group 6A element, Group 7A element, Co and / or Ni 8th
It is at least one kind of group transition element, group 1B element, group 2B element, group 4B element, and lanthanoid element. )

Note that the periodic table here is based on IUPAC. Here, M is preferably at least one selected from manganese, molybdenum, rhodium, ruthenium, platinum, palladium, copper, silver, zinc, tin, lead, lanthanum, and cerium. Further, in this composition, the content (a) of M is 0 ≦ a ≦ 0.10, preferably 0 ≦ a ≦ 0.05, and more preferably 0 ≦ a ≦.
0.03. When the content (a) of M exceeds 0.10, the activity of the reforming reaction is lowered, which is disadvantageous.

The cobalt content (b) is 0 ≦ b ≦ 0.3
And preferably 0 ≦ b ≦ 0.25, and more preferably 0 ≦ b ≦ 0.20. When the cobalt content (b) exceeds 0.3, high dispersion described later is hindered, and the effect of preventing carbonaceous deposition cannot be sufficiently obtained.

The nickel content (c) is 0 ≦ b ≦ 0.3
And preferably 0 ≦ b ≦ 0.25, and more preferably 0 ≦ b ≦ 0.20. When the nickel content (c) exceeds 0.3, high dispersion described later is hindered, and the effect of preventing carbonaceous deposition cannot be sufficiently obtained.

Further, the total amount (b + c) of the cobalt content (b) and the nickel content (c) is 0.001 ≦ b +
c ≦ 0.3, preferably 0.001 ≦ b + c ≦
0.25, more preferably 0.0001 ≦ b + c ≦
0.20. When the total content (b + c) exceeds 0.3, high dispersion described later is hindered, and the effect of preventing carbonaceous deposition cannot be sufficiently obtained. If it is less than 0.001, the reaction activity is low.

The total amount (d + e) of the magnesium content (d) and the calcium content (e) is 0.6 ≦ (d +
e) ≦ 0.9998, preferably 0.70 ≦ (d
+ E) ≤0.9998, more preferably 0.77≤
(D + e) ≦ 0.9998. Among these, the magnesium content (d) is 0 <d ≦ 0.999, preferably 0.20 ≦ d ≦ 0.9998, more preferably 0.37 ≦ d ≦ 0.9998, and the calcium content (E) is 0 ≦ d <0.999, preferably 0 ≦ d ≦ 0.
5, more preferably 0 ≦ d ≦ 0.3, and may be one lacking calcium.

The total amount (d + e) of the magnesium content (d) and the calcium content (e) is the M content (a),
It is determined by the balance between the cobalt content (b) and the nickel content (c). (D + e) exhibits an excellent effect on the reforming reaction at any ratio as long as it is within the above range, but a large content of calcium (e) and M (a) is effective in suppressing carbonaceous precipitation. , The catalytic activity is lower than when magnesium (d) is high. Therefore, if the activity is emphasized, it is not preferable that the calcium content (e) exceeds 0.5 and the M content (a) exceeds 0.1 because the activity is reduced.

The composite oxide in the present invention is MgO,
CaO has a rock salt type crystal structure, and M
It is a kind of solid solution in which a part of g or Ca atoms is replaced by Co, Ni or M, and forms a single phase, and does not mean a mixture of single oxides of each element. In the present invention, at least one of Co, Ni and M is in a highly dispersed state in the composite oxide.

The dispersion in the present invention is generally defined in the field of catalysts, and is, for example, as described in “Catalyst Course Vol. 5, Catalyst Design”, page 141 (edited by the Catalysis Society of Japan, published by Kodansha). And the ratio of the number of atoms exposed on the catalyst surface to the total number of atoms of the supported metal.

This will be described in detail with reference to the schematic diagram of FIG. 2 of the present invention.
On the surface of 1, microparticles 10 such as hemispheres serving as active centers
2, 102... Are present innumerably.
Is composed of Co and M metal elements or compounds thereof after the activation (reduction) treatment described later. Assuming that the number of atoms of the metal element of Co, Ni or M or the compound thereof constituting the microparticle 102 is A, and the number of atoms of these atoms exposed on the surface of the particle 102 is B,
/ A is the degree of dispersion.

It is the fine particles 102 that participate in the catalytic reaction.
If it is considered that the atoms are exposed on the surface, many atoms are distributed on the surface if the dispersity is close to 1, so that the number of active centers is increased, and it is considered that the atoms can be highly active. Also, if the particle diameter of the microparticles 102 becomes infinitely small, most of the atoms forming the microparticles 102 will become particles 10
As a result, the degree of dispersion approaches one.
Therefore, the particle size of the fine particles 102 can be an index indicating the degree of dispersion.

In the catalyst used in the present invention, fine particles 1
The diameter of 02 is less than the measurement limit of 3.5 nm in various measurement methods, for example, an X-ray diffraction method, and it can be said that the dispersion has a high degree of dispersion and a high dispersion state. For this reason,
The number of atoms of cobalt, nickel or M involved in the reaction increases, the activity becomes high, the reaction proceeds stoichiometrically, and the deposition of carbonaceous (carbon) is prevented.

As a method for producing such a reforming catalyst, any method may be used as long as it can obtain the above-mentioned highly dispersed state of cobalt, nickel or M, but a particularly preferable method is Examples thereof include an impregnation-supporting method, a coprecipitation method, a sol-gel method (hydrolysis method), a uniform precipitation method, and the like. Further, Japanese Patent Application No. 6-301645 filed earlier by the present applicant (Japanese Patent Application Laid-open No. Can be used.

For example, to prepare by the coprecipitation method, first, cobalt, nickel, magnesium, calcium, a group 6A element, a group 7A element, a group 8 transition element excluding Co and / or Ni, A complete aqueous solution is prepared by dissolving water-soluble salts such as organic salts such as acetates of Group 1B elements, Group 2B elements, Group 4B elements and lanthanoid elements, and inorganic salts such as nitrates in water. While the aqueous solution is being stirred, a precipitant is added at 20 to 120 ° C., preferably 40 to 100 ° C. to form a precipitate. In order to highly disperse the catalyst component, it is preferable to stir when generating the precipitate, and it is preferable to stir for 10 minutes or more after the formation of the precipitate to complete the formation of the precipitate.

Preferred sedimenting agents are sodium and / or potassium carbonates, bicarbonates, oxalates and hydroxides. Also, ammonium carbonate, ammonium hydroxide, ammonia (aqueous ammonia) and the like can be used as the precipitating agent. The addition of a sedimentation agent raises the pH,
The compound consisting of the above components precipitates in the form of a thermally decomposable hydroxide. The final pH of the mixture is preferably 6 or more, more preferably a pH in the range of 8-11. When a precipitate is obtained, the precipitate is filtered, washed repeatedly with water or an aqueous solution of ammonium carbonate, and then dried at a temperature of 100 ° C. or higher. Next, the dried sediment is put in air at 500 to 1500 ° C., preferably 1000 to 130 ° C.
By calcining at 0 ° C. for 20 hours, the thermally decomposable hydroxide is thermally decomposed to obtain a target reforming catalyst. In addition, the precipitate is 400 ~
Primary sintering at 600 ° C.
A secondary calcination at 0 to 1300 ° C. may be used as a reforming catalyst.

The catalyst thus obtained has a specific surface area of 0.2 to ⁵ m ² / g. The obtained catalyst can be pulverized and used as a powder. However, if necessary, the catalyst can be molded by a compression molding machine and used as a tablet. In addition, these catalysts can be used in combination with quartz sand, alumina, magnesia, calcia, and other diluents.

Next, the method for producing hydrogen of the present invention will be described in detail. First, the reforming catalyst is activated in advance. In this activation treatment, the catalyst is heated in the presence of a reducing gas such as hydrogen gas at 500 to 1000 ° C., preferably 600 to 1000 ° C.
This is carried out by heating at a temperature in the range of １０００1000 ° C., more preferably 650０〜1000 ° C., for about 0.5 to 30 hours. The reducing gas may be diluted with an inert gas such as nitrogen gas. This activation treatment can be performed in a reactor for performing a reforming reaction. By this activation treatment, the fine particles 102, 1 on the surface of the catalyst 101 in FIG.
02 is reduced to at least one of Co, Ni and M
The species becomes a metal element or its compound, and the catalytic activity is exhibited. The activation treatment here is performed at a higher temperature than the activation of the conventional Co oxide-based catalyst. All of the conventional Co oxide-based catalysts are performed at a temperature lower than 500 ° C., and such an activation treatment at a high temperature may contribute to the above-mentioned high dispersion.

FIG. 3 shows a manufacturing apparatus for carrying out an example of the manufacturing method of the present invention. In this example, the description will be given using natural gas containing methane as a main component as a hydrocarbon. Natural gas as a raw material gas is sent from a pipe 1 to a preheating furnace 2, where it is heated to 300 to 500 ° C., and is sent to a desulfurizer 4 through a pipe 3. In the desulfurizer 4,
The sulfur that accompanies the natural gas is removed by the separately introduced hydrogen, and the desulfurized natural gas passes through the pipe 5 and joins with the steam supplied from the separate pipe 6 to be re-heated.
And heated to 500 to 600 ° C. and sent to the reactor 7. The steam / carbon ratio at the inlet of the reactor 7 is between 1.3 and 2.5.

At the bottom of the reactor 7 are mounted burners 8, 8 to which air is supplied from a pipe 9 and fuel (natural gas) is supplied from a pipe 10, respectively.
The inside of the reactor 7 is maintained at a temperature required for the reaction. The reactor 7 is provided with a catalyst bed 7a filled with the above-mentioned reforming catalyst. The form of the catalyst bed 7a is as follows.
Any form such as a fixed bed, a moving bed, and a fluidized bed can be selected. The space velocity of the raw material gas is 500 to 20,000.
0 / Hr, preferably 1000 to 100000 / Hr,
More preferably, it is in the range of 1000 to 70000 / Hr. The temperature at the outlet of the reactor 7 is 750-950 ° C.,
Preferably 850-900 ° C., pressure is 5-40 kg /
cm ² , preferably 15 to 25 kg / cm ² .

After the reaction, the hydrogen-containing gas (hereinafter also referred to as reformed gas) has a temperature of 750 to 950 ° C. and a pressure of 5 to 950 ° C.
４０40 kg / cm ² , carbon monoxide and hydrogen
vol.%, the balance having the composition of carbon dioxide, water vapor and unreacted methane.
Is sent to the first heat exchanger 12 through the pipe 11, and the heat is recovered.

The reformed gas cooled to 350 to 450 ° C. in the first heat exchanger 12
Where, in the presence of a catalyst, carbon monoxide in the gas reacts with water vapor and is converted into hydrogen and carbon dioxide, and carbon monoxide is converted to a gas having a volume of 0.5 vol% or less and a temperature of 400 to 500 ° C. And sent from the pipe 14 to the second heat exchanger 15,
Here, heat is further recovered, cooled, and sent to the separation tank 16. In the separation tank 16, water in the gas is condensed and removed.

The gas from which water has been removed passes through a pipe 17 and
The hydrogen is sent to the PSA unit 18 where the hydrogen is separated and concentrated to a purity of 99 to 99.99% and a pressure of 5 to 40 kg / cm.
^2. Hydrogen at a temperature of 30 to 40 ° C is extracted as a product. The PSA device 18 is based on a pressure swing adsorption method (pressure swing absorption) using a known adsorbent and a separation membrane, and exhaust gas (off gas) from the PSA device 18 is used.
Contains carbon monoxide, hydrogen, methane, carbon dioxide and the like, and is sent from a pipe 19 to the burners 8 and 8 of the reactor 7 as fuel.

On the other hand, pure water is sent from the pipe 20 to the second heat exchanger 15, where it is heated by exchanging heat with the reformed gas from the high-temperature shift converter 13 and then sent to the steam drum 21. Here, it is further heated by the heat recovered in the first heat exchanger 12 to form steam at a temperature of 180 to 310 ° C. and a pressure of 10 to 100 kg / cm ² ,
Is mixed with the natural gas of the raw material flowing through the pipe 5 and sent to the preheating furnace 2. Excess steam is branched off from the pipe 22 and discharged out of the system.

FIG. 4 shows an apparatus for carrying out the second example of the method for producing hydrogen of the present invention. In this example, as a raw material hydrocarbon, a hydrocarbon having a main component of 3 to 8 carbon atoms, such as oil accompanying gas, naphtha, and heavy oil, and a mixture thereof (in the present invention, referred to as heavy hydrocarbon). In this example, the description will be made using an example using naphtha. In the production method of this example, naphtha is introduced into a pre-converter in advance and pre-converted to be converted into a light hydrocarbon having 2 or less carbon atoms and then sent to a reactor. For this reason, in FIG. 4, the same components as those shown in FIG. 3 are denoted by the same reference numerals, and description thereof will be omitted.

The raw material naphtha is sent from a pipe 1 to a preheating furnace 2 where it is heated to be in a gaseous state and sent from a pipe 3 to a desulfurizer 4 where the accompanying sulfur is desulfurized. The naphtha from the desulfurizer 4 is sent again from the pipe 5 to the preheating furnace 2 where the steam from the pipe 6 is mixed therewith. The mixture of naphtha and steam heated to a temperature of 400 to 550 ° C. in the preheating furnace 2 is sent to the pre-converter 22.

The pre-converter 22 is filled with a known nickel-based catalyst, and has a temperature of 400 to 550 ° C., a pressure of 5.5 to 55 kg / cm ² , and a steam / carbon ratio of 1 to 1.
The conversion reaction proceeds under the conditions of 4, wherein naphtha is converted to low-quality hydrocarbon methane. The low-quality hydrocarbon discharged from the pre-converter 22 is sent again to the preheating furnace 2 from the pipe 23, and at this time, the steam from the pipe 24 branched from the pipe 6 is mixed therein. The mixed gas of low-quality hydrocarbon and steam is heated again in the preheating furnace 2 and supplied to the reactor 7. The processing operations after the reactor 7 are as follows:
This is the same as in the example of natural gas.

In such a method for producing hydrogen, the above-mentioned high-activity reforming catalyst is used in the reforming reaction, so that low-cost operation is possible as a reaction condition.
The steam / carbon ratio is around 1.5, and the equipment cost can be reduced.
^{Even under} about ² reaction conditions, no carbonaceous material is deposited, and hydrogen can be produced stably for a long period of time.

Further, since the activity of the reforming catalyst is high,
Steam / carbon ratio 1.3-2.5, temperature 750-9
Under a wide range of conditions of 50 ° C. and a pressure of 5 to 40 kg / cm ² , the reforming reaction can be favorably advanced without causing precipitation of carbonaceous material. For this reason,
According to the method for producing hydrogen of the present invention, it is possible to reduce operating costs and equipment costs.

For the purification of hydrogen from the hydrogen-containing gas, a membrane separation method using a separation membrane such as a palladium membrane may be used instead of the PSA method.

Hereinafter, specific examples will be shown, but the present invention is not limited to these specific examples. (1) Preparation Example of Reforming Catalyst 1.62 kg of cobalt nitrate hexahydrate and 27.1 kg of magnesium nitrate hexahydrate were dissolved in 50 L of water. Then
While maintaining the solution temperature at 50 ° C., the pH was adjusted to 9 by adding 59 L of a 2 mol / L aqueous calcium carbonate solution,
A precipitate consisting of two components, cobalt and magnesium, was formed. The precipitate was filtered and washed. 12 in the air
Dry at 0 ° C. for at least 12 hours. Then, in the air, 450
The mixture was fired at 4 ° C. for 4 hours to obtain a primary fired product. Mold this,
Then, it was calcined in air at 1180 ° C. for 5 hours to obtain a catalyst.

(2) Production Example 1 4 L of the reforming catalyst obtained in the above-mentioned Preparation Example was treated with an inner diameter of 50 m.
m, a flowable reaction tube having an effective length of 2000 mm was filled into a reactor. After the reactor was activated by flowing hydrogen at a temperature of 700 ° C. in advance, methane and steam were mixed at a steam / carbon ratio of 0.9, a methane supply of 5 Nm ³ / hour, and a steam supply of 4.5 Nm. ^The reactor was fed at 550 ° C. for ³ / hour. The temperature at the reactor outlet was 900 ° C., and the pressure was 20 kg / cm ² .

Table 1 shows the results of the reaction. In Table 1,
The “calorific value unit” is a value obtained by multiplying the total amount of methane for raw material and methane for fuel by the calorific value and dividing the resulting value by the amount of generated hydrogen. The “heat recovery system equipment capacity” is the heat recovery system (steam generator) equipment capacity divided by the amount of hydrogen generated.

(3) Production Examples 2 to 4 The reaction was carried out in the same manner as in Production Example 1 except that the steam supply amount was changed to change the steam / carbon ratio, and the other conditions were the same. Table 1 shows the results.

[0044]

[Table 1]

From the results shown in Table 1, it was found that when the steam / carbon ratio was 1.5, the unit heat consumption and the capacity of the heat recovery system were minimized, and the most economical hydrogen production was possible. It is also evident that no carbonaceous deposition occurs at steam / carbon ratios of 3 or less.

[0046]

As described above, according to the method for producing hydrogen of the present invention, at least one of CoO, NiO and MOx is converted into a composite oxide with MgO or MgO / CaO,
Since a reforming catalyst in which at least one of Co, Ni and M is highly dispersed is used to obtain a hydrogen-containing gas from a hydrocarbon and steam by a reforming reaction, the operating cost and the equipment cost are the lowest. Even under cheap reaction conditions, there is no precipitation of carbonaceous material, and stable production can be performed for a long period of time.

Further, if a preliminary conversion step is provided in the preceding stage to convert heavy hydrocarbons such as naphtha into light hydrocarbons such as methane and react them with steam, heavy hydrocarbons can be converted into raw materials without any problem. can do. Furthermore, if the off-gas discharged from the hydrogen separation step is used as a heat source for the reaction, or the heat of the hydrogen-containing gas from the reactor is recovered and used as a heat source for the steam, the operating cost can be reduced.

[Brief description of the drawings]

FIG. 1 is a chart showing a relationship between a reaction pressure and a steam / carbon ratio when a conventional reforming catalyst is used.

FIG. 2 is an explanatory view schematically showing a surface state of a catalyst used in the present invention.

FIG. 3 is a schematic configuration diagram of an apparatus used in an example of the method for producing hydrogen of the present invention.

FIG. 4 is a schematic configuration diagram of an apparatus used in another example of the method for producing hydrogen of the present invention.

[Explanation of symbols]

7 ... reactor, 12 ... first heat exchanger, 18 ... PSA device,
21: Steam drum, 22: Pre-converter

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] December 11, 2000 (200.12.
11)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction contents]

The nickel content (c) is 0 ≦ c ≦ 0.3
And preferably 0 ≦ c ≦ 0.25, more preferably 0 ≦ c ≦ 0.20. When the nickel content (c) exceeds 0.3, high dispersion described later is hindered, and the effect of preventing carbonaceous deposition cannot be sufficiently obtained.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction contents]

The total amount (d + e) of the magnesium content (d) and the calcium content (e) is 0.6 ≦ (d +
e) ≦ 0.9998, preferably 0.70 ≦ (d
+ E) ≤0.9998, more preferably 0.77≤
(D + e) ≦ 0.9998. Among these, the magnesium content (d) is 0 <d ≦ 0.999, preferably 0.20 ≦ d ≦ 0.9998, more preferably 0.37 ≦ d ≦ 0.9998, and the calcium content (E) is 0 ≦ e <0.999, preferably 0 ≦ e ≦ 0.
5, more preferably 0 ≦ e ≦ 0.3, and may lack calcium.

Continued on the front page F-term (reference) 4G040 EA03 EA06 EB18 EB43 EB44 EC02 EC04 EC05 4G069 AA02 AA08 BB06A BB06B BC09A BC09B BC10A BC10B BC21A BC22A BC30A BC31A BC32A BC34A BC35A BC41A BC42A BC43ABC BCA BCBC BC BC DA05 FA01 FB15 FC08 4G140 EA03 EA06 EB18 EB43 EB44 EC02 EC04 EC05

Claims (4)

[Claims] 1. A method for producing a hydrogen-containing gas by reacting a hydrocarbon and steam in a reactor in the presence of a reforming catalyst, wherein the steam / carbon ratio at the reactor inlet is 1.3. ~ 2.5
The temperature at the outlet of the reactor is 750 to 950 ° C., the pressure is 5 to 40 kg / cm ² , and the reforming catalyst is a composite oxide having a composition represented by the following formula: And at least one of Ni and Ni is highly dispersed in the composite oxide. aM · bCo · cNi · dMg · eCa · fO (where a, b, c, d, and e are mole fractions and a + b
+ C + d + e = 1, 0 ≦ a ≦ 0.1, 0.001 ≦
(B + c) ≦ 0.3, 0 ≦ b ≦ 0.3, 0 ≦ c ≦ 0.
3,0.6 ≦ (d + e) ≦ 0.999,0 <d ≦ 0.9
99,0 ≦ e ≦ 0.999, f = the number of elements required to maintain charge balance with oxygen, M excluding Group 6A element, Group 7A element, Co and / or Ni 8th
It is at least one kind of group transition element, group 1B element, group 2B element, group 4B element, and lanthanoid element. ) 2. When the hydrocarbon is a heavy hydrocarbon having 3 to 8 carbon atoms, a preliminary reforming step is provided in a preceding stage to convert the heavy hydrocarbon into a light hydrocarbon having 2 or less carbon atoms in advance. Convert
The method for producing hydrogen according to claim 1, wherein the hydrogen is sent to a reactor. 3. The method according to claim 1, wherein the hydrogen-containing gas discharged from the reactor is sent to a hydrogen separation step to concentrate the hydrogen, and the off-gas discharged from the hydrogen separation step is used as a heat source for the reaction. The method for producing hydrogen described in 1. 4. The method according to claim 1, wherein heat of the hydrogen-containing gas led out of the reactor is recovered, steam is generated by the heat, and the steam is sent to the reactor. Manufacturing method.