JP2015131768A - Production method of hydrocarbon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of hydrocarbons by Fisher-Tropsch reaction in which the yield of hydrocarbons having the carbon number of 5 or larger and 20 or smaller generating a liquid fuel component by one-step reaction using an inexpensive catalyst.SOLUTION: In a production method of hydrocarbons having the carbon number of 5 or larger and 20 or smaller, which is a method for producing hydrocarbons from hydrogen and carbon monoxide in the presence of a catalyst, the catalyst is a Fisher-Tropsch catalyst and a catalyst composition containing β-type zeolite having the average particle diameter of 0.05 μm or larger and 0.20 μm or smaller.

Description

  The present invention relates to a method for producing hydrocarbons by Fischer-Tropsch reaction. More specifically, the present invention relates to a method for producing hydrocarbons by a Fischer-Tropsch reaction using a solid acid catalyst and a Fischer-Tropsch catalyst.

As a method for producing hydrocarbons, a Fischer-Tropsch reaction using hydrogen and carbon monoxide as raw materials has been proposed. In particular, in order to obtain a hydrocarbon having a high industrial utility value, such as butane, decane, didecane, etc., a method for producing a hydrocarbon that performs a Fischer-Tropsch reaction using a solid acid catalyst and a Fischer-Tropsch catalyst Is being considered.
Patent Document 1 discloses a method for producing lower isoparaffin by a two-stage reaction using Fischer-Tropsch reaction. In this method, the first-stage reaction for synthesizing straight chain hydrocarbons from synthesis gas using a Fischer-Tropsch catalyst, and the synthesis of lower isoparaffins having 4 to 6 carbon atoms from straight chain hydrocarbons obtained using a solid acid catalyst. This was a production method comprising a second-stage reaction.

On the other hand, Patent Document 2 discloses a method for producing a liquid fuel by a one-stage reaction process using a Fischer-Tropsch reaction. Patent Document 2 shows that the use of a capsule catalyst in which the surface of a Fischer-Tropsch catalyst is coated with beta zeolite improves the decrease in selectivity of isoparaffin and the like, which is a problem of one-step reaction.
In Patent Document 3, by using a Fischer-Tropsch catalyst using ZSM-12 zeolite supporting cobalt, a hydrocarbon having 5 to 20 carbon atoms can be obtained by a one-step reaction, and solid wax is used. A method is disclosed in which a free product is obtained.

JP 2001-288123 A Japanese Patent No. 2007-197628 JP2013-511591A

The production method described in Patent Document 1 was a production method based on a two-stage reaction. Since such a manufacturing method requires a large manufacturing facility, costs such as manufacturing cost and facility management are likely to be higher than those of a one-step reaction. The production methods of Patent Documents 2 and 3 are both production methods by a one-step reaction. However, in the production method described in Patent Document 2, a catalyst using aluminum isopropoxide is essential, and in the production method described in Patent Document 3, a special organic mineralizer (methyltriethylammonium chloride + 1,6-bis (2 , 3-dimethylimidazolium) hexabromide salt) is essential. Since these catalysts require these very expensive reagents, the catalyst costs are high. The production method using these high-cost catalysts is not preferable for production on an industrial scale involving catalyst exchange or for long-term production.
The present invention provides a method for producing hydrocarbons by Fischer-Tropsch reaction, in which the yield of hydrocarbons having 5 to 20 carbon atoms, which is a liquid fuel component, is higher than before by a one-step reaction using an inexpensive catalyst. The purpose is to do.

The present inventors have studied a method for producing hydrocarbons by Fischer-Tropsch reaction and hydrocarbon reforming reaction in the presence of a solid acid catalyst and a Fischer-Tropsch catalyst. As a result, by using a Fischer-Tropsch catalyst and a zeolite whose particle size is controlled as a solid acid catalyst, hydrocarbons as light fuel components, kerosene components, and gasoline components as liquid fuel components can be obtained in high yield. As a result, the present invention has been completed.
That is, the present invention is a method for producing hydrocarbons from hydrogen and carbon monoxide in the presence of a catalyst, wherein the catalyst is a Fischer-Tropsch catalyst and an average particle size of 0.05 μm or more and 0.20 μm or less β A method for producing a hydrocarbon having 5 or more and 20 or less carbon atoms, characterized in that it is a catalyst composition containing type zeolite.

The present invention provides a method for producing hydrocarbons by Fischer-Tropsch reaction in which the yield of hydrocarbons having 5 to 20 carbon atoms, which is a liquid fuel component, is higher than before by a one-step reaction using an inexpensive catalyst. can do.
In the present invention, the liquid fuel component can be obtained by a one-step reaction. Therefore, since the process of the manufacturing method of the present invention can be simplified, the manufacturing equipment and the manufacturing process can be simplified as compared with the two-stage reaction, and an economical process can be provided.
In addition, since the production method of the present invention uses an inexpensive catalyst, it is more suitable for industrial use than the FT reaction using a special catalyst.
Furthermore, since the liquid fuel component can be obtained in a high yield with an inexpensive catalyst, the production method of the present invention is suitable for production over a long period of time or production of a liquid fuel component on an industrial scale.

Hereinafter, the production method of the present invention will be described.
The production method of the present invention is a production method for producing hydrocarbons from hydrogen (H ₂ ) and carbon monoxide (CO) in the presence of a catalyst, so-called Fischer-Tropsch process (hereinafter referred to as “FT reaction”). )).

In the case of producing hydrocarbons in the production method of the present invention, a gas containing hydrogen and carbon monoxide (hereinafter referred to as “source gas”) may be brought into contact with the catalyst. The source gas may be a gas mainly composed of hydrogen and carbon monoxide, and if the total amount of hydrogen and carbon monoxide in the source gas is 50 mol% or more, further 70 mol% or more, and further 90 mol% or more. Alternatively, it may be a gas substantially composed of hydrogen and carbon monoxide (that is, a gas containing 100 mol% of hydrogen and carbon monoxide). As components other than hydrogen and carbon monoxide contained in the raw material gas, any one or more components contained in the group of nitrogen, carbon dioxide, water and methane, and nitrogen can be exemplified. Specific examples of the raw material gas include gas obtained by steam reforming or partial oxidation of any one selected from the group consisting of natural gas, coal, biomass, organic waste, heavy oil, and residual oil.
The ratio of hydrogen and carbon monoxide in the raw material gas is arbitrary, but the molar ratio of hydrogen to carbon monoxide (hereinafter referred to as “H ₂ / CO ratio”) is 0.4 or more and 4.0 or less. Furthermore, 1.5 or more and 2.5 or less can be illustrated.

  The catalyst in the production method of the present invention is a catalyst composition containing a Fischer-Tropsch catalyst and a β-type zeolite having an average particle size of 0.05 μm or more and 0.20 μm or less. By using such a catalyst composition, it is considered that the FT reaction and the reforming reaction of the hydrocarbon obtained by the FT reaction proceed simultaneously and in a balanced manner. As a result, the yield of hydrocarbons having 5 to 20 carbon atoms (hereinafter referred to as “liquid fuel component”) is higher than in the conventional method for producing hydrocarbons by FT reaction in the presence of a solid acid catalyst. Become.

  The Fischer-Tropsch catalyst (hereinafter referred to as “FT catalyst”) may be any catalyst having catalytic ability to convert the raw material gas into hydrocarbon. As such an FT catalyst, a catalyst containing at least one metal or compound consisting of the group of ruthenium (Ru), cobalt (Co) and iron (Fe), preferably at least one metal or compound of ruthenium or cobalt is used. And a catalyst in which these are supported on a carrier. Examples of the carrier include one or more selected from the group consisting of silica, alumina, titania, zirconia, and a carbon material.

  β-type zeolite is a zeolite having a structure of * BEA type according to a structure code defined by the International Zeolite Society. The β-type zeolite in the production method of the present invention may be * BEA-type zeolite, and may be at least one selected from the group of β-type aluminosilicate, β-type ferrosilicate, and β-type ferroaluminosilicate. , Β-type aluminosilicate or β-type ferrosilicate is preferable, and β-type aluminosilicate is more preferable.

The average particle size of β-type zeolite is 0.05 μm or more and 0.2 μm or less. When the average particle size is less than 0.05 μm, the operability (handling property) is lowered, for example, the aggregation of primary particles becomes strong. In addition to this, the production cost tends to be high, for example, a large amount of organic structure directing agent is required for the production of β-type zeolite. On the other hand, β-type zeolite having an average particle size of more than 0.2 μm has a low yield of liquid fuel component when used as a catalyst composition.
From the viewpoint of improving the yield and operability of the liquid fuel component, the average particle size of the β-type zeolite is preferably 0.05 μm or more and 0.15 μm or less, and 0.05 μm or more and 0.12 μm or less. Is more preferably 0.07 μm or more and 0.1 μm or less.

In the present invention, the average particle diameter is a value obtained by measuring the diameters of 10 or more primary particles randomly extracted by observation with a scanning electron microscope (hereinafter referred to as “SEM”) and averaging the diameters. Here, the primary particles in the present invention are particles of an independent minimum unit observed in SEM observation. Therefore, the secondary particle diameter, which is the diameter of the secondary particles in which the primary particles are aggregated, and the aggregate diameter, which is the diameter of the molded particles obtained by press-molding the primary particles or the secondary particles, are different from the average particle diameter.
As long as the β-type zeolite has the above average particle diameter, the composition thereof is arbitrary. Examples of the composition of β-type zeolite include a molar ratio of SiO ₂ to X ₂ O ₃ (hereinafter referred to as “SiO ₂ / X ₂ O ₃ ratio”) of 20 or more and 200 or less. Since β-type zeolite has a high acid amount and is easily obtained industrially, the SiO ₂ / X ₂ O ₃ ratio is preferably 25 or more and 50 or less, more preferably 30 or more and 45 or less. .

“X” in the SiO ₂ / X ₂ O ₃ ratio is a metal other than Si contained in the zeolite skeleton. For example, the SiO ₂ / X ₂ O ₃ ratio when the β-type zeolite is β-type aluminosilicate is the SiO ₂ / Al ₂ O ₃ ratio, and the SiO ₂ / X when the β-type zeolite is the β-type ferrosilicate. _{The 2} O ₃ ratio is the SiO ₂ / Fe ₂ O ₃ ratio, and the SiO ₂ / X ₂ O ₃ ratio when the β-type zeolite is β-type ferroaluminosilicate is SiO ₂ / (Fe, Al) ₂ O ₃ ratio.

The cation type of β-type zeolite is monovalent cation such as ammonia (NH ₄ ⁺ ) type or proton (H ⁺ ) type, divalent cation such as calcium (Ca ²⁺ ) type, manganese (Mn ²⁺ ) type, or iron ( Any cation type of trivalent cations such as Fe ³⁺ ) and lanthanum (La ³⁺ ) types may be used. It is preferable that the cation type of the β-type zeolite is a proton type because the acid strength becomes high and the production cost becomes lower.

The catalyst composition contains the above FT catalyst and β-type zeolite. The ratio of the FT catalyst to the β-type zeolite contained in the catalyst composition can be 10 wt% or more and 70 wt% or less, and preferably 15 wt% or more and 60 wt% or less. When the amount of the β-type zeolite and the FT catalyst in the catalyst composition is the above ratio, the yield of the liquid fuel component tends to increase.
Although the shape of the catalyst composition is arbitrary, for example, a powdered catalyst composition obtained by mixing a powdery FT catalyst and β-type zeolite can be mentioned. Furthermore, a catalyst composition molded body in which a mixture of an FT catalyst and a β-type zeolite is molded, and a catalyst molded body composition in which a molded body of an FT catalyst and a molded body of β-type zeolite are mixed. In addition, the catalyst composition molded body and the catalyst molded body composition can also be exemplified by arbitrary shapes such as a columnar shape, a pellet shape, a spherical shape, and a substantially spherical shape. Further, the catalyst composition molded body and the catalyst molded body composition may have an aggregate diameter of 0.5 mm or more and 10 mm or less.

  In the production method of the present invention, the raw material gas is brought into contact with the catalyst composition. Thereby, the yield of a liquid fuel component becomes high. The temperature at which the source gas is brought into contact with the catalyst composition can be 200 ° C. or higher and 300 ° C. or higher. Moreover, the pressure which makes source gas and a catalyst composition contact can mention 0.5 Mpa or more and 5 Mpa or less.

  The following examples illustrate the invention. However, the present invention is not limited to these examples. Each evaluation method is as follows.

(Average particle size)
SEM observation was performed using a general SEM (trade name: JSM-6390LV, manufactured by JEOL Ltd.). Ten or more primary particles were randomly selected from the obtained SEM observation drawing, and the maximum diameter in the fixed direction (Krummmbein diameter) was measured. The obtained maximum unidirectional diameter was averaged to obtain an average particle diameter.

(Manufacture of hydrocarbons)
The catalyst composition was placed in a reaction tube having a diameter of 12 mm. The catalyst composition was reduced by flowing hydrogen through the reaction tube at 0.2 MPa and 230 ° C. for 8 hours. After the reduction treatment, a raw material gas was passed through the catalyst composition at 260 ° C. to obtain a product gas.
Gas chromatography was used to measure carbon monoxide, methane, and liquid fuel components in the product gas. Measurement was performed on the product gas 48 hours after and 72 hours after the flow of the raw material gas, and carbon monoxide, methane, and liquid fuel components in the product gas were quantified with the average value of the measured values of both hours.

The conversion rate of carbon monoxide was determined from the amount of carbon monoxide in the raw material gas and the amount of carbon monoxide in the product gas. The ratio of the number of carbon atoms of methane or liquid fuel component in the product gas to the number of carbon atoms in carbon monoxide in the raw material gas was determined and used as each yield.
One of the following mixed gases was used as the raw material gas.
Source gas A: 60 mol% hydrogen
Carbon monoxide 30mol%
Nitrogen 10 mol%
Source gas B: Hydrogen 50 mol%
Carbon monoxide 25mol%
Nitrogen 25 mol%

Example 1
Precipitated silica, aluminum hydroxide, and 5 wt% tetraethylammonium hydroxide (hereinafter referred to as “TEAOH”) aqueous solution are mixed at 150 ° C. for 5 hours to form a solution having the following composition (hereinafter referred to as “TEA solution”). "). In addition, the ratio of each component in the following compositions is a molar ratio.
SiO ₂ / Al ₂ O ₃ = 50
H ₂ O / SiO ₂ = 6.5
TEAOH / SiO ₂ = 0.40
The TEA solution contained particles having a mode particle diameter of 0.01 to 0.2 μm, exhibited a highly transparent brown color, and was a highly viscous liquid.
An amorphous silica alumina gel having a SiO ₂ / Al ₂ O ₃ ratio of 48, a 35% by weight TEAOH aqueous solution, a 48% sodium hydroxide solution, pure water, and a TEA solution were mixed so as to have the following composition to obtain a reaction solution. Obtained. In addition, the ratio of each component in the following compositions is a molar ratio.
SiO ₂ / Al ₂ O ₃ = 48
H ₂ O / SiO ₂ = 10
TEA / SiO ₂ = 0.13
Na / SiO ₂ = 0.10
OH / SiO ₂ = 0.23

The reaction solution was hydrothermally treated in an autoclave at 150 ° C. for 50 hours, and then heat was released to room temperature to obtain a crystallized product. The crystallized product was washed with pure water, mixed with a 10% aqueous ammonium chloride solution, and washed again with pure water. The crystallized product after washing was dried at 110 ° C. in air and then calcined at 600 ° C. in air to obtain zeolite.
The obtained zeolite was a β-type zeolite having a carbon content of 0.3% by weight or less, a SiO ₂ / Al ₂ O ₃ ratio of 41, an average particle size of 0.09 μm, and an ion type of proton type.
The β-type zeolite was pressure-molded and pulverized to obtain a pellet-shaped β-type zeolite molded body having an average particle diameter of 0.09 μm and an aggregate diameter of 0.5 to 1.5 mm.

Next, an FT catalyst was synthesized. γ-Al ₂ O ₃ was used as a carrier, and 5% by weight of manganese was supported with respect to the weight of the carrier. The manganese-supported carrier is dried at 100 ° C. and then calcined at 600 ° C. for 5 hours to obtain 5 wt% Mn-supported γ-Al ₂ O ₃ (hereinafter referred to as “5% Mn / γ-Al ₂ O ₃ ”). .) Next, 3% by weight of ruthenium was supported with respect to the weight of 5% Mn / γ-Al ₂ O ₃ . 5% Mn / γ-Al ₂ O ₃ after supporting ruthenium is dried and then baked at 300 ° C. for 5 hours to form γ-Al ₂ O ₃ supporting 3% by weight of ruthenium and 5% by weight of manganese. A ruthenium-based FT catalyst was obtained. The obtained FT catalyst was used for FT reaction after hydrogen reduction treatment.
The FT catalyst was pressure-molded and pulverized to obtain a pellet-shaped FT catalyst molded body having an aggregate diameter of 0.5 to 1.5 mm.
The β-type zeolite molded body and the FT catalyst molded body were mixed so that the FT catalyst was 25% by weight with respect to the weight of the β-type zeolite to obtain a catalyst composition.
Using the obtained catalyst composition molded body, a mixed gas A was used as a raw material gas, and a reaction pressure was 1 MPa to produce hydrocarbons. The evaluation results are shown in Table 1.

Example 2
A catalyst composition was obtained in the same manner as in Example 1. Hydrocarbons were produced in the same manner as in Example 1 except that the obtained catalyst composition was used and the reaction pressure was 2 MPa. The results are shown in Table 1.

Example 3
A catalyst composition was obtained in the same manner as in Example 1. Hydrocarbons were produced in the same manner as in Example 1 except that the obtained catalyst composition was used, the mixed gas B was used instead of the mixed gas A, and the reaction pressure was 5 MPa. It was. The results are shown in Table 1.

Example 4
In the same manner as in Example 1, an FT catalyst and β-type zeolite having an average particle size of 0.09 μm were obtained in powder form. β-zeolite and FT catalyst were mixed so that the FT catalyst with respect to β-type zeolite was 25% by weight to obtain a powdery catalyst composition. The obtained catalyst composition was pressure-molded and pulverized to obtain a pellet-shaped catalyst composition having an aggregate diameter of 0.5 to 1.5 mm.
A hydrocarbon was produced in the same manner as in Example 1 except that the obtained catalyst composition was used and the reaction pressure was 2 MPa. The results are shown in Table 1.

Example 5
A catalyst composition was obtained in the same manner as in Example 1 except that the FT catalyst with respect to β-type zeolite was mixed so as to be 50% by weight.
A hydrocarbon was produced in the same manner as in Example 1 except that the obtained catalyst composition was used. The results are shown in Table 1.

Example 6
A catalyst composition was obtained in the same manner as in Example 1 except that the amount of FT catalyst relative to β-type zeolite was 17% by weight.
A hydrocarbon was produced in the same manner as in Example 1 except that the obtained catalyst composition was used. The results are shown in Table 1.

Example 7
No. 3 sodium silicate (SiO ₂ ; 30%, Na ₂ O; 9.1%, Al ₂ O ₃ ; 0.01%), 98% sulfuric acid, pure water and iron nitrate nonahydrate were mixed to form a gel. Obtained. The resulting gel, 35% TEAOH aqueous solution, 48% sodium hydroxide aqueous solution, and pure water were mixed by stirring to obtain a reaction mixture.
The composition of the resulting reaction _{mixture, SiO 2: 0.015Fe 2 O 3} : 0.00033Al 2 O 3: 0.18Na 2 O: 0.15TEAOH: was 10H ₂ O.
The reaction mixture was sealed in a stainless steel autoclave. A crystallized product was obtained by heating at 150 ° C. for 90 hours while rotating the autoclave. The obtained crystallized product was calcined in air at 600 ° C., mixed with 200 mL of 0.1N hydrochloric acid at 80 ° C., and stirred for 2 hours. After stirring, it was washed and dried to obtain β-type ferrosilicate. In the β-type ferrosilicate, SiO ₂ / Fe ₂ O ₃ was 37, the cation type was proton type, and the average particle size was 0.10 μm.
The β-type ferrosilicate molded in the same manner as in Example 1 is pressure-molded and pulverized, and the pellet-shaped β-type ferrosilicate molded product has an average particle size of 0.10 μm and an aggregated size of 0.5 to 1.5 mm. It was.
A catalyst composition was obtained in the same manner as in Example 1 except that the β-type ferrosilicate molded body was used. A hydrocarbon was produced in the same manner as in Example 1 except that the obtained catalyst composition was used. The results are shown in Table 1.

Example 8
A β-type zeolite compact was obtained in the same manner as in Example 1.
Spherical silica (hereinafter referred to as “Q30”) was used as a carrier, and 20% by weight of cobalt was supported on the weight of the carrier. The cobalt-supported Q30 was dried at 100 ° C. and then calcined at 600 ° C. for 5 hours to obtain a cobalt-based FT catalyst comprising Q30 supporting 20 wt% cobalt. The obtained FT catalyst was used for FT reaction after hydrogen reduction treatment.
The FT catalyst was pressure-molded and pulverized to obtain a pellet-shaped FT catalyst molded body having an aggregate diameter of 0.5 to 1.5 mm.
A catalyst composition was obtained in the same manner as in Example 1 except that the β-type zeolite compact and the FT catalyst were used. A hydrocarbon was produced in the same manner as in Example 1 except that the obtained catalyst composition was used. The results are shown in Table 1.

Comparative Example 1
As a solid acid catalyst, a proton type β-type zeolite having a carbon content of 0.3% by weight or less, a SiO ₂ / Al ₂ O ₃ ratio of 39, and an average particle diameter of 0.5 μm (trade name: HSZ-941HOA, Tosoh Corporation A catalyst composition was obtained in the same manner as in Example 1 except that the product manufactured by the company was used.
A hydrocarbon was produced in the same manner as in Example 1 except that the obtained catalyst composition was used. The results are shown in Table 1.

Comparative Example 2
As a solid acid catalyst, a ZSM-5 zeolite having a carbon content of 0.3% by weight or less, a SiO ₂ / Al ₂ O ₃ ratio of 40, a cation type of proton type, and an average particle size of 3 μm (trade name: HSZ-840HOA) The catalyst composition was obtained by the same method as Example 1 except having used Tosoh Corporation.
A hydrocarbon was produced in the same manner as in Example 1 except that the obtained catalyst composition was used. The results are shown in Table 1.

Comparative Example 3
A catalyst composition was obtained in the same manner as in Example 1 except that γ-alumina having an average particle size of 2 to 3 μm was used instead of β-type zeolite.
A hydrocarbon was produced in the same manner as in Example 1 except that the obtained catalyst composition was used. The results are shown in Table 1.

From these examples, in the production method of the present invention, the yield of the liquid fuel component exceeds 45%, more than 50%, and even more than 60%, and the production method using only the FT catalyst It can be seen that it has a higher yield of liquid fuel components. Furthermore, it can be seen that the yield of methane is 6% or less, and lower hydrocarbons are difficult to produce.
On the other hand, even in the case of β-type zeolite, in Comparative Example 1 in which an average particle size exceeding the method of the present invention was used as a solid acid catalyst, the yield of methane was higher than that in Examples, and liquid fuel was used. The component yield was low. In addition to this, the conversion of carbon monoxide was shown to be low.

  The present invention can be used as a hydrocarbon production process as a Fischer-Tropsch reaction to obtain liquid fuel components with higher yield / selectivity.

Claims (4)

  A method for producing hydrocarbons from hydrogen and carbon monoxide in the presence of a catalyst, the catalyst comprising a Fischer-Tropsch catalyst and a β-type zeolite having an average particle size of 0.05 μm or more and 0.20 μm or less A method for producing a hydrocarbon having 5 to 20 carbon atoms, which is a composition.   The production method according to claim 1, wherein the ratio of the Fischer-Tropsch catalyst to the β-type zeolite contained in the catalyst composition is 10 wt% or more and 70 wt% or less.   The production method according to claim 1 or 2, wherein the β-type zeolite is at least one selected from the group of β-type aluminosilicate, β-type ferrosilicate, and β-type ferroaluminosilicate.   The production method according to any one of claims 1 to 3, wherein the Fischer-Tropsch catalyst is a catalyst containing at least one metal or compound made of ruthenium, cobalt, and iron.