JPH0528278B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for producing liquid hydrocarbons, particularly gasoline fractions, in high yield from a mixed gas of hydrogen and carbon monoxide (hereinafter referred to as synthesis gas). (Prior Art) In recent years, there has been an urgent need to develop alternative products due to oil shortages, and as part of this effort, there has been a demand for producing useful hydrocarbons directly from synthesis gas. The Fischer-Tropschew (FT) process has long been known as a method for producing hydrocarbons using synthesis gas as a raw material. It is used. However, this method produces a relatively large amount of carbon dioxide gas as a by-product, has a low selectivity for hydrocarbons, and the resulting hydrocarbons have a very wide carbon number distribution, ranging from gaseous hydrocarbons to wax, and are useful as specific components. Alternatively, it is extremely difficult to selectively obtain hydrocarbons of specific boiling point fractions. Therefore, recently, zeolites have been utilized, by contacting the synthesis gas with carbon monoxide reduction catalysts (FT synthesis catalyst and methanol synthesis catalyst) and then contacting the product with the zeolite in a separate or the same reactor. Conversion methods have been investigated to selectively obtain liquid hydrocarbons, particularly gasoline fractions, from synthesis gas. This conversion method includes a two-stage conversion method in which these reactions are carried out in separate reactors, a method in which a specific zeolite is supported with a metal component active in reducing carbon monoxide, or a method in which a catalyst for reducing carbon monoxide is used. There is a one-step method using a mixed catalyst in which zeolite and a specific zeolite are physically mixed. The one-stage process simplifies the process and can be a more economical process compared to the two-stage process, but compared to the two-stage process, which allows the use of carbon monoxide reduction catalysts and zeolite catalysts under their respective optimal conditions. However, in the one-stage method, since the optimal operating conditions (especially reaction temperature and pressure) of both catalysts are different from each other, fully satisfactory results cannot be obtained in terms of reaction activity or the distribution or composition of the resulting hydrocarbon product. For example, a method for selectively producing a gasoline fraction in one stage using this type of catalyst containing ruthenium is disclosed in US Pat. No. 4,157,338.
No. 1986-19386, Japanese Patent Application Laid-open No. 127784-1984, and Japanese Patent Application Laid-open No. 192834-1983. (Problems to be Solved by the Invention) However, in U.S. Pat. Although the conversion rate of carbon oxide or the selectivity for the production of hydrocarbons with a carbon number of 5 or more are relatively high, there are disadvantages in that the amount of methane produced is large and the yield of gasoline fraction is low. There are many problems in practical operation, such as requiring a high reaction pressure of more than cm ² ·G, and the distribution of the resulting hydrocarbon products varying significantly depending on the reaction conditions. In addition, JP-A-1989-1983 uses a crystalline silicate-based zeolite catalyst with ion-exchange supported ruthenium.
In No. 19386, the yield of C ₁ + C ₂ hydrocarbons produced is
Although relatively high-quality gasoline can be selectively obtained, with a low yield of 4 wt% and a high yield of _C5 to _C12 hydrocarbons, there is a problem in that the conversion rate of carbon monoxide is low. In addition, JP-A No. 58-192834 discloses that when using a catalyst consisting of a mixture of crystalline zeolite and manganese oxide supporting ruthenium or a mixture of manganese oxide supporting ruthenium and crystalline zeolite, gasoline It is stated that the fraction can be obtained in high yield, but it is said that 40Kg/
Since it requires a high reaction pressure of more than cm ² ·G and produces a large amount of carbon dioxide, it has the disadvantage that the selectivity to hydrocarbons calculated from the raw material composition of the synthesis gas is extremely low. Therefore, how to narrow the difference in the optimal reaction conditions between carbon monoxide reduction catalysts and zeolite catalysts is an important issue for conversion reactions that produce hydrocarbons, mainly high-octane gasoline fractions, from synthesis gas in one step. It is becoming. (Means for Solving the Problems) The present inventors have conducted various studies to efficiently produce hydrocarbons mainly composed of gasoline fractions from synthesis gas in one step, and as a result, the present inventors have previously discovered manganese. Carbon monoxide reduction catalyst consisting of oxides, alkali metals, sulfur and ruthenium (patent application 1983-
211137 (Japanese Patent Publication No. 3-70692)) and a crystalline zeolite catalyst as a catalyst, it is possible to convert synthesis gas into liquid hydrocarbons, especially high-octane gasoline fractions, in one step. The present invention was completed by discovering that hydrocarbons can be efficiently produced. The reason why the catalyst used in the present invention exhibits excellent performance in gasoline distillate production is due to the oxidation number or crystal structure of the manganese oxide constituting the catalyst, as shown in the Examples and Comparative Examples below, and also due to the This is due to the coexistence of alkali metals and sulfur components contained in complexes, and also due to the coexistence of crystalline zeolite. That is, the gist of the present invention is to provide a carbon monoxide reduction catalyst containing at least one kind of manganese oxide selected from the group consisting of MnO ₂ , Mn ₂ O ₃ and Mn ₃ O ₄ , an alkali metal, sulfur and ruthenium as essential components. If the total weight of the alkali metal is
Consisting of a carbon monoxide reduction catalyst and crystalline zeolite containing 0.01 to 8 wt%, 0.001 to 3 wt% of sulfur, and 0.1 to 50 wt% of ruthenium, based on the total amount of the carbon monoxide reduction catalyst and the crystalline zeolite. The present invention provides a method for producing hydrocarbons, characterized in that hydrocarbons are produced by bringing a mixed gas containing hydrogen and carbon monoxide into contact with a catalyst composition containing 5 to 95 wt % of the carbon monoxide reduction catalyst. The catalyst used in the present invention is a catalyst composition comprising a carbon monoxide reduction catalyst comprising manganese oxide, an alkali metal, sulfur and ruthenium, and a crystalline zeolite catalyst. That is, the catalyst of the present invention has ruthenium supported on manganese oxide and contains an alkali metal, a sulfur component, and crystalline zeolite, but it may further contain other carrier substances, activators, etc., if necessary. . These catalyst components may be combined in any order. Regarding the carbon monoxide reduction catalyst, for example, ruthenium may be supported on a mixture of an alkali metal, a sulfur component, a carrier substance, and an activator with manganese oxide, or, like ruthenium, it may be supported on manganese oxide. Alternatively, the carrier material may be a physical mixture with a mixture of manganese oxides, alkali metals, sulfur, ruthenium, and other catalyst components may be supported on the carrier material. Preferred are manganese oxides or mixtures of manganese oxides and carrier materials with other catalyst components, and carrier materials with other catalyst components. As a preparation method, various conventionally known techniques can be used, such as impregnation into manganese oxide, gel mixing during synthesis of manganese oxide, or dry mixing. The crystalline zeolite catalyst may be incorporated into the carbon monoxide reduction catalyst at any stage during the preparation of the carbon monoxide reduction catalyst, or may be mixed with the prepared carbon monoxide reduction catalyst.
If crystalline zeolite is incorporated during the preparation of the carbon monoxide reduction catalyst, for example, the crystalline zeolite may be prepared by mixing with manganese oxide or a carrier material and then supporting ruthenium and other catalyst components; Crystalline zeolites may be prepared with ruthenium and other catalyst components supported on oxide or carrier materials. When blending crystalline zeolite with the carbon monoxide reduction catalyst that has been prepared, for example, the crystalline zeolite may be mixed with the carbon monoxide reduction catalyst, or a carrier material may be added and mixed to prepare the mixture. . A preferred catalyst is one prepared by blending a crystalline zeolite catalyst with the prepared carbon monoxide reduction catalyst. Next, the individual catalyst components will be explained. First, the carbon monoxide reduction catalyst will be explained. The manganese oxide used for catalyst preparation is subjected to thermal transition by heating in air, or hydrothermal transition, or
Various manganese oxide types can be obtained by reduction with CO, H ₂ , etc., and the manganese oxides used here include oxides such as MnO ₂ , Mn ₂ O ₃ , Mn ₃ O ₄ , etc. Oxides can have various crystal structures. For example, MnO ₂ with an α, β, γ, δ, and ε crystal structure is used, and Mn ₂ O ₃ with an α, γ crystal structure is used. In order to improve the dispersion state of ruthenium as an active metal in the reaction and maintain high reactivity, it is advantageous for the surface area of the manganese oxide to be larger. In addition, from the viewpoint of utilizing the redox reaction of manganese oxide, in order to improve the desolvation activity and selectively obtain a high-quality gasoline fraction, the charge number of manganese must be in a high oxidation state, that is, Mn ⁴⁺ or It is desirable to use a material containing a larger amount of Mn ³⁺ charge component (MnO ₂ , Mn ₂ O ₃ , etc.). The method of supporting the alkali metal and sulfur content on the manganese oxide used here is, for example, immersing the manganese oxide in a solution of an alkali metal compound or sulfur compound and adsorbing it onto the manganese oxide, or ion exchange. Ordinary methods in which manganese oxide is supported by contact with a solution containing an alkali metal compound or sulfur compound, such as by depositing the solution on the manganese oxide, by evaporating the solution to dryness, or by dropping the solution onto the manganese oxide. Impregnation techniques can be used. Further, the alkali metal and sulfur components can be supported before or after the ruthenium is supported, or at the same time as the ruthenium, but preferably the alkali metal and sulfur components are supported before the ruthenium is supported. Examples of alkali metal compounds that can be used in these cases include LiOH, NaOH, KOH, CsOH,
Alkali metal hydroxides such as RbOH or
Alkali metal carbonates such as Li ₂ CO ₃ , Na ₂ CO ₃ , K ₂ CO ₃ , Cs ₂ CO ₃ , Rb ₂ CO ₃ , or inorganic salts such as alkali metal halides and nitrates, alkali metal acetates, etc. There are various alkali metal compounds such as organic salts and alcoholates. Examples of sulfur compounds include thiocyanates, sulfates, hydrogen sulfates, pyrosulfates, sulfites, hydrogen sulfites, thiosulfates, sulfides, polysulfides, etc. of various metals or ammonium cations, etc., or sulfur. hydrocarbons, sulfuric esters, etc. The sulfur component can also be added onto a finished catalyst containing catalyst components other than the sulfur component. For example, sulfur is catalyzed by passing sulfur in the form of a gaseous sulfur compound, such as hydrogen sulfide, carbon disulfide or carbonyl sulfide, or a sulfur-containing hydrocarbon, to a finishing catalyst preferably filled in a reaction vessel. It can also be added inside. The alkali metal and sulfur components may be added during or after the preparation of the manganese oxide, or before or after supporting Ru as _an active metal. , CS ₂ or the like, it is possible to add the compound after reducing the catalyst with the zeolite catalyst described below or during the reaction. Either alkali metal and sulfur may be added first, and compounds containing both alkali metal and sulfur components, such as alkali metal sulfides, various sulfur-containing oxyacids, etc. For example, K ₂ SO ₄ , K ₂ S ₂ O ₇ ,
_{K2S , K2S5 , K2SO3} , _{KHSO3 , K2S2O3 ,}
It is also possible to dissolve the alkali metal (KSCN, NHSO ₄ , etc.) in a suitable solvent and add the alkali metal and sulfur at the same time. Alternatively, it is also possible to mix a predetermined amount of alkali metal and sulfur during the synthesis of manganese oxide. For example, mixing alkali metals during the electrolytic oxidation synthesis of α-type MnO ₂ or leaving an appropriate amount of alkali metals or sulfate radicals remaining during water washing during the synthesis of γ-type MnO ₂ by air oxidation of manganese carbonate. good. A preferred carbon monoxide reduction catalyst of the present invention is one in which ruthenium is supported on manganese oxide containing a small amount of alkali metal and sulfur. The preferred amount of alkali metal is about 0.01 to 8 wt%, preferably about 0.01 to 8 wt% based on the total weight of the carbon monoxide reduction catalyst.
It is 0.05-6wt%. The amount of sulfur to be blended is approximately 0.001 to 3 wt%, and preferably 0.07 to 1.5 wt%, based on the total weight of the carbon monoxide reduction catalyst. If the catalyst with the above composition is deficient in either the alkali metal or sulfur component, it will not be possible to selectively obtain a high quality gasoline fraction, the temperature dependence of the product distribution will be high, and Too much of the component does not provide significant improvement in catalyst activity. It is also possible to include other sparingly soluble materials in the catalyst as carrier materials that do not substantially inhibit the hydrocarbon synthesis properties of the ruthenium supported on the catalyst. For example, TiO ₂ , SiO ₂ , Al ₂ O ₃ ,
Inorganic metal oxides such as Cr ₂ O ₃ , V ₂ O ₅ , WO ₃ , MoO ₃ and natural clay minerals are mixed with manganese oxides, manganese oxides containing alkali metals and sulfur are mixed, and alkali It can be mixed with a manganese oxide containing metal and sulfur on which ruthenium is supported, or it can be supported on another carrier. Also applicable are methods in which predetermined amounts of manganese oxide, alkali metals, sulfur and ruthenium are supported on these carrier materials. The preferred loading of the carrier material is about 0.01 to 90 wt%, especially about 5 to 60 wt%, based on the total weight of the carbon monoxide reduction catalyst. These carrier materials are effective in increasing catalyst surface area, increasing mechanical strength, improving formability, improving reaction heat removal, or lowering catalyst cost. Ruthenium can be supported on a mixture of manganese oxide, an alkali metal, and sulfur by, for example, immersing this mixture in a solution of a ruthenium compound and adsorbing it onto the mixture, or depositing it by ion exchange, or by precipitating an alkali, etc. The above mixture and a solution containing a ruthenium compound are brought into contact with each other to support the ruthenium compound. Impregnation techniques are available. Examples of ruthenium compounds that can be used in these cases include ruthenium chloride, ruthenium nitrate, ruthenium acetate, hexaammonium ruthenium chloride ([Ru
(NH ₃ ) ₆ ]Cl ₃ ), and organic solvent-soluble compounds such as ruthenium carbonyl cluster and ruthenium acetylacetonate (Ru(C ₅ H ₇ O ₂ ) ₃ ). The blending amount of ruthenium is about 0.1 to 50 wt%, preferably about 0.1 to 50 wt%, based on the total weight of the carbon monoxide reduction catalyst.
It is supported at a concentration of 30 wt%, most preferably between 0.5 and 25 wt% (calculated as Ru). If the amount of ruthenium blended is too small, the catalyst activity will be low, and if it is too large, the selectivity for producing a gasoline fraction will be reduced. The majority of ruthenium in the catalyst is usually an elemental metal, but it may also be in the form of a compound such as an oxide. Furthermore, the timing of adding ruthenium is not limited to the above-mentioned addition to the mixture consisting of manganese oxide, alkali metal, and sulfur components, but after combining the above mixture and crystalline zeolite, ruthenium is added to the resulting mixture. It is also possible to support it. Further, the catalyst may further contain an activator to increase its activity. Examples of the activator include magnesium, zinc, copper, iron, etc., and the activator may be in the form of an elemental metal or a compound such as a chloride, ammonium salt, nitrate, or oxide in the catalyst.
Examples of activator components used as raw materials during catalyst preparation include magnesium chloride, subchloride, copper chloride, iron chloride, and iron nitrate. The blending amount of the activator is preferably about 0.01 to 35 wt%, particularly about 0.1 to 20 wt% in terms of elemental metal, based on the total weight of the carbon monoxide reduction catalyst.
The preferred total loading of activator and carrier material is about 0.01 to 90 wt%. These activators may be added during synthesis of manganese oxide or mixed with manganese oxide, but it is preferable to carry them before, after, or simultaneously with ruthenium after synthesis of manganese oxide. The activator can be mixed not only at the time of preparing the carbon monoxide reduction catalyst, but also into a prepared carbon monoxide reduction catalyst or a composite of this and crystalline zeolite. Next, the crystalline zeolite catalyst, which is another component of the catalyst composition used in the present invention, will be explained. Zeolite used as a crystalline zeolite catalyst is a crystalline aluminosilicate, in which some or all of the aluminum atoms of the crystalline aluminosilicate are replaced with other metals such as iron, chromium, vanadium, bismuth, lanthanum, cerium, titanium, boron,
It includes crystalline silicates synthesized in place of trivalent metals such as gallium, and crystalline silicates that contain almost no aluminum atoms and consist of 90 wt% or more of silica. These crystalline zeolites are H-type zeolites in which the ion-exchangeable cation species is hydrogen, but some or all of the hydrogen is Li,
Alkali metals such as Na, K, Rb, Cs or Ca,
It may be ion-exchanged zeolite with alkaline earth metals such as Ba, Mg, Sy, etc., or zeolite containing these metals. Examples of these crystalline zeolites have a pore size of about 5
erionite, offretite, ferriolite, phosiasite type X or Y zeolite with a pore size of about 9Å, mordenite type zeolite,
Zeolites such as the ZSM series have intermediate pore diameters in the range of about 5 to 9 Å and have a silica to alumina ratio of about 10 or more. (These crystalline zeolites were published in "Comprehensive Data Collection of Recent Advances in Zeolite Technology and Applications" published by Japan Technology and Economic Center Publishing Department, January 11, 1981, edited by Hiroshi Takahashi et al., Showa
29~ of “Zeolite” published by Kodansha on February 1, 1950
32, pages 46-47, or the specification of JP-A-57-70828. ) Among these zeolites, the most preferable zeolite for obtaining gasoline fraction in high yield has a pore size of 5 to 9.
ZSM− is a zeolite with a silica to alumina molar ratio of 10 or more as this type of zeolite.
5, ZSM-11, ZSM-12, ZSM-21, ZSM-
In addition to the ZSM series zeolites developed by Mobil Oil, such as 35 and ZSM-38, Ciel
X, which is similar to ZSM-5 made of silica-iron-alumina developed by International Research.
Zeolite gives a ray diffraction pattern, and even though the manufacturing method is different, the X-ray diffraction pattern is ZSM-5
ZSM-5 type crystalline zeolite, which is the same as
Also included are zeolites in which part or all of the alumina of the above zeolites is replaced with other trivalent metals, or those in which part or all of these H-type zeolites are ion-exchanged with alkali metals or alkaline earth metals. This type of zeolite is synthesized by hydrothermal synthesis in the presence of silica source, alumina source, alkali source, and organic reagents such as tetrapropylammonium salt, organic amine, alcohol amine or diglycol amine, and their precursors. Zeolite obtained by this method can be preferably used. Crystalline zeolites typically contain sodium, potassium, or organic nitrogen cations as ion-exchangeable cations, but for use in the conversion reactions of the present invention, at least 50% of these cations must be replaced by hydrogen ions, ammonium ions, etc. It is preferable to use cations that have been exchanged with ions, alkaline earth ions, rare earth ions, transition metal ions, etc. to create acidic points, and the cation exchange treatment is usually performed using a known ion exchange technique in which an aqueous solution containing the cations to be exchanged is used. It can be achieved. Also, substances containing organic nitrogen cations have a concentration of 400% in the air.
Decomposes organic nitrogen cations by heating to a temperature range of ~700℃,
It can easily become a hydrogen ion type by firing. The above-mentioned carbon monoxide reduction catalyst and crystalline zeolite catalyst can be combined by a conventionally known combination method. For example, a method of physically mixing a carbon monoxide reduction catalyst and a crystalline zeolite catalyst to form a homogeneous mixture, a method of filling a carbon monoxide reduction catalyst in the first stage and a crystalline zeolite catalyst in the second stage in the same reactor, or A method can be used in which a carbon monoxide reduction catalyst and a crystalline zeolite catalyst are mutually packed in multiple layers in the same reactor. The composite catalyst composition may be in any form such as powder, granules, or extrudates, and carrier materials as described above may be added to improve formability or removal of heat of reaction.
The proportion of the carbon monoxide reduction catalyst in the catalyst composition is about 5 to 95 wt%, preferably about 30 to 80 wt%, based on the total amount of the carbon monoxide reduction catalyst and the crystalline zeolite catalyst.
%. In this case, if the proportion of the carbon monoxide reduction catalyst is too small, the yield of the desired hydrocarbons will decrease, and if the proportion of the crystalline zeolite catalyst is too small, the yield of the desired hydrocarbons, such as high quality gasoline or kerosene with a high octane number, will be reduced. It becomes difficult to obtain a good yield. The carbon monoxide reduction catalyst, crystalline zeolite catalyst, or a catalyst composition obtained by combining both of them can be prepared using conventional methods. Dry with or without shaping. For example, dry at room temperature
This can be done by holding at 300°C for about 10 to 48 hours. The most preferred drying method is to dry at room temperature and then heat in the air to about 90-110℃ for several hours, or immediately in the air to about 90-110℃.
This method involves heating for several hours. The dried catalyst composition may be calcined by conventional methods if necessary. Calcination is preferably carried out by heating at a temperature of about 150 to 600°C, preferably about 300 to 600°C, for about 30 minutes to 48 hours.
Drying or calcination may be carried out at a stage during the preparation of the carbon monoxide reduction catalyst, for example at the stage of manganese oxide before supporting ruthenium etc., or at the stage of manganese oxide supporting an alkali metal, sulfur or ruthenium on manganese oxide. It may be done once. The catalyst composition prepared as described above is heated in a reducing atmosphere such as hydrogen or carbon monoxide at temperatures above about 300°C, preferably about 400°C, before loading with synthesis gas.
It is preferable to carry out the heat treatment at the above temperature for about 0.5 to 4 hours. In this case it is preferred to maintain a pressure of about 1 atm atmospheric pressure. When performing reduction treatment with hydrogen, etc., the catalyst surface is treated through a pretreatment step in which water, an oxygen-containing compound such as methanol or ethanol, or hydrogen sulfide, etc. is introduced simultaneously with hydrogen, etc., and this activation and sulfurization treatment is performed. It is also possible to control the product distribution. The reaction operating conditions of the method of the present invention are that the pressure is 0 to
100Kg/cm ² ·G, preferably 0 to 50Kg/cm ² ·G. It may also be carried out under reduced pressure. Temperature is about 100-500
°C, preferably about 200 to 450 °C, and the hydrogen to carbon monoxide molar ratio ( _H2 /CO ratio) is about 0.1 to 10, preferably about
0.5 to 4, most preferably 0.5 to 2, and the gas standard superficial velocity (GHSV) of the syngas fed is about 100 hr ^-1 to 20,000 hr ^-1 in terms of atmospheric pressure. The gas mixture leaving the reaction chamber is fed completely or partially back into the apparatus after removal of the hydrocarbon products produced. The catalyst used in the process of the invention is generally applied in fixed bed form. However, fluidized beds, suspended beds, etc., in which this is used in a finely dispersed form, are also applicable. The catalyst may also be removed from the reaction vessel for continuous or discontinuous regeneration. In this case, the catalyst is regenerated by combustion with air in a special vessel to remove impurities deposited on the catalyst surface and subsequent reduction using known methods. It is considered that most of the ruthenium compound in the catalyst becomes an elemental metal during the reduction step or reaction as a pretreatment of the catalyst, and a portion may become a sulfide or an oxide. Furthermore, during the preparation of the catalyst, manganese oxide is thought to change into other crystal forms or other manganese oxides during the reaction. In the catalyst of the present invention, ruthenium and manganese oxide work like a composite catalyst, and the alkali metal and sulfur work like a promoter. (Effects of the Invention) According to the method of the present invention, liquid hydrocarbons, particularly hydrocarbons mainly composed of gasoline fractions, can be obtained with good selectivity and yield. The resulting gasoline fraction has a high aromatic hydrocarbon content and can be used as a high-octane automobile fuel or as a petrochemical raw material. Furthermore, the catalyst of the present invention has strong sulfur resistance, and raw material gas containing sulfur as an impurity can also be used. (Example) The present invention will be explained below with reference to Examples. The H ₂ /CO molar ratio in the reaction conditions in the following examples is 1.0 unless otherwise specified.
I did it at Example 1, Comparative Example 1 Preparation of carbon monoxide reduction catalyst Ruthenium-manganese oxide-alkali metal-
A carbon monoxide reduction catalyst consisting of a sulfur component was prepared as follows. For manganese oxide, platinum is used as an anode.
A mixed warm aqueous solution (approximately 60°C) of 1N-manganese sulfate and 0.2N-sulfuric acid is anodized at a current density of 3.0A/ ^dm2 , and the electrolytic manganese dioxide produced on the electrode plate is peeled off from the electrode plate. , the electrolyte adhering to the precipitate is thoroughly washed with hot water, and then 80~
A drying treatment was performed at 100°C for 3 hours to obtain γ-type manganese dioxide. The obtained manganese oxide was ground into a fine powder in an agate mortar, immersed in an aqueous sulfuric acid solution with a sulfur content of 0.5 wt% based on the total weight of the carbon monoxide reduction catalyst, and then heated at 110°C for 3 hours. dry.
After that, it was immersed again in an aqueous potassium hydroxide solution with a potassium content of 1.35 wt% of the total weight of the carbon monoxide reduction catalyst, dried at 110°C for 3 hours, and further calcined at 450°C for 3 hours. A mixture consisting of manganese oxide-alkali metal-sulfur components was prepared. Next, this mixture has a ruthenium content of 2.0wt% based on the total weight of the carbon monoxide reduction catalyst.
After immersing in an amount of ruthenium chloride aqueous solution,
Carbon monoxide reduction catalyst A (abbreviation: 2%Ru-1.35
%K-0.5%S/ _MnO2 ) was obtained. Preparation of crystalline zeolite catalyst ZSM-5 type zeolite was synthesized as follows. Add 17.1 g of aluminum sulfate, 18.5 g of concentrated sulfuric acid, and 22.6 g of tetrapropylammonium bromide to water.
Solution A dissolved in 180g, water glass No. 3 (silica)
28.9%) 207g dissolved in 140g of water and Solution C prepared by dissolving 78.8g of sodium chloride in 320g of water. The C solution was vigorously stirred, and the A and B solutions were simultaneously added dropwise and mixed, and then charged into a stainless steel 1 autoclave. Stir at 100-150 rpm,
Gradually raise the temperature and carry out the reaction at 160℃ under autogenous pressure for 20 hours, then naturally cool the reaction mixture, filter the formed fine white crystals, repeat washing with water,
Repeat this operation until the pH of the washing water reaches approximately 8. After further drying at 120°C, it was fired in air at 550°C for 6 hours. Thereafter, ion exchange was carried out at a temperature of 80 to 90°C using 5 ml of a 2N ammonium chloride aqueous solution per 1 g of zeolite to obtain H-type zeolite. After filtering and washing with water, repeat the same treatment 5 times using fresh ammonium chloride aqueous solution, then wash with water.
After drying at 120°C for 3 hours, it was calcined again in air at 550°C for 6 hours to obtain an H-type ZSM-5 type zeolite catalyst. Catalyst of the present invention The above carbon monoxide reduction catalyst A and the above H type ZSM-
5. After thoroughly mixing equal volumes of zeolite catalysts in a mortar, molding them into a size of 1 to 2 mm and preparing the catalysts (ruthenium content: 1.6 wt% based on the total weight of the catalyst,
Potassium is 1.0wt% and sulfur is 0.4wt%. Abbreviation of this catalyst: 1.6%Ru-1.0%K-0.4%S/MnO ₂ +
ZSM-5. ) was prepared. Comparative Catalyst For comparison, a ruthenium-manganese oxide-alkali metal component was prepared without treatment with an aqueous sulfuric acid solution when preparing the carbon monoxide reduction catalyst A, and a ruthenium-manganese oxide without a treatment with an aqueous potassium hydroxide solution was prepared. - A carbon monoxide reduction catalyst consisting of a sulfur component or a ruthenium-manganese oxide component that is not subjected to aqueous treatment with both sulfuric acid and potassium hydroxide is prepared, and then the catalyst is mixed with zeolite in the same proportion and manufacturing method as the catalyst. , , were obtained respectively. Alternatively, a catalyst consisting of a ruthenium-manganese oxide component or a ruthenium-manganese oxide-alkali metal-sulfur component alone as a carbon monoxide reduction catalyst not mixed with zeolite was obtained. Reaction Fill the prepared catalyst into a reaction container and
After hydrogen reduction at 400℃ for 2 hours, using synthesis gas consisting of carbon monoxide and hydrogen (H ₂ /CO = 1)
Temperature of 300℃, 270℃ or 330℃, 10Kg/cm ²・G
The reaction was carried out under the conditions of GHSV 600 hr ^-1 or 1200 hr ^-1 and the results shown in Table 1 were obtained. The amount of catalyst charged is 4 ml for each catalyst.
(3.39 g) and catalyst were each 2 ml. Ruthenium - manganese oxide - alkali metal -
Carbon monoxide reduction catalyst consisting of sulfur component and -H-
With the catalyst mixed with ZSM-5 type zeolite,
The production of methane is significantly lower than that of a catalyst lacking either or both of alkali metals and sulfur components, or a carbon _monoxide reduction catalyst alone without _zeolite . The production of gasoline fraction is dramatically improved, and the content of aromatic components in the produced hydrocarbons is also high. In addition, the methane production rate is low over a wide temperature range, so
It is particularly noteworthy that stable yields of high quality gasoline fraction yields are achieved.

[Table] (Note) (1) Aromatic content indicates the content in the produced hydrocarbons. same as below.
(2) Oxygenated compounds were also produced, but the amount produced was very small and the selectivity was ignored. same as below.
Example 2, Comparative Example 2 Various manganese oxides (commercially available amorphous MnO ₂ , β-type MnO ₂ , M ₂ O ₃ ,
A carbon monoxide reduction catalyst was prepared by supporting a predetermined amount of sulfur and various alkali metals on MnO) and supporting 2 wt% of ruthenium. The following catalysts were prepared by mixing these carbon monoxide reduction catalysts and the same H-type ZSM-5 zeolite catalyst as that used in the catalyst of Example 1. That is, a carbon monoxide reduction catalyst containing potassium as an alkali metal component using commercially available amorphous MnO ₂ was mixed with zeolite at a volume ratio of 70:30, and a catalyst was prepared by mixing commercially available β-MnO ₂ with potassium as an alkali metal component. A catalyst is a mixture of a carbon monoxide reduction catalyst using sodium as a carbon monoxide reduction catalyst and zeolite at a volume ratio of 40:60, a carbon monoxide reduction catalyst using commercially available Mn ₂ O ₃ and rubidium as an alkali metal component, and zeolite. Catalysts mixed at a volume ratio of 50:50 were obtained, respectively. In addition, as a comparative example, a catalyst was prepared by mixing a carbon monoxide reduction catalyst using MnO and potassium as an alkali metal component and zeolite at a volume ratio of 50:50. A catalyst containing no and a was prepared. When a reaction was carried out using these catalysts in the same manner and under the same conditions as in Example 1, the results shown in Table 2 were obtained. (Catalyst filling amount is 4ml,
The catalyst loading amount was 2 ml. ) Compared to the catalyst shown in the comparative example that does not contain zeolite and does not contain alkali metals and sulfur components, the catalysts ~ according to the present invention produce a lower amount of methane, and in particular, the amount of hydrocarbons of C5 or higher and the amount of hydrocarbons produced are _lower . The aromatic content has been improved, and a catalyst containing zeolite and a Ru-manganese oxide-based carbon monoxide reduction catalyst in which alkali metals and sulfur components coexist shows excellent effects in producing high-quality gasoline fractions. I understand that. In addition, the catalyst of the comparative example containing MnO as a catalyst component was compared to the catalyst of the example.
It can be seen that the selectivity of C ₅ to C ₁₂ and the aromatic content are inferior.

【table】

[Table] Example 3 A catalyst was prepared in the same manner as the method for producing the catalyst, except that calcination was not performed when preparing the carbon monoxide reduction catalyst A used in the catalyst of Example 1, and hydrogen was heated at 400°C. After reduction, the catalyst filling amount is 4ml,
At a temperature of 360℃, pressure 5.7Kg/cm ²・G,
When the reaction was carried out by passing synthesis gas with a H ₂ /CO ratio of 0.5 (molar ratio) at GHSV 300 hr ^-1 , the results shown in Table 3 were obtained. Example 4, Comparative Example 3 Using the catalyst shown in Comparative Example 1, hydrogen treatment was performed at 400°C, and then at a temperature of 330°C and a pressure of 10 kg/
The reaction was carried out under the conditions of cm ² ·G and GHSV -900 hr ^-1 (Comparative Example 3). After that, the pressure is returned to normal pressure and the temperature inside the reactor is
While maintaining the temperature at 330°C, hydrogen sulfide gas was injected nine times in pulses of 5 ml each using a syringe while the reaction gas was flowing, and the reaction was carried out by raising the pressure again on the catalyst whose surface had been partially sulfurized (Example 4) ) The results of the above Examples and Comparative Examples are shown in Table 4.
Sulfur can be doped onto the catalyst using various methods, but by directly introducing the gaseous sulfur compound exemplified here together with the reaction gas, the sulfur content can be doped into the catalyst in the form of sulfuric acid groups, etc. It can be said that it is a simple method for catalyst preparation because it exhibits almost the same catalytic performance as the catalyst introduced during preparation.

【table】

[Table] Example 5 When preparing the crystalline zeolite catalyst blended with the catalyst of Example 1, 5.10 g of ferric chloride FeCl ₃ 6H ₂ O or potassium sulfate was used instead of 17.1 g of aluminum sulfate.
Crystalline iron silicate and crystalline gallium silicate prepared in the same manner as the zeolite catalyst preparation except that 8.10 g was used, and commercially available Y-type zeolite (SK-41 manufactured by Union Carbide)
Using these crystalline zeolite catalysts, Example 1
The same carbon monoxide reduction catalyst A mixed with the catalyst of
They were mixed in equal volumes with each other to obtain catalysts. A reaction was carried out in the same manner as in Example 1 using these catalysts. The results are shown in Table-5. As shown in the examples above, by using the catalyst of the present invention which is a mixture of a carbon monoxide reduction catalyst consisting of a ruthenium-manganese oxide-alkali metal-sulfur component and zeolite, hydrocarbons can be directly utilized as gasoline from synthesis gas. can be obtained with high selectivity.

Claims (1)

[Claims] 1 A carbon monoxide reduction catalyst containing at least one manganese oxide selected from the group consisting of MnO ₂ , Mn ₂ O ₃ and Mn ₃ O ₄ , an alkali metal, sulfur and ruthenium as essential components, and its total weight As a standard, alkali metals are 0.01 to 8wt%, sulfur is
The carbon monoxide reduction catalyst is composed of a carbon monoxide reduction catalyst and crystalline zeolite containing 0.001 to 3 wt% and 0.1 to 50 wt% of ruthenium, based on the total amount of the carbon monoxide reduction catalyst and the crystalline zeolite. A method for producing hydrocarbons, which comprises producing hydrocarbons by bringing a mixed gas containing hydrogen and carbon monoxide into contact with a catalyst composition in which carbon monoxide is 5 to 95 wt%.