JPH11106770A - Method and apparatus for power generation with dimethyl ether modification gas - Google Patents

Abstract

PROBLEM TO BE SOLVED: To generate power at a high efficiency by using, as a motor fuel, a hydrogen gas or a synthetic gas obtd. by the catalytic modification of dimethyl ether with steam or a carbon dixide gas. SOLUTION: Examples of a catalyst used for the modification reaction of dimethyl ether are copper catalysts [e.g. metal copper, copper (I) oxide, or copper (II) oxide], iron catalysts [e.g. metal iron, iron (II) oxide, or iron (III) oxide], cobalt catalysts [e.g. metal cobalt, cobalt (II) oxide, or cobalt (III) oxide], and palladium catalysts each comprising palladium carried by a metal, oxide having a basic group. Based on 1 mol of dimethyl ether, 1-20 mol, pref. 1-10 mol, of steam or 0.8-2.0 mol, pref. 0.9-1.5 mol, of carbon dioxide is used; and when both steam and carbon dioxide are used, their total amt. is 1-10 mol, pref. 1-5 mol. The reaction is conducted pref. at 250-450 deg.C under a pressure of from normal pressure to 10 kg/cm<2> .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for generating electricity by reforming dimethyl ether to obtain synthesis gas or hydrogen gas, and using this gas as fuel for a motor.

[0002]

2. Description of the Related Art Heretofore, several methods for generating power using dimethyl ether have been known.

For example, JP-A-2-9833 and JP-A-3-52835 disclose that dimethyl ether and methanol are produced together from syngas and stored, and this is stored in a combined gasification combined cycle power plant, and natural gas is produced. A power generation method used at the peak of power generation is disclosed.

[0004] On the other hand, a power generation method using a methanol reformed gas is known. In this method, synthesis gas or hydrogen gas used as a fuel for power generation is obtained by reforming or decomposing methanol.

[0005] In the methanol reforming power generation method, there has been proposed a method of increasing the heat by utilizing the exhaust gas or combustion exhaust gas of a power generation turbine in the reforming or decomposition reaction which is an endothermic reaction. For example, Japanese Unexamined Patent Publication (Kokai) No. 62-132701 discloses that in a methanol decomposition apparatus for producing a synthesis gas from methanol and water, the combustion exhaust gas of a heating medium heating furnace for supplying heat necessary for the progress of the reaction and the evaporative heating of the raw material gas is disclosed. There is disclosed a heat recovery method that utilizes heat for heating a raw material.

[0006]

However, in the power generation methods disclosed in JP-A-2-9833 and JP-A-3-52835, there is no description about a specific power generation method.

In the methanol reforming power generation method, the efficiency of power generation is improved by increasing the temperature of the raw material methanol by using the exhaust heat of the turbine for power generation and the waste heat of the combustion exhaust gas in reforming or decomposing the raw material methanol. However, the amounts of heat that can be recovered by the steam reforming reaction of methanol and the decomposition reaction of methanol are not necessarily large as shown by the equations (1) and (2), respectively. CH ₃ OH + H ₂ O → CO ₂ + 3H ₂ −11.8 kcal / mol (1) CH ₃ OH → CO + 2H ₂ −21.7 kcal / mol (2)

[0008] Further, methanol has toxicity, so that there is a problem in that it requires careful handling.

An object of the present invention is to solve the above-mentioned conventional problems and to provide a highly efficient power generation method.

[0010]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, a method for obtaining a synthesis gas or a hydrogen gas by reforming dimethyl ether, which has been previously developed by the present inventors. And came up with a method of generating electricity by using this gas as fuel for a motor.

That is, the present invention is characterized in that dimethyl ether is reformed by adding steam or carbon dioxide gas to the dimethyl ether to cause a catalytic reaction, thereby obtaining a synthesis gas or a hydrogen gas, and using this gas as a fuel for a motor. A power generation method using a dimethyl ether reformed gas, the above-mentioned power generation method characterized in that dimethyl ether is reformed by using medium to low temperature waste heat at 200 to 500 ° C., and dimethyl ether and steam or carbon dioxide gas. Power generation having a reforming reactor filled with a catalyst that reacts to produce synthesis gas or hydrogen gas, a combustor that burns the synthesis gas or hydrogen gas, and a gas turbine that is rotated by combustion exhaust gas generated in the combustor The present invention is to provide a power generation device including a power generator.

The reforming reaction of dimethyl ether according to the present invention has a large amount of heat in the endothermic reaction as shown in the following formulas (3) to (5). , 1.5 to 2.5 times the waste heat recovery, and the amount of heat during combustion of the reformed gas increases accordingly. CH ₃ OCH ₃ + H ₂ O → 2CO + 4H ₂ −48.9 kcal / mol (3) CH ₃ OCH ₃ + 3H ₂ O → 2CO ₂ + 6H ₂ −29.3 kcal / mol (4) CH ₃ OCH ₃ + CO ₂ → 3CO + 3H ₂ − 58.8 kcal / mol (5)

For example, 1 Nm ³ of dimethyl ether having a total calorific value of 15,580 kcal / Nm ³ is converted into (3)
When steam reforming according to the equation, obtained synthesis gas 6 Nm ³ consisting of hydrogen carbon monoxide and 4 Nm ³ of 2 Nm ^3, the synthesis gas gross heating value 18,240kcal, and the increasing amount of heat is 2,660Kcal, The rate of heat increase (value obtained by dividing the amount of heat increase by the total heat value of dimethyl ether and multiplying by 100) is calculated as 17.1%. On the other hand, in the methanol reforming reaction, when 1Nm ³ methanol vapor having a total calorific value of 8,150 kcal / Nm ³ is decomposed according to, for example, the formula (2), 1Nm ³ of carbon monoxide and 2N
3Nm ³ of synthesis gas consisting of m ³ of hydrogen was obtained, the total calorific value of the syngas was 9,120 kcal, the amount of heat increase was 970 kcal, and the rate of heat increase (the amount of heat increase was divided by the total heat amount of methanol vapor). 100 times) is 11.9%
Is calculated.

In addition, dimethyl ether has already been used as a propellant for spraying, and it has been confirmed that dimethyl ether has extremely low toxicity as compared with methanol.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention comprises reforming of dimethyl ether and power generation using the obtained reformed gas.

Catalysts for reforming dimethyl ether to generate synthesis gas or hydrogen gas include copper catalysts, iron catalysts, cobalt catalysts and palladium catalysts developed by the present inventors.

The copper-based catalyst contains a copper metal and / or compound. The copper compound is preferably a copper oxide, and the copper oxide is cuprous oxide (Cu ₂ O), cupric oxide (CuO), or a mixture thereof.

The iron-based catalyst contains an iron metal and / or compound. The iron compound is preferably an iron oxide, and the iron oxide is ferrous oxide (FeO), ferric oxide (Fe ₂ O ₃ ), or a mixture thereof.

The cobalt-based catalyst contains a metal and / or a compound of cobalt. The cobalt compound is preferably a cobalt oxide, and the cobalt oxide is cobaltous oxide (CoO), cobaltic oxide (Co ₂ O ₃ ), or a mixture thereof.

The copper-based catalyst, iron-based catalyst, and cobalt-based catalyst can be used by being supported on a catalyst carrier. Preferred catalyst supports are oxides such as alumina, silica gel, silica-alumina, zeolite, titania, zirconia, zinc oxide, tin oxide, lanthanum oxide, and cerium oxide.Alumina is particularly suitable for collecting synthesis gas and hydrogen gas. It is preferable because the rate is high. The content of copper in the copper-based catalyst is about 1 to 50% by weight, preferably 3 to 30% by weight.
The iron content in the iron-based catalyst is about 10 to 100% by weight, preferably 30 to 100% by weight. The content of cobalt in the cobalt-based catalyst is about 1 to 30% by weight, preferably 3 to 15% by weight. If the content is out of the above range, the yield of the synthesis gas or hydrogen decreases.

The catalyst of the present invention can use other metals or compounds in addition to iron metals and / or compounds. Examples of other metals and compounds include zinc, nickel, chromium, manganese, tin, cerium, lanthanum and their compounds for copper-based and iron-based catalysts, and for cobalt-based catalysts. , Nickel, iron and their compounds. Among them, in the case of an iron-based catalyst, oxides of zinc, nickel, chromium and manganese are particularly preferred. Preferred examples of the catalyst include a copper-based catalyst including a copper oxide-nickel monoxide-zinc oxide-alumina catalyst, an iron-based catalyst including an iron oxide-chromium oxide-alumina catalyst, and a cobalt-based catalyst including a cobalt-alumina catalyst. These metals and compounds may be used alone or in combination of two or more. The content of these third components is
70% by weight or less, especially 50% by weight in the case of a copper-based catalyst
The content is as follows, and when it is contained, it is usually about 1 to 30% by weight. In the case of an iron-based catalyst, the content is 50% by weight or less, particularly 30% by weight or less.
It is about 0% by weight. In the case of a cobalt-based catalyst, the content is 20% by weight or less, particularly 10% by weight or less, and when it is contained, it is usually about 1 to 5% by weight.

For the production of these catalysts, general methods for preparing such catalysts can be applied. For example, as a raw material for producing a catalyst, as a copper, iron or cobalt compound, an inorganic acid salt such as nitrate, carbonate or halide and an organic acid salt such as acetate or oxalate are used. For the operation of supporting copper, iron and cobalt on the catalyst carrier, techniques such as ordinary precipitation, kneading, impregnation and ion exchange can be used. The catalyst composition thus prepared is calcined by a conventional method, if necessary. The calcination is preferably performed by heating at 350 to 800 ° C. for 1 to 10 hours in nitrogen or air.

The palladium-based catalyst is obtained by supporting palladium on a basic metal oxide. Basic metal oxides include Li ₂ O, Na ₂ O, K ₂ O, and Rb ₂
Oxides of alkali metals such as O and Cs ₂ O, BeO, Mg
O, CaO, SrO, oxides of alkaline earth metals of BaO or the _{like, Y 2 O 3, La 2} O 3, oxides of rare earth elements such as CeO _{2, ZnO, SnO 2, ZrO 2} , Al 2 O 3, TiO ₂
And mixtures of two or more of the foregoing metal oxides. Preferred are palladium-zinc oxide catalysts, palladium-
Sodium oxide-alumina catalyst and the like. Further, the above-described basic metal oxide can be used in combination with another non-basic metal oxide, for example, silica gel, or another non-basic compound, for example, silicon carbide, activated carbon, or the like. . The loading rate of palladium is
It is about 0.1 to 30% by weight, preferably 0.2 to 20% by weight, based on the basic metal oxide. When the loading of palladium is less than about 0.1% by weight and 30% by weight or more, the yield of synthesis gas decreases.

The method for producing a palladium-based catalyst is characterized in that palladium is supported on a basic metal oxide and then treated with a basic aqueous solution. As a method for producing this catalyst, a basic metal oxide is charged into an aqueous solution containing a metal salt of palladium, for example, an aqueous solution containing palladium chloride, and evaporated to dryness, dried, and then calcined. The calcination is preferably performed by heating at 350 to 600 ° C. for 1 to 10 hours in nitrogen or air. This is then treated with a basic aqueous solution. Examples of the basic aqueous solution include aqueous solutions of hydroxides and carbonates of alkali metals and hydroxides of alkaline earth metals.
The concentration of these basic compounds is suitably about 0.5 to 20, usually about 1 to 10. The treatment is carried out by bringing a basic aqueous solution into contact with the catalyst and then removing the basic aqueous solution. This treatment is performed at a temperature between room temperature and 80 ° C.
It is preferably performed for 5 hours. After treatment with a basic aqueous solution, for example, a small amount of the above-mentioned basic compound (for example, 0.
(About 1 to 1.0).

The catalyst is subjected to an activation treatment at the final stage of the preparation, which is preferably carried out in a hydrogen atmosphere at a temperature of 350 to 600 ° C. for 1 to 10 hours.

By passing a mixed gas of dimethyl ether, steam and / or carbon dioxide through the catalyst thus prepared, a synthesis gas and / or a hydrogen gas can be obtained in high yield.

In the present invention, steam and / or carbon dioxide are supplied together with the raw material dimethyl ether. The steam to be supplied may be a stoichiometric amount or more with respect to the dimethyl ether as the raw material, and is 1 to 20 times by mole, preferably 1 to 20 times.
It is 10 mole times. If the supply of steam is less than 1 mole, a high dimethyl ether conversion cannot be obtained, and
It is not economical if it is more than mole times. The supplied carbon dioxide is 0.8 to 2.0 times, preferably 0.9 to 1.5 times, the molar amount of dimethyl ether as the raw material. If the supply of carbon dioxide is less than 0.8 mol times, a high conversion of dimethyl ether cannot be obtained, and if it is more than 2.0 mol times, a large amount of carbon dioxide remains in the synthesis gas, and the carbon dioxide is converted into synthesis gas. Is necessary, which is not preferable. When both steam and carbon dioxide are supplied, the sum of the steam and carbon dioxide is 1 to 10 times, preferably 1 to 5 times the molar amount of dimethyl ether.
If the sum of water vapor and carbon dioxide is less than 1 mole, a high dimethyl ether conversion cannot be obtained, and if it is more than 10 moles, it is not economical, and carbon dioxide must be removed from the synthesis gas, which is not preferable. This source gas contains
Components other than dimethyl ether, water vapor and carbon dioxide can also be included. Other reaction inert gas as a component, such as nitrogen, inert gas, CO, H _2, may include methane. The content of these is suitably not more than 30% by volume. If the content is more than 30% by volume, the reduction of the reaction rate becomes a problem. On the other hand, air (oxygen) burns dimethyl ether, so it is better to exclude it as much as possible, and the allowable content is 5% or less as air.

[0028] The reaction temperature is 200 to 500 ° C, preferably 250 to 450 ° C. If the reaction temperature is lower than 200 ° C., a high conversion of dimethyl ether cannot be obtained, and 50
If the temperature is higher than 0 ° C., the generation of hydrocarbons mainly composed of methanol, carbon monoxide or methane as by-products becomes remarkable, and the proportions of synthesis gas and hydrogen gas in the products are undesirably reduced.

In the method of the present invention, it is preferable that the reaction heat required for the dimethyl ether reforming reaction is provided by medium to low temperature waste heat of 200 to 500 ° C. generated in a steel mill or a power plant. For example, by using the sensible heat of a cooler exhaust gas generated in a sintering plant at a steel mill or by using the exhaust gas of a gas turbine at a power plant, the resulting reformed gas increases the calorific value corresponding to the calorific value of the reforming reaction. Can be expected. Moreover, the dimethyl ether reforming reaction proceeds at a temperature of 200 to 500 ° C. by being carried out in the presence of the above-mentioned catalyst, and is suitable for recovery of waste heat or exhaust gas at medium to low temperatures.

The reaction pressure is preferably normal pressure to 10 kg / cm ² . If the reaction pressure is higher than 10 kg / cm ² , the conversion of dimethyl ether decreases.

The space velocity (supply rate m ³ / h of the mixed gas in a standard state per m ^{3 of the} catalyst) is 1000 to 5
0000 m ³ / m ³ · h is preferred. Space velocity 5000
If it is greater than 0 m ³ / m ³ · h, the conversion of dimethyl ether is low, and if it is less than 1000 m ³ / m ³ · h, the reactor becomes extremely large and is not economical.

In the method of the present invention, a fixed bed,
Any apparatus of a fluidized bed may be used.

The reformed gas of dimethyl ether is a gaseous fuel mainly composed of hydrogen or hydrogen and carbon monoxide, and is used as a fuel for a power generating motor such as a gas turbine. As a combustion method, in addition to a normal combustion method, low-temperature combustion such as catalytic combustion or lean gas combustion is also possible. In this case, suppression of generation of nitrogen oxides can be expected.

The combustion conditions may be the same as in the conventional method using LNG or LPG.

[0035]

【Example】

Catalyst Example 1-4 copper nitrate _{(Cu (NO 3) 2 ·} 3H 2 O) 91g, zinc nitrate (Z
an aqueous solution in which 73 g of n (NO ₃ ) ₂ .6H ₂ O) and 368 g of aluminum nitrate (Al (NO ₃ ) ₃ .9H ₂ O) were dissolved in about 2 liters of ion-exchanged water, and sodium carbonate (Na ₂ C)
O ₃ ) An aqueous solution in which about 250 g is dissolved in about 2 liters of ion-exchanged water is placed in a stainless steel container containing about 5 liters of ion-exchanged water kept at about 80 ° C., and the pH is maintained at 8.0 ± 0.5. It dripped over about 2 hours, adjusting so that it might be.
After the completion of the dropping, the mixture was kept for about 1 hour for aging.
If the pH deviates from 8.0 ± 0.5 during this time, about 1 mol / l nitric acid aqueous solution or about 1 mol / l
1 sodium hydroxide solution was added dropwise to adjust the pH to 8.0 ±.
Adjusted to 0.5. Next, after filtering the formed precipitate,
Washing was performed using ion-exchanged water until no nitrate ion was detected in the washing solution. The obtained cake is heated at 120 ° C. for 24 hours.
After drying for an hour, it was further fired in air at 350 ° C. for 5 hours. Further, this was classified into 20 to 40 mesh to obtain a target catalyst.

The composition of the obtained catalyst is CuO: ZnO: A
l ₂ O ₃ = 30: 20: 50 (weight ratio).

Catalyst Examples 5 to 8 In the same manner as in Catalyst Examples 1 to 4, except that 105 g of chromium nitrate (Cr (NO ₃ ) ₂ .3H ₂ O) was used instead of zinc nitrate. A catalyst was prepared.

The composition of the obtained catalyst was CuO: Cr ₂ O ₃ :
Al ₂ O ₃ = 30: 20: 50 (weight ratio).

[Reaction Method] A predetermined amount of the above catalyst was filled in a stainless steel reaction tube having an inner diameter of 20 mm. A predetermined amount of dimethyl ether and carbon dioxide were supplied to the reaction tube and reacted at a predetermined temperature.

The reaction products and unreacted products obtained by the above operations were analyzed by gas chromatography.

[Reaction Conditions and Experimental Results] The reaction conditions and experimental results are shown in Tables 1 and 2.

[0042]

(Equation 1)

[0043]

(Equation 2) All units of each speed are [mol / g-cat · h]

[0044]

[Table 1]

[0045]

[Table 2]

Catalyst Examples 9 to 11 91 g of copper nitrate (Cu (NO ₃ ) ₂ .3H ₂ O), 39 g of nickel nitrate (Ni (NO ₃ ) ₂ .6H ₂ O), zinc nitrate (Zn
_{(NO 3) 2 · 6H 2} O) 37g and aluminum nitrate (A
_{l (NO 3) 3 · 9H} 2 O) 368g of ion-exchanged water of about 2l
And about 200 g of sodium hydroxide dissolved in about 2 liters of ion-exchanged water were placed in a stainless steel container containing about 5 liters of ion-exchanged water kept at about 60 ° C., and the pH was adjusted to 8.0 ±. The solution was added dropwise over about 1 hour while adjusting the temperature to be maintained at 0.5. After the completion of the dropping, the mixture was kept for about 1 hour for aging. If the pH deviates from 8.0 ± 0.5 during this time, about 1 mol /
1 nitric acid aqueous solution or about 1 mol / l sodium hydroxide aqueous solution was added dropwise to adjust the pH to 8.0 ± 0.5.
Next, the resulting precipitate was filtered and washed with ion-exchanged water until no nitrate ion was detected in the washing solution. After drying the obtained cake at 120 ° C. for 24 hours,
Furthermore, it baked at 350 degreeC in air for 5 hours. Further, this was classified into 20 to 40 mesh to obtain a target catalyst.

The composition of the obtained catalyst was CuO: NiO: Z
nO: Al ₂ O ₃ = 30: 10: 10: 50 (weight ratio).

Catalyst Example 12 A catalyst was prepared in the same manner as in Catalyst Examples 9 to 11, except that 53 g of chromium nitrate (Cr (NO ₃ ) ₂ .3H ₂ O) was used instead of nickel nitrate. Prepared.

The composition of the obtained catalyst was CuO: Cr ₂ O ₃ :
ZnO: Al ₂ O ₃ = 30: 10: 10: 50 (weight ratio)
Met.

Catalyst Example 13 A catalyst was prepared in the same manner as in Catalyst Examples 9 to 11, except that 33 g of manganese nitrate (Mn (NO ₃ ) ₂ .6H ₂ O) was used instead of nickel nitrate. Prepared.

The composition of the obtained catalyst was CuO: MnO ₂ :
ZnO: Al ₂ O ₃ = 30: 10: 10: 50 (weight ratio)
Met.

Catalyst Example 14 In the method of Catalyst Example 13, except that 53 g of chromium nitrate (Cr (NO ₃ ) ₂ .3H ₂ O) was used instead of zinc nitrate,
Catalysts were prepared in the same manner as in Catalyst Examples 9 to 11.

The composition of the obtained catalyst was CuO: Cr
₂ O ₃ : MnO ₂ : Al ₂ O ₃ = 30: 10: 10: 50
(Weight ratio).

[Reaction Method] A predetermined amount of the above catalyst was charged into a stainless steel reaction tube having an inner diameter of 20 mm. A predetermined amount of dimethyl ether and water vapor were supplied to the reaction tube and reacted at a predetermined temperature.

The reaction products and unreacted products obtained by the above operations were analyzed by gas chromatography.

[Reaction Conditions and Experimental Results] The reaction conditions and experimental results are shown in Tables 3 and 4.

[0057]

(Equation 3)

[0058]

(Equation 4)

[0059]

(Equation 5) All units of each speed are [mol / g-cat · h]

[0060]

[Table 3]

[0061]

[Table 4]

[0062] Catalyst Examples 15-17 ferric nitrate _{(Fe (NO 3) 3 ·} 9H 2 O) 405g, chromium nitrate _{(Cr (NO 3) 2 ·} 3H 2 O) 79g, and aluminum nitrate (Al (NO _{3) 3} 9H ₂ O) An aqueous solution in which 37 g was dissolved in about 2 liters of ion-exchanged water and an aqueous solution in which about 180 g of sodium hydroxide was dissolved in about 2 liters of ion-exchanged water were filled with about 5 liters of ion-exchanged water kept at about 80 ° C. The solution was dropped into a stainless steel container over about 1 hour while adjusting the pH to be maintained at 8.0 ± 0.5. After the completion of the dropping, the mixture was kept for about 1 hour for aging. If the pH deviates from 8.0 ± 0.5 during this time, about 1 mol / l nitric acid aqueous solution or about 1 mol / l
of sodium hydroxide solution was added dropwise to adjust the pH to 8.0.
Adjusted to ± 0.5. Next, the resulting precipitate was filtered and washed with ion-exchanged water until no nitrate ion was detected in the washing solution. After the obtained cake was dried at 120 ° C. for 24 hours, it was further baked at 350 ° C. in air for 5 hours. Further, this was classified into 20 to 40 mesh to obtain a target catalyst.

The composition of the obtained catalyst was Fe ₂ O ₃ : Cr
₂ O ₃ : Al ₂ O ₃ = 80: 15: 5 (weight ratio).

Catalyst Examples 18 to 20 In the same manner as in Catalyst Examples 15 to 17, except that 55 g of zinc nitrate (Zn (NO ₃ ) ₂ .6H ₂ O) was used instead of chromium nitrate, A catalyst was prepared.

The composition of the obtained catalyst was Fe ₂ O ₃ : ZnO:
Al ₂ O ₃ = 80: 15: 5 (weight ratio).

[Reaction method] A predetermined amount of the above catalyst was filled in a stainless steel reaction tube having an inner diameter of 20 mm. A predetermined amount of dimethyl ether and water vapor were supplied to the reaction tube and reacted at a predetermined temperature.

The reaction products and unreacted products obtained by the above operations were analyzed by gas chromatography.

[Reaction Conditions and Experimental Results] The reaction conditions and experimental results are shown in Tables 5 and 6.

[0069]

[Table 5]

[0070]

[Table 6]

Catalyst Examples 21-28 49.4 g of cobalt acetate (Co (NO ₃ ) ₂ .6H ₂ O) was dissolved in about 300 ml of ion-exchanged water, and 90 g of γ-alumina (Nikki Chemical, N612) was added to the aqueous solution. And evaporated to dryness. And put this in the air, 120
C. for 24 hours, and calcined in air at 500.degree. C. for 3 hours. Then, a treatment was performed at 500 ° C. for 3 hours in a hydrogen stream to obtain a catalyst.

The composition of the obtained catalyst was Co: Al ₂ O ₃ =
The ratio was 10:90 (weight ratio).

[Reaction Method] A predetermined amount of the above catalyst was charged into a stainless steel reaction tube having an inner diameter of 20 mm. A predetermined amount of dimethyl ether, steam and / or carbon dioxide was supplied to the reaction tube and reacted at a predetermined temperature.

The reaction products and unreacted products obtained by the above operations were analyzed by gas chromatography.

[Reaction Conditions and Experimental Results] The reaction conditions and experimental results are shown in Tables 7 and 8.

[0076]

(Equation 6) All units of each speed are [mol / g-cat · h]

[0077]

[Table 7]

[0078]

[Table 8]

Catalyst Examples 29 and 30 6 ml of hydrochloric acid and 8.3 of palladium chloride (PdCl ₂ )
100 g of zinc oxide (manufactured by Kanto Chemical Co., Ltd., reagent grade) was added to an aqueous solution in which 3 g was dissolved in about 500 ml of ion-exchanged water, and evaporated to dryness. This was dried in air at 120 ° C. for 24 hours and fired in air at 500 ° C. for 3 hours.
Then, this was put into an aqueous solution in which 10 g of sodium hydroxide was dissolved in about 1000 ml of ion-exchanged water, and 50 g of the solution was added.
After heating to about 1 hour and performing a treatment for about 1 hour, the substrate was washed until no chloride ion was detected, and dried at 120 ° C. for 24 hours. Furthermore, this is compression molded to 20 to 4
After sizing to 0 mesh, the mixture was treated in a hydrogen stream at 500 ° C. for 3 hours to obtain a catalyst.

The composition of the obtained catalyst was Pd: ZnO =
5: 100 (weight ratio).

Catalyst Examples 31 and 32 In the methods of Catalyst Examples 29 and 30, except that cerium oxide (manufactured by Kanto Chemical Co., Ltd., reagent grade) was used instead of zinc oxide.
Catalysts were prepared in the same manner as in Catalyst Examples 29 and 30.

The composition of the obtained catalyst was Pd: CeO ₂ =
5: 100 (weight ratio).

Catalyst Examples 33 and 34 6 ml of hydrochloric acid and 8.3 of palladium chloride (PdCl ₂ )
100 g of γ-alumina (manufactured by JGC Chemicals, N612) was added to an aqueous solution obtained by dissolving 3 g in about 500 ml of ion-exchanged water, evaporated to dryness, dried in air at 120 ° C. for 24 hours, and further dried in air. It was baked at 500 ° C. for 3 hours. Then, this was put into an aqueous solution in which 50 g of sodium hydroxide was dissolved in about 1000 ml of ion-exchanged water, heated to 50 ° C., and treated for about 1 hour. Dried. This was further sized by compression molding to 20 to 40 mesh, and then treated in a hydrogen stream at 500 ° C. for 3 hours to obtain a catalyst.

The composition of the obtained catalyst was Pd: Na ₂ O:
Al ₂ O ₃ = 5: 0.4: 100 (weight ratio).

Catalyst Examples 35 and 36 6 ml of hydrochloric acid and 8.3 of palladium chloride (PdCl ₂ )
Silica gel (Fuji Divison Chemical, ID) 100 was added to an aqueous solution in which 3 g was dissolved in about 500 ml of ion exchanged water.
g, and evaporated to dryness. This is 120 ° C in air
And calcined at 500 ° C. for 3 hours in the air. Then, this was put into an aqueous solution in which 10 g of calcium hydroxide was dissolved in about 1000 ml of ion-exchanged water, heated to 50 ° C., and treated for about 1 hour, followed by washing and drying. Further, about 80 g of this was put into an aqueous solution in which about 6.6 g of calcium hydroxide was dissolved in about 200 ml of ion-exchanged water, evaporated to dryness, and then dried. This was sized to 20 to 40 mesh by compression molding, and then treated in a hydrogen stream at 500 ° C. for 3 hours to obtain a catalyst.

The composition of the obtained catalyst was Pd: CaO: S
iO ₂ = 5: 5: 100 (weight ratio).

[Reaction Method] A predetermined amount of the above catalyst was charged into a stainless steel reaction tube having an inner diameter of 20 mm. A predetermined amount of dimethyl ether, steam and / or carbon dioxide was supplied to the reaction tube and reacted at a predetermined temperature.

The reaction products and unreacted products obtained by the above operations were analyzed by gas chromatography.

[Reaction Conditions and Experimental Results] The reaction conditions and experimental results are shown in Tables 9 and 10.

[0090]

[Table 9]

[0091]

[Table 10] Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG.
FIG. 1 is a system diagram showing an example of a power generation method using a dimethyl ether reformed gas of the present invention.

In the sinter cooler 1, the sinter is cooled by air, and the exhaust gas generated at this time at 200 to 500 ° C.
It is sent to a heat exchanger 2 for water heating, a heat exchanger 3 for raw material gas heating, and a heat exchanger 4 for heating medium heating. The heat medium heated by the exhaust gas sensible heat of the cooler of the sintering machine is sent to the dimethyl ether reforming reactor 5. In this apparatus, a mixed gas composed of dimethyl ether, steam and carbon dioxide gas preheated by exhaust gas from a sintering machine is introduced into a plurality of reaction tubes arranged inside a reformer. The inside of the reaction tube is filled with a dimethyl ether reforming catalyst, and a mixed gas of dimethyl ether, steam and carbon dioxide gas is brought into contact with the catalyst to generate a mixed gas of carbon monoxide and hydrogen. The internal temperature of the reforming reactor varies depending on the type of the catalyst to be charged, but is generally in a temperature range of 200 to 500C. The generated reformed gas contains a small amount of unreacted dimethyl ether, but dimethyl ether itself is a fuel gas having a large calorific value.Therefore, the reformed gas containing dimethyl ether is used as a fuel for a gas turbine combustor. No problem at all. The obtained reformed gas is sent to the combustor 6 and burns with the combustion air supplied from the compressor 7. Exhaust gas generated in the combustor is sent to the gas turbine 8 and rotates the generator 9 to generate power. The gas discharged from the gas turbine is sent to a gas turbine exhaust heat recovery boiler 10. The steam obtained from the gas turbine exhaust heat recovery boiler is used as a process steam in a steel mill (not shown).

Power Generation Examples 1 to 4 and Comparative Power Generation Examples Using a dimethyl ether reformed gas obtained by a predetermined catalyst example, a power generation test using a simple open gas turbine was performed.

[0094]

[Table 11]

[0095]

[Table 12]

[0096]

As described above, according to the present invention, dimethyl ether is reformed using waste heat, and the resulting reformed gas is configured to generate power as fuel for a motor. The medium to low temperature waste heat of 200 to 500 ° C., which has been used, can be effectively used, and the obtained reformed gas has a large rate of increase in heat, so that it has remarkable effects such as improvement in power generation efficiency.

[Brief description of the drawings]

FIG. 1 is a system diagram showing a general configuration of a prime mover power generation system according to the present invention.

[Explanation of symbols]

 Reference Signs List 1 Exhaust gas cooler of sintering machine 2, 3, 4 Heat exchanger 5 Reforming reactor 6 Combustor 7 Compressor 8 Gas turbine 9 Generator 10 Waste heat recovery boiler

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI B01J 23/80 C01B 3/38 23/889 F02C 7/22 D 23/86 B01J 23/56 M C01B 3/38 23/74 311M F02C 7/22 23/84 311M (72) Inventor Norio Inoue 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Inside Nihon Kokan Co., Ltd. (72) Inventor Kaoru Fujimoto 6-18-1, Minamioi, Shinagawa-ku, Tokyo −1031

Claims (3)

[Claims] 1. A dimethyl ether reforming method characterized in that dimethyl ether is reformed by adding water vapor or carbon dioxide gas to dimethyl ether to cause a catalytic reaction, thereby obtaining synthesis gas or hydrogen gas, and using this gas as a fuel for a motor. Power generation method using high quality gas 2. The modification of dimethyl ether is carried out from 200 to 5
The power generation method according to claim 1, wherein the heat generation is performed by using middle / low temperature waste heat of 00 ° C. 3. A reforming reactor filled with a catalyst for reacting dimethyl ether with steam or carbon dioxide to generate a synthesis gas or hydrogen gas, a combustor for burning the synthesis gas or hydrogen gas, and the combustor Generator consisting of a generator having a gas turbine rotated by the combustion exhaust gas generated in the plant