JP5482708B2 - Gasoline base material and method for producing gasoline base material - Google Patents

Description

  The present invention relates to a gasoline base material produced by a Fischer-Tropsch (FT) reaction from a mixed gas containing hydrogen and carbon monoxide as main components (hereinafter referred to as “synthesis gas”). More specifically, a gasoline base material obtained by the FT reaction using a catalyst composition for the production of hydrocarbons containing a metal having activity in the FT reaction, manganese carbonate, and a zeolite showing a solid acid, and its production Regarding the method.

  As a method for synthesizing hydrocarbons from synthesis gas, a Fischer-Tropsch reaction (hereinafter referred to as “FT reaction”), a methanol synthesis reaction, and the like are well known. The FT reaction is a catalyst that uses an iron group element of iron, cobalt, nickel, or a platinum group element such as ruthenium as an active metal. On the other hand, it is known that methanol synthesis reaction proceeds with a copper-based catalyst, and C2 oxygen-containing (ethanol, acetaldehyde, etc.) synthesis proceeds with a rhodium-based catalyst (see, for example, Non-Patent Document 1).

By the way, in recent years, gas oil with low sulfur content has been desired from the viewpoint of the preservation of the air environment, and this trend is expected to become stronger in the future. In addition, from the viewpoint that crude oil resources are limited and from the viewpoint of energy security, the development of alternative fuels for oil is desired, and it is expected that this will become increasingly desirable in the future. As a technology to meet these demands, GTL (gas to liquids) is a technology that synthesizes liquid fuel such as kerosene from natural gas (main component methane), which is said to have recoverable reserves equivalent to crude oil in terms of energy. is there. Since natural gas does not contain sulfur or is hydrogen sulfide (H ₂ S) or the like that is easy to desulfurize even if it contains, liquid fuel such as kerosene obtained has almost no sulfur in it. In addition, because of the advantage that it can be used for high-performance diesel fuel having a high cetane number, this GTL has been increasingly attracting attention in recent years.

  As part of the GTL, methods for producing hydrocarbons from synthesis gas by the FT reaction have been actively studied. The hydrocarbons obtained by this FT reaction are a wide range of hydrocarbons ranging from methane to wax and trace amounts of oxygen-containing compounds such as various alcohols, and cannot selectively produce a specific fraction. Therefore, for example, in order to efficiently obtain a kerosene fraction by the FT reaction, in addition to the straight kerosene fraction produced by the FT reaction, a heavier wax fraction is hydrocracked. It is common practice to produce a kerosene fraction and increase the yield of the kerosene fraction.

  On the other hand, a gasoline fraction can also be obtained by FT reaction. However, since the hydrocarbons produced by the FT reaction are mainly composed of linear paraffin, the gasoline fraction obtained by the FT reaction has a very low octane number and is not practical. Normally, the octane number of hydrocarbons is the highest for aromatic hydrocarbons, and then decreases in the order of naphthenic hydrocarbons, olefinic hydrocarbons, and paraffinic hydrocarbons. In the case of the same family hydrocarbons, the lower the number of carbon atoms, the lower the boiling point, the higher the octane number, and the higher the number of carbon atoms with the same number of branches.

  Conventionally, a method for producing a gasoline fraction by decomposing and isomerizing a hydrocarbon produced by an FT reaction with a solid acid catalyst such as zeolite has been proposed. For example, using a FT synthesis catalyst containing FT active metal species such as ruthenium and cobalt (metal species showing activity in FT reaction) and a catalyst in which ZSM-5 and β zeolite coexist, the synthesis gas is converted into gasoline by a one-step reaction. A method for producing a fraction (one-stage method) has been proposed (see, for example, Patent Documents 1 and 2). In addition, a method (two-stage method) for producing a gasoline fraction by reacting at an optimum temperature by a two-stage reaction of a reaction with an FT synthesis catalyst and a reaction with a solid acid catalyst has also been proposed (for example, (See Patent Document 3). In addition, a method for highly selective synthesis of isoparaffin is proposed by using a catalyst for FT synthesis in which a FT active metal species such as cobalt or ruthenium is dispersed or supported by sputtering on the surface of a powdery carrier made of zeolite. (For example, refer to Patent Document 4).

  By the way, the production of product gasoline is made according to seasonal changes. For example, in summer, the vapor pressure of product gasoline is lower than other seasons from the viewpoint of suppressing the generation of evaporative gas. Further, in the summer, the yield of gasoline base material, that is, the yield of product gasoline, is improved by fractionating the naphtha fraction, which is one of the gasoline base materials, to have a wide boiling range. Therefore, the yield of the obtained gasoline base material with respect to crude oil is higher than that in winter, which is preferable in terms of energy security and energy saving. Thus, in summer, a gasoline base having a low vapor pressure, a high yield, and a high octane number is required.

JP 62-109888 A JP 2007-197628 A JP 2001-288123 A JP 2009-106863 A

“C1 Chemistry”, edited by the Catalysis Society of Japan, published by Kodansha, 1984, page 25.

The conventional one-stage method has a problem that both reactions cannot be performed efficiently because the optimum reaction temperature ranges of the FT synthesis catalyst and the solid acid catalyst are different. For example, when the reaction is carried out at a relatively low temperature that is optimal for an FT synthesis catalyst, the production of lower hydrocarbons such as CH ₄ is suppressed and higher hydrocarbons having 5 or more carbon atoms are efficiently produced. The activity of the catalyst is low, the decomposition and isomerization reaction of the produced hydrocarbons are lowered, the gasoline yield is lowered, and the production of high octane hydrocarbons such as aromatic hydrocarbons and branched hydrocarbons is also lowered. Conversely, when the reaction is carried out at an optimum temperature for the solid acid catalyst, the FT reaction promotes the generation of gas components such as lower hydrocarbons such as CH ₄ and CO _2, resulting in a decrease in gasoline yield. .

  On the other hand, in the two-stage method, the reaction can proceed at the optimum temperature of each catalyst, and a gasoline fraction can be efficiently produced. However, since hydrogen is introduced before the second stage reaction to proceed with hydrocracking, isoparaffin in the product is produced, but there is a problem that the olefin content is reduced and the octane number is lowered.

  Moreover, although the hydrocarbons synthesized by the FT synthesis catalyst described in Patent Document 4 have a high isoparaffin content, the content of aromatic compounds is low and the octane number is not sufficient, and they are used as a gasoline base material. Is not enough.

  The present invention provides a gasoline base material that is a product obtained by the FT reaction and has a high content of high octane components such as aromatics, naphthenes, olefins, and branched paraffin hydrocarbons, and a method for producing the same. With the goal.

  As a result of researches to achieve the above-mentioned object, the inventors of the present invention contain a metal that exhibits activity in the FT reaction, manganese carbonate, and a zeolite that exhibits a solid acid, and the content of the zeolite relative to the catalyst composition. By using a catalyst composition with a specific ratio, it is possible to produce a high-octane gasoline fraction rich in aromatics, naphthenes, olefins and branched paraffins while maintaining a high gasoline yield by the FT reaction. As a result, the present invention has been completed.

That is, the present invention
(1) One or more metals showing activity in the Fischer-Tropsch reaction, manganese carbonate, and H-ZSM-5 , which is a zeolite showing a solid acid, and the content of the zeolite relative to the catalyst composition From a gas mainly composed of hydrogen and carbon monoxide using a catalyst composition for producing hydrocarbons having a mass of 30% by mass to 65% by mass,
(A) Research method octane number of 80-93,
(B) Motor method octane number of 74 to 83,
(C) The aromatic ratio is 3% by volume or more and less than 30% by volume,
(D) The proportion of olefins is 70% by volume or less,
(E) Oxygen content is 0.5 mass% or less,
(F) A method for producing a gasoline base material, comprising producing a gasoline base material having a benzene content of 0.5% by volume or less, and (g) a sulfur content of 0.5 mass ppm or less,
(2) The gasoline base material is
(H) 10% by volume distillation temperature (T10) is 25.0-40.0 ° C, 50% by volume distillation temperature (T50) is 90.0-125.0 ° C, and 90% by volume distillation. The temperature (T90) is 160.0-180.0 ° C,
The method for producing a gasoline base material according to (1),
( 3 ) One or more metals showing activity in the Fischer-Tropsch reaction, manganese carbonate, and H-ZSM-5 , which is a zeolite showing a solid acid, and the content of the zeolite relative to the catalyst composition Is a gasoline fraction of a product synthesized from a gas mainly composed of hydrogen and carbon monoxide using a catalyst composition for producing hydrocarbons having a mass of 30% to 65% by mass,
(A) Research method octane number of 80-93
(B) Motor method octane number of 74 to 83
(C) Aromatic ratio is 3 volume% or more and less than 30 volume% (d) Olefin ratio is 70 volume% or less (e) Oxygen content is 0.5 mass% or less (f) benzene is 0.5 volume% below,
(G) the sulfur content is 0.5 mass ppm or less, and
(H) 10% by volume distillation temperature (T10) is 25.0-40.0 ° C, 50% by volume distillation temperature (T50) is 90.0-125.0 ° C, and 90% by volume distillation. Temperature (T90) is 160.0-180.0 ° C
Gasoline base material, characterized in that
( 4 ) The catalyst composition contains a Fischer-Tropsch synthesis catalyst containing one or more metals and manganese carbonate which are active in Fischer-Tropsch reaction, and a zeolite showing a solid acid. ( 3 ) Gasoline base material according to the description,
( 5 ) The gasoline base material according to ( 3 ) or ( 4 ), wherein the metal is ruthenium,
Is to provide.

  According to the present invention, the content of high-octane components such as aromatics, naphthenes, olefins, and branched paraffin hydrocarbons is not only contained, but also contains only sulfur content that does not contain sulfur or can be easily desulfurized. It is possible to provide an excellent gasoline base material having a high value and a method for producing the same.

<Gasoline base material>
The gasoline base material of the present invention contains one or more metals that are active in the FT reaction, manganese carbonate, and a zeolite that shows a solid acid, and the content of the zeolite relative to the catalyst composition is 30% by mass. A gasoline fraction of a product synthesized from a gas mainly composed of hydrogen and carbon monoxide, using a catalyst composition for producing hydrocarbons that is 65% by mass or less and having the following properties: It is characterized by.
(A) Research method octane number of 80-93
(B) Motor method octane number of 74 to 83
(C) Aromatic ratio is 3 volume% or more and less than 30 volume% (d) Olefin ratio is 70 volume% or less (e) Oxygen content is 0.5 mass% or less (f) benzene is 0.5 volume% And (g) the sulfur content is 0.5 mass ppm or less.

Hereinafter, the contents of the present invention will be described in more detail.
The research octane number (RON) of the gasoline base of the present invention is 80 to 93, preferably 81 to 93, and more preferably 81 to 92. Moreover, the motor method octane number (MON) of the gasoline base material of this invention is 74-83, Preferably it is 75-83, More preferably, it is 75-82. When RON and MON are within this range, the octane number of gasoline containing the gasoline base material of the present invention can be increased. That is, the gasoline base material of the present invention is preferable from the viewpoint of CO ₂ reduction. In addition, in this invention and this-application specification, RON and MON of a gasoline base material mean the value measured according to JISK2280.

  The proportion of aromatics in the gasoline base of the present invention is 3% by volume or more and less than 30% by volume, preferably 10% by volume or more and less than 30% by volume. The proportion of olefins in the gasoline base of the present invention is 70% by volume or less, preferably more than 5% by volume and 70% by volume or less, more preferably more than 5% by volume and 30% by volume or less. Since the aromatic content is 3% by volume or more and the olefin content is 70% by volume or less, the gasoline base material of the present invention has high RON and MON, and is suitable as a gasoline base material. . In addition, in this invention and this-application specification, an aromatics ratio and an olefins ratio mean the value measured according to JISK2536.

  The oxygen content of the gasoline base material of the present invention is 0.5% by mass or less, preferably 0.1% by mass. Many oxygen-containing compounds have low oxidation stability, and may cause metal corrosion and rubber deterioration. When the oxygen content is 0.5% by mass or less, the gasoline base material of the present invention has excellent oxidation stability and is suitable as a gasoline base material. In addition, in this invention and this-application specification, the oxygen content of a gasoline base material means the value measured according to JISK2536.

  The content of benzene in the gasoline base material of the present invention is 0.5% by volume or less, preferably 0.4% by volume or less. When the content ratio of benzene is as low as 0.5% by volume or less, the gasoline in which the gasoline base material of the present invention is blended may prevent an increase in the concentration of benzene in the atmosphere and reduce environmental pollution. In addition, in this invention and this-application specification, the content rate of benzene of a gasoline base material means the value measured according to JISK2536.

  The sulfur content of the gasoline base material of the present invention is 0.5 mass ppm or less, preferably 0.2 mass ppm or less. Since the sulfur content is as low as 0.5 mass ppm or less, the gasoline base material of the present invention is preferable because poisoning of the automobile exhaust gas catalyst can be suppressed. In addition, in this invention and this-application specification, the sulfur content of a gasoline base material means the value measured according to JISK2541.

  The other hydrocarbon composition of the gasoline base material of the present invention is not particularly limited. For example, n-paraffins are 10 to 20% by volume, preferably 11 to 17% by volume, and i-paraffins. Is 10 to 40% by volume, preferably 20 to 40% by volume, and naphthenes are 3 to 11% by volume, preferably 5 to 11% by volume. In addition, in this specification, the composition ratio of each hydrocarbon of a gasoline base means the value measured according to JISK2536.

The density at 15 ° C. of the gasoline base material of the present invention is preferably 0.7000 to 0.7600 g / cm ³ , more preferably 0.7050 to 0.7600 g / cm ³ . When the density at 15 ° C. is in this range, good fuel efficiency can be secured when blended with product gasoline. In addition, in this invention and this-application specification, the density in 15 degreeC means the value measured according to JISK2249.

  The 10% by volume distillation temperature (T10) of the gasoline base of the present invention is preferably 25.0 to 40.0 ° C, more preferably 26.0 to 39.0 ° C, and even more preferably 29. 0-37.0 ° C. The 50% by volume distillation temperature (T50) of the gasoline base material of the present invention is preferably 90.0 to 125.0 ° C, more preferably 92.0 to 120.0 ° C, still more preferably 95. It is 0-120.0 degreeC. Moreover, 90 volume% distillation temperature (T90) of the gasoline base material of this invention becomes like this. Preferably it is 160.0-180.0 degreeC, More preferably, it is 165.0-175.0 degreeC, More preferably It is 166.0-174.0 degreeC. The end point temperature (EP) of the gasoline composition of the present invention is preferably 180.0 to 200.0 ° C, more preferably 185.0 to 200.0 ° C, and further preferably 190.0 to 200.0 ° C. When T10, T50, T90, and EP are within this range, the distillation properties of the gasoline base material and the distillation properties of the product gasoline become equivalent. Therefore, even when this gasoline base material is highly blended, it is possible to prevent the occurrence of problems in the startability, drivability and acceleration of the obtained gasoline. In addition, in this invention and this-application specification, the distillation property of a gasoline composition means the value measured according to JISK2249.

  The lead vapor pressure (RVP) of the gasoline base material of the present invention is preferably 30.0 to 65.0 kPa, more preferably 35.0 to 65.0 kPa. For summer product gasoline, the RVP is lowered in order to suppress the generation of evaporative gas, but the RVP of this gasoline base is within this range, so even if the gasoline base is highly blended, the product gasoline evaporative gas Can be suppressed, which is preferable.

  Since the gasoline base material of the present invention has both high RON and MON and low sulfur content, it can be used as it is by blending it with gasoline. Further, in order to further reduce the sulfur content, the gasoline base material of the present invention which has been further desulfurized may be blended into gasoline.

<Catalyst composition for hydrocarbon production>
The gasoline base material of the present invention contains, from synthesis gas, carbonization containing, for example, one or more metals showing activity in FT reaction, manganese carbonate, and zeolite showing a predetermined ratio of solid acid as shown below. By using the catalyst composition for hydrogen production, it can be synthesized by FT reaction. Hereinafter, a catalyst composition for producing hydrocarbons suitable for producing the gasoline base material of the present invention (hereinafter, sometimes referred to as “catalyst composition used in the present invention”) will be described.

  Examples of the FT active metal species constituting the catalyst composition used in the present invention include nickel, cobalt, iron, and ruthenium. Among them, ruthenium is preferably selected as a more active metal species. Moreover, these metal seed | species can also be used independently and can also be used in mixture of 2 or more types.

  As manganese carbonate which comprises the catalyst composition used for this invention, a commercially available reagent may be used and what was manufactured by the conventionally well-known method may be used. A conventionally known method for producing manganese carbonate includes a method of reacting a soluble manganese salt solution with ammonia or an alkali carbonate solution. Manganese carbonate can also be obtained by reaction of divalent manganese ions with carbonate ions or bicarbonate ions.

  The zeolite constituting the catalyst composition used in the present invention is not particularly limited as long as it is a zeolite showing a solid acid, and can be appropriately selected from known zeolites. The solid acid is one in which the surface of the solid exhibits Bronsted acidity or Lewis acidity, and is active in homogeneous or heterogeneous acid-catalyzed reactions. Hydrocarbons synthesized by the FT reaction are hydrocracked or isomerized by contacting the acid on the solid surface of the zeolite.

  Preferred zeolites include ZSM-5, β zeolite, Y-type zeolite, USY zeolite, mordenite and the like, with ZSM-5 being particularly preferred. As the zeolite, a commercially available product may be used, or a product hydrothermally synthesized by a known method may be used. These zeolites usually contain an alkali metal as an ion-exchangeable cation. However, the zeolite used in the catalyst composition used in the present invention contains 50% or more of protons, alkaline earth metal ions, transitions. Those substituted with metal ions or rare earth metal ions and having solid acidity are preferred, and H (proton) -ZSM-5 is particularly preferably used.

  The catalyst composition used for this invention should just contain FT active metal seed | species, manganese carbonate, and a zeolite, and may contain the other component, unless the effect of this invention is impaired. Further, the catalyst composition used in the present invention may be prepared using any conventionally known method. For example, the catalyst composition used in the present invention can be prepared by separately preparing an FT synthesis catalyst containing FT active metal species and manganese carbonate and a zeolite, and then physically mixing the two. . The catalyst composition used in the present invention can also be prepared by impregnating and supporting an FT active metal on a composite molded body of manganese carbonate and zeolite.

  As a method for synthesizing an FT synthesis catalyst containing FT active metal species and manganese carbonate, for example, there is a method of impregnating and supporting FT active metal species on manganese carbonate. The loading of the FT active metal species on the manganese carbonate is carried out by ordinary impregnation loading. For example, manganese carbonate is immersed in an aqueous solution of ruthenium salt so that the ruthenium salt is impregnated in manganese carbonate, and then dried and fired. When two or more metals are supported on manganese carbonate as the FT active metal species, an aqueous solution containing both a ruthenium salt and a cobalt salt is prepared, and the aqueous solution is impregnated with manganese carbonate, followed by drying and firing. There may be a stage system in which a ruthenium salt aqueous solution and a cobalt salt aqueous solution are impregnated separately in manganese carbonate and then dried and fired, and there is no particular limitation.

  Examples of the ruthenium salt include water-soluble ruthenium salts such as ruthenium chloride, ruthenium nitrate, ruthenium acetate, and ruthenium hexaammonium chloride. The ruthenium salt solution used for impregnation support can be replaced with an aqueous solution and an organic solvent such as alcohol, ether, or ketone. In this case, a salt that is soluble in various organic solvents is selected.

  The content of ruthenium in the FT synthesis catalyst is 0.1 to 5% by mass, preferably 0.3 to 4.5% by mass, more preferably 0.5 to 4% in terms of metal amount based on the FT synthesis catalyst standard. % By mass. The ruthenium content is related to the number of active sites. If the ruthenium content is less than 0.1% by mass, the number of active sites may be insufficient and sufficient catalytic activity may not be obtained. On the other hand, when the content of ruthenium exceeds 5% by mass, the ruthenium is not sufficiently supported on the carrier such as manganese carbonate, and the dispersibility is reduced and the ruthenium species not interacting with the carrier component is expressed. Is likely to occur. Therefore, excessive loading of ruthenium is not preferable because it simply increases the catalyst cost.

  The FT synthesis catalyst constituting the catalyst composition used in the present invention may contain other components as long as the FT reaction by manganese carbonate and FT active metal species is not inhibited. Examples of other components include inorganic oxides that are usually used as carriers, such as silica, alumina, and silica-alumina. The content of these carrier (inorganic oxide) components in the FT synthesis catalyst can be appropriately set as long as the effects of manganese carbonate and FT active metal species are not impaired. Generally, the carrier (content of these carrier components) 5-50% by mass is appropriate on the basis of the sum of the total content of manganese carbonate and manganese carbonate.

  Furthermore, the FT synthesis catalyst constituting the catalyst composition used in the present invention may contain an alkali metal species in addition to manganese carbonate and FT active metal species. Examples of the alkali metal species include lithium, sodium, potassium, rubidium and the like, among which sodium and potassium are preferably selected. These alkali metal species can be used alone or in combination of two or more.

  A method for adding an alkali metal species to the FT synthesis catalyst in addition to the manganese carbonate and the FT active metal species is not particularly limited. For example, in the same manner as the FT active metal species, manganese carbonate can be impregnated with an alkali metal species. Specifically, for example, an aqueous solution of sodium salt or potassium salt is impregnated with manganese carbonate, and then dried and fired. The order in which the FT active metal species and the alkali metal species are supported on the manganese carbonate is not particularly limited, and the manganese carbonate may be immersed in an aqueous solution containing both and supported simultaneously. The sodium salt or potassium salt impregnated and supported on manganese carbonate is preferably a water-soluble salt such as chloride, nitrate, acetate or carbonate.

  The content of alkali metals such as sodium and potassium in the FT synthesis catalyst is preferably 0.05 to 3% by mass, more preferably 0.05 to 2% by mass, more preferably 0.05 to 2% by mass, based on the FT synthesis catalyst standard. Preferably it is 0.1-1.5 mass%. By making the content of sodium or potassium 0.05% by mass or more, the effect of suppressing the generation amount of gas components becomes remarkable. Moreover, by setting it as 3 mass% or less, it becomes possible to suppress the production amount of a gas component, without reducing FT activity.

  After impregnating manganese carbonate with an FT active metal species such as ruthenium, drying and firing are performed. The drying at this time is performed in order to evaporate a solvent such as water used when impregnating and supporting the FT active metal species in manganese carbonate, and the temperature is preferably 80 to 200 ° C, more preferably 100 to 150 ° C. . By setting the drying temperature to 80 ° C. or higher, transpiration of water or the like can be sufficiently promoted. On the other hand, by setting the drying temperature to 200 ° C. or less, it is possible to suppress non-uniformity of the active metal component due to rapid evaporation of water or the like.

  Moreover, 150-350 degreeC is preferable, as for baking temperature, 150-300 degreeC is more preferable, and 150-250 degreeC is further more preferable. If the calcination temperature greatly exceeds 350 ° C., manganese carbonate in the catalyst component decomposes into manganese oxide and carbon dioxide gas, which is not preferable. In order to produce the gasoline base material of the present invention, it is essential that manganese carbonate, which is an FT synthesis catalyst component, be present in the form of a carbonate, and manganese oxide has a high aromatic content and an octane number. It is difficult to obtain highly FT-reactive organisms. On the other hand, if the firing temperature is too low, activation of the FT active metal species cannot be achieved, which is not preferable.

  The time for drying and firing is not generally determined depending on the amount of treatment, but is usually 1 to 10 hours. If the treatment time is less than 1 hour, the transpiration of moisture may be insufficient, and the activation of the FT active metal species is diluted, which is not preferable. Further, even if the treatment time exceeds 10 hours, the catalytic activity is almost the same as the case of 10 hours or less. Therefore, in consideration of workability and productivity, 10 hours or less is preferable. The drying or baking treatment may be performed in the air, or may be an inert gas atmosphere such as nitrogen or helium, or a reducing gas atmosphere such as hydrogen, and is not particularly defined.

  In addition to the impregnation support method described above, as a method for producing an FT synthesis catalyst containing manganese carbonate and FT active metal species, an aqueous slurry containing manganese carbonate and FT active metal species is prepared and spray-dried. Can be mentioned. The concentration of the slurry at this time is not particularly specified, but if the slurry concentration is too low, manganese carbonate precipitates and the catalyst components become non-uniform, which is not preferable. On the other hand, if the slurry concentration is too high, it becomes difficult to feed the slurry, so an appropriate slurry concentration is selected. Further, at this time, silica sol or the like can be added as a binder component for the purpose of adjusting the concentration of the slurry, improving the moldability of the catalyst, and making it spherical. The amount of the binder added at this time is preferably such that the catalyst activity is not lowered, and is generally selected in the range of 5 to 20% by mass.

  When obtaining an FT synthesis catalyst by spray drying, a method of spraying a slurry containing manganese carbonate, an FT active metal species, and a binder component at the same time, or a slurry containing manganese carbonate and a binder is sprayed, and then the impregnation described above. In accordance with the loading method, there is a method of adding FT active metal species to the obtained spray-dried product. In addition, it is preferable to implement the ventilation temperature in spray-drying method within said drying and baking temperature.

  Other methods for preparing the FT synthesis catalyst constituting the catalyst composition used in the present invention include immersing manganese carbonate in an aqueous solution of FT active metal species to adsorb the active metal on manganese carbonate, Examples include a method of attaching an active metal to manganese carbonate by ion exchange, and a method of depositing an active metal on manganese carbonate by adding a precipitant such as an alkali when immersing manganese carbonate in an aqueous solution of an FT active metal species. It is done.

  Although the above-mentioned baking treatment has the objective of activating the FT active metal species, the activation can also be achieved by an alkaline aqueous solution treatment in addition to or in addition to the baking treatment. Specifically, a post-treatment is performed in which an FT synthesis catalyst in which FT active metal species is supported on manganese carbonate is immersed in an alkaline aqueous solution. As the alkaline aqueous solution, ammonia water, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution and the like can be used, and preferably ammonia water can be used. The alkali concentration in the alkaline aqueous solution is 0.05 to 1N, preferably 0.05 to 0.5N, more preferably 0.05 to 0.2N. When the alkali concentration is less than 0.05N, the effect of treating the alkaline aqueous solution becomes dilute, and there is a possibility that the catalytic activity is not so much improved even if the calcination treatment is performed thereafter. Conversely, if it exceeds 1N, the amount of unreacted alkali increases, which is uneconomical and increases the amount of water and time required for the cleaning treatment. In addition, although the time of alkaline aqueous solution treatment is based also on the density | concentration of an alkali component, 1 to 10 hours are preferable normally.

  After the treatment with an alkaline aqueous solution, the product is washed with water and the excess alkali content is sufficiently washed, and then the above-described drying and baking treatments are performed. The alkaline aqueous solution treatment is not particularly limited, and may be performed after drying or after firing after impregnating and supporting FT active metal species in manganese carbonate. Furthermore, it can also implement with respect to the catalyst obtained by performing spray drying, and the shape | molded catalyst.

  As a method of mixing the separately prepared FT synthesis catalyst and zeolite, for example, the FT synthesis catalyst and zeolite may be physically mixed to form a uniform mixture. The FT synthesis catalyst and zeolite are laminated in one container. It is good also as the laminated body filled up. In the case of a laminated body, it is sufficient that both of them are formed at least one layer. One container is filled with FT synthesis catalyst and zeolite alternately, and a layer made of FT synthesis catalyst and a layer made of zeolite are formed. It may be a laminated body laminated alternately.

  Moreover, when using a catalyst composition for an actual apparatus, shaping | molding is required, However A conventionally well-known method can be used also about shaping | molding. For example, the catalyst composition used in the present invention can be molded by subjecting a mixture of FT synthesis catalyst and zeolite to a known molding method. In addition, a catalyst composition obtained by impregnating and supporting an FT active metal on a composite molded body of manganese carbonate and zeolite by the above-described method is subjected to a known molding method, whereby the catalyst composition used in the present invention is obtained. Can be molded. Examples of such known molding methods include tableting molding, extrusion molding, and beading. In addition, these molding methods can be performed by a conventional method.

  When molding, the catalyst composition is mixed with silica or alumina as a binder component in order to improve moldability, or in order to improve extrudability, cellulosic molding aid or epoxy molding aid. It is also possible to add a molding aid such as PVA as long as it does not affect the catalytic activity.

  As a catalyst composition used for this invention, content of the zeolite in a catalyst composition is 30 mass% or more and 65 mass% or less. As the zeolite content in the catalyst composition increases, the decomposition or isomerization of n-paraffins and olefins is promoted, and the production amount of i-paraffins and aromatics having higher octane numbers increases. On the other hand, when the content of the zeolite in the catalyst composition is too large, overdecomposition occurs and the gasoline liquid yield becomes small. By setting the zeolite content in the catalyst composition within the above range, the gasoline yield can be increased while maintaining a high octane number of the product obtained by the FT reaction.

  When the catalyst composition used in the present invention is a composition containing an FT synthesis catalyst and a zeolite, the content of the FT synthesis catalyst in the catalyst composition is 10 to 70% by mass, preferably 35 to 70% by mass. It is. When the FT synthesis catalyst is contained in an amount of 10% by mass or more, hydrocarbon generation by the FT reaction proceeds sufficiently, which is preferable. When the content of the FT synthesis catalyst is 70% by mass or less, a sufficient amount of zeolite can be contained in the catalyst composition.

By using the catalyst composition used in the present invention, the CO conversion rate of the raw synthesis gas is high, the production of gas components is small, and high octane number components such as aromatics, naphthenes, olefins, and branched paraffin hydrocarbons are used. A gasoline fraction with high selectivity can be obtained in high yield from the synthesis gas by a one-stage reaction. Details regarding the ability to produce a high-octane gasoline fraction very efficiently as compared with the conventionally known methods using the catalyst composition have not yet been elucidated and are currently under intensive investigation, It is guessed as follows. In the reaction using the catalyst composition used in the present invention, the hydrocarbons synthesized from the synthesis gas by the FT synthesis catalyst are appropriately decomposed or isomerized by contacting with the zeolite showing the solid acid. In general, in order to efficiently perform the decomposition or isomerization reaction of hydrocarbons with zeolite, it is preferable to react the zeolite at 230 ° C. or higher. In the present invention, the use of an FT synthesis catalyst containing manganese carbonate as the FT synthesis catalyst suppresses the generation of gas components such as lower hydrocarbons having 1 to 4 carbon atoms and CO ₂ even at a high reaction temperature. It is speculated that hydrocarbons can be produced, and that a solid acid catalyst (zeolite) acts effectively at high temperatures, making it possible to produce a high-octane gasoline fraction.

<Method for Producing Gasoline Base Material of the Present Invention>
The gasoline fraction (20-200 ° C. fraction) of the product obtained by carrying out the one-step FT reaction using the catalyst composition used in the present invention can be used as the gasoline base material of the present invention. . The gasoline fraction can be recovered by a conventional method such as distillation.

  Examples of the type of the reactor for the FT reaction using the catalyst composition used in the present invention include a fixed bed, a fluidized bed, a suspension bed, and a slurry bed, and are not particularly limited. As an example, a method for producing hydrocarbons using a fixed bed will be described below.

  When evaluating the activity of the catalyst in a fixed bed, since the powder catalyst is concerned about the occurrence of differential pressure in the reactor, the shape of the catalyst is preferably a molded product such as an extruded product or a bead product. . The size of the catalyst composition depends on the scale of the reactor, but the particle size of the catalyst shape is preferably 0.5 mm to 5 mm, more preferably 1.0 mm to 3 mm. When the particle diameter is 0.5 mm or more, an increase in the differential pressure in the reactor can be sufficiently suppressed. On the other hand, when the particle diameter is 3 mm or less, the effectiveness factor of the catalyst can be improved, and the reaction can proceed efficiently.

  The catalyst composition used in the present invention is subjected to a reduction treatment (activation treatment) in advance before being subjected to the reaction. By this reduction treatment, the catalyst is activated so as to exhibit a desired catalytic activity in the reaction. If this reduction treatment is not performed, the FT active metal species are not sufficiently reduced and do not exhibit the desired catalytic activity. The reduction treatment temperature is preferably 140 to 350 ° C, more preferably 150 to 300 ° C. If it is less than 140 degreeC, FT active metal seed | species will not fully be reduced, and sufficient reaction activity will not be obtained. Further, at a high temperature significantly exceeding 350 ° C., there is a high possibility that decomposition of the catalyst component, manganese carbonate, into manganese oxide proceeds, leading to a decrease in activity.

  For this reduction treatment, a reducing gas mainly containing hydrogen can be preferably used. The reducing gas to be used may contain a certain amount of components other than hydrogen, for example, water vapor, nitrogen, rare gas, etc. within a range that does not hinder the reduction. This reduction treatment is affected by the hydrogen partial pressure and the treatment time as well as the treatment temperature. The hydrogen partial pressure in the reduction treatment is preferably 0.1 to 10 MPa, more preferably 0.5 to 6 MPa, and most preferably 0.9 to 3 MPa. The reduction treatment time varies depending on the amount of catalyst, the amount of hydrogen flow, etc., but is generally preferably 0.1 to 72 hours, more preferably 1 to 48 hours, and most preferably 3 to 48 hours. If the treatment time is less than 0.1 hour, the activation of the catalyst may be insufficient. On the other hand, even if the reduction treatment is performed for a long time exceeding 72 hours, there is no adverse effect on the catalyst, but no improvement in the catalyst performance is observed.

The FT reaction can be carried out by passing a synthesis gas through the catalyst composition used in the present invention subjected to the reduction treatment as described above.
The synthesis gas used may be mainly composed of hydrogen and carbon monoxide, and other components may be mixed as long as the reaction is not hindered. For example, as an example, in order to manufacture the gasoline base material of the present invention, synthesis gas obtained by gasifying biomass can be used. The types of biomass in this case include agricultural, forestry and fishery resource biomass such as food, building materials and pulp, waste biomass such as agriculture, forestry and livestock waste, and plantation biomass such as sugar cane, palm palm and seaweed. Among them, it is preferable to use unused waste biomass that does not compete with food. There is no particular limitation on the biomass gasification method. For example, biomass gasification methods include various types such as direct gasification, indirect gasification, atmospheric pressure gasification, and pressurized gas. Gasification furnace types include a fixed bed, a fluidized bed, and a spouted bed. When the gasoline base material of the present invention is produced using the catalyst composition used in the present invention, biomass gasified using any of these methods may be used.

Since the reaction rate (k) depends on the hydrogen partial pressure in the first order, the partial pressure ratio of hydrogen and carbon monoxide (H ₂ / CO molar ratio) is desirably 0.6 or more. Since this reaction is a reaction accompanied by volume reduction, it is preferable that the total value of the partial pressures of hydrogen and carbon monoxide is higher. The partial pressure ratio between hydrogen and carbon monoxide varies depending on the raw material type and gasification method in the above-described biomass gasification, but the upper limit is not particularly limited when the gasoline base material of the present invention is manufactured. .

  As a practical range of the hydrogen / carbon monoxide partial pressure ratio, 0.6 to 2.7 is appropriate, preferably 0.8 to 2.5, and more preferably 1 to 2.3. If the partial pressure ratio is less than 0.6, the yield of the generated hydrocarbons tends to decrease, and if the partial pressure ratio exceeds 2.7, the generated hydrocarbons tend to increase in gas components. It is done.

  Furthermore, when the gasoline base material of the present invention is produced using the catalyst composition used in the present invention, there is no problem even if carbon dioxide coexists in the synthesis gas. As carbon dioxide to be coexisted in the synthesis gas, for example, those obtained from a reforming reaction of petroleum products or natural gas can be used without any problem. Carbon dioxide mixed with other components that do not interfere with the FT reaction can also coexist in the synthesis gas. For example, carbon dioxide containing water vapor, partially oxidized nitrogen, or the like, such as that from a steam reforming reaction of petroleum products or the like, may be used.

  A gas obtained by positively adding such carbon dioxide to synthesis gas not containing carbon dioxide may be passed through the catalyst composition used in the present invention. Further, the catalyst composition used in the present invention as it is, without subjecting the synthesis gas containing carbon dioxide obtained by reforming natural gas by the self-thermal reforming method or the steam reforming method to the carbon dioxide. It can also be made to react by making it ventilate. By subjecting the synthesis gas containing carbon dioxide to the reaction as it is, it is possible to reduce the equipment construction cost and operation cost required for the decarboxylation treatment, and it is possible to reduce the production cost of the resulting hydrocarbons.

  The total pressure (total value of partial pressures of all components) of the synthesis gas (mixed gas) subjected to the reaction is preferably 0.3 to 10 MPa, more preferably 0.5 to 7 MPa, and further preferably 0.8 to 5 MPa. Low pressure is not preferable because chain growth becomes insufficient and the yield of gasoline, kerosene, wax, etc. tends to decrease. In terms of equilibrium, the higher the partial pressure of hydrogen and carbon monoxide, the more advantageous. However, the higher the partial pressure, the more expensive the plant construction costs, and the larger the compressors required for compression, the higher the operating costs. Tend to rise. Therefore, the upper limit of the partial pressure is restricted from an industrial viewpoint.

  The contact time between the synthesis gas and the catalyst in the FT reaction (hereinafter referred to as W / F: weight / flow [g · h / mol]) is preferably 1 to 100, more preferably 1.5 to 90, and even more preferably. 2-80. Although the value of W / F varies depending on the throughput and the performance of the catalyst used, generally, when W / F is 1 or more, a sufficient CO conversion is obtained and the yield of the liquid product is improved. Moreover, if W / F is 100 or less, an unnecessary increase in the size of the reactor due to an increase in the amount of catalyst used can be suppressed.

On the FT synthesis catalyst, generally, if the H ₂ / CO molar ratio of the synthesis gas is the same, the lower the reaction temperature, the higher the chain growth probability and C 5 + selectivity (selectivity for synthesis of hydrocarbons having 5 or more carbon atoms). Increases, but the CO conversion decreases. Conversely, if the reaction temperature increases, the chain growth probability and C5 + selectivity decrease, but the CO conversion increases. Also, the higher the H ₂ / CO ratio, the higher the CO conversion rate, the lower the chain growth probability and C5 + selectivity, and vice versa when the H ₂ / CO ratio is low. The effect of these factors on the FT reaction varies depending on the type of catalyst used, etc., but when the gasoline base material of the present invention is produced using the catalyst composition used in the present invention, the reaction temperature is 230-350 degreeC is employ | adopted, 240-310 degreeC is preferable and 250-300 degreeC is more preferable. If the reaction temperature is 230 ° C. or higher, both the FT synthesis catalyst and the zeolite work effectively, and it becomes possible to produce a high-octane gasoline fraction by the generation of hydrocarbons and their decomposition and isomerization reactions. . In addition, by setting the reaction temperature to 350 ° C. or lower, it is possible to suppress generation of undesirable gas components on the FT synthesis catalyst and to suppress generation of gas components due to overdecomposition on zeolite.

  In addition, CO conversion rate and the selectivity of various products are defined by the following formula. In the following formula, “C2-4 product” means a product having 2 to 4 carbon atoms.

[CO conversion rate]
CO conversion rate = [(number of CO moles in raw material gas per unit time) − (number of CO moles in outlet gas per unit time)] / (number of CO moles in raw material gas per unit time) × 100
[CH ₄ selectivity]
CH ₄ selectivity = (number of moles of CH _{4 in} outlet gas per unit time) / [number of moles of CO in raw material gas per unit time) − (number of moles of CO in outlet gas per unit time)] × 100
[CO ₂ selectivity]
CO ₂ selectivity = (number of moles of CO _{2 in} outlet gas per unit time) / [number of moles of CO in raw material gas per unit time) − (number of moles of CO in outlet gas per unit time)] × 100
[C2-4 selectivity]
C2-4 selectivity = (number of C moles in C2-4 product in outlet gas per unit time) / [number of CO moles in raw material gas per unit time) − (in outlet gas per unit time) Of CO moles)] × 100
[C5 + selectivity]
C5 + selectivity = 100 − [(CH ₄ selectivity) + (CO ₂ selectivity) + (C2-4 selectivity)]
[Gasoline selection rate]
Gasoline selectivity = C5 + selectivity x gasoline fraction ratio / 100
[C5 + yield]
C5 + yield = (CO conversion) × (C5 + selectivity) / 100
[Gasoline yield]
Gasoline yield = (C5 + yield) x gasoline fraction ratio / 100

  When a one-step FT reaction is performed using the catalyst composition used in the present invention, the product preferably has a gasoline yield of 40% or more and a gasoline selectivity of 50% or more. Since the gasoline yield is 40% or more and the gasoline selectivity is 50% or more, the raw material gas can be efficiently converted to gasoline, and more than half of the obtained product can be used as a gasoline fraction. It is preferable from the viewpoint of reducing the environmental load due to efficiency and energy saving. In particular, if the raw material gas is derived from biomass, the effect becomes greater. In addition, it is preferable to obtain a gasoline fraction with a high yield because it can contribute to an increase in gasoline production corresponding to gasoline demand especially in summer.

  EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not restrict | limited at all by these examples.

In the following examples, CO analysis was performed using a thermal conductivity gas chromatograph (TCD-GC) using Active Carbon (60/80 mesh) as a separation column. As the source gas, a synthesis gas (mixed gas of H ₂ and CO) added with 25% by volume of Ar as an internal standard was used. Qualitative and quantitative analysis was performed by comparing the peak position and peak area of CO with Ar. The composition analysis of the product was performed using a capillary column (TC-1) and a flame ion detector gas chromatograph (FID-GC). The chemical component of the catalyst was identified by ICP emission spectroscopy (CQM-10000P, manufactured by Shimadzu Corporation).

[Example 1]
Manganese carbonate (II) n hydrate manufactured by Wako Pure Chemical Industries was used as manganese carbonate. 15.5 g of manganese carbonate was weighed and manufactured by JGC Catalysts & Chemicals, silica sol SI-550 (SiO ₂ content: 20.6%) 18.8 g and ruthenium chloride (manufactured by Kojima Chemical Co., Ltd., Ru Assay: 40.79% by mass) 1 After mixing with .47 g and allowing to stand for 1 hour, it was calcined in air at 200 ° C. overnight. The obtained fired product was pulverized in a mortar to obtain catalyst a which is an FT synthesis catalyst. As a result of chemical composition analysis of the catalyst a by ICP emission spectroscopic analysis, ruthenium was 3.2% by mass in terms of metal.
3 g of catalyst a and 1.29 g of zeolite H-ZSM-5 (manufactured by Zude Chemie, MFI-90) showing a solid acid were sufficiently mixed to obtain catalyst A as a catalyst composition.
The total amount of catalyst A was diluted with 34.6 g of 100 mesh silicon carbide, filled into a reaction tube having an inner diameter of 15.5 mm, hydrogen partial pressure 0.9 MPa · G, temperature 170 ° C., flow rate 100 (STP) ml / min (STP : Standard temperature and pressure) for 3 hours. After the reduction, the reaction was carried out at a temperature of 270 ° C. and a total pressure of 0.9 MPa · G by switching to a synthesis gas (containing about 25% by volume of Ar) with an H ₂ / CO ratio of about 2.
The contact time (W / F: weight / flow [g · h / mol]) of the synthesis gas (H ₂ + CO) to the catalyst A was about 13.4 g · hr / mol. Since the mixed H-ZSM-5 does not show any activity for the FT reaction, W / F is represented by the contact time of the synthesis gas with the FT synthesis catalyst. Table 1 shows the results of the reaction and the fraction composition of the obtained liquid product, and Table 2 shows the results of composition analysis (including RON and MON) in the gasoline fraction of the liquid product.
In addition, the 20-200 degreeC fraction was made into the gasoline fraction. The fraction contains hydrocarbons having 5 to 11 carbon atoms.

[Example 2]
The reaction was performed in the same manner as in Example 1 except that the amount of H-ZSM-5 mixed with the catalyst a was 3 g. Tables 1 and 2 show the reaction results, the fraction composition of the obtained liquid product, and the results of composition analysis in the gasoline fraction.

[Example 3]
The reaction was performed in the same manner as in Example 1 except that the amount of H-ZSM-5 mixed with the catalyst a was 5.57 g. Tables 1 and 2 show the reaction results, the fraction composition of the obtained liquid product, and the results of composition analysis in the gasoline fraction.

[Reference Example 1]
The reaction was performed in the same manner as in Example 1 except that the amount of H-ZSM-5 mixed with the catalyst a was 0.33 g. Tables 1 and 2 show the reaction results, the fraction composition of the obtained liquid product, and the results of composition analysis in the gasoline fraction.

[Reference Example 2]
The reaction was performed in the same manner as in Example 1 except that the amount of H-ZSM-5 mixed with the catalyst a was 27 g. Tables 1 and 2 show the reaction results, the fraction composition of the obtained liquid product, and the results of composition analysis in the gasoline fraction.

From the results of Tables 1 and 2, when the catalyst compositions of Examples 1 to 3 containing 30 to 65% by mass of H-ZSM-5 are used, the gasoline selectivity in the FT reaction is 50% or more, and The gasoline yield was as high as 40% or more, and the gasoline fraction was efficiently produced from the raw material gas. Moreover, the octane number of the gasoline fraction of the obtained liquid product was also high. A gasoline selectivity of 50% or more is preferable from the viewpoint of reaction efficiency. On the other hand, when the catalyst composition of Reference Example 1 was used, the gasoline yield was 34.3%, not 50%, and a large amount of kerosene oil fraction and wax were produced. That is, it was not preferable as a gasoline fraction production. In addition, the octane number of the gasoline fraction of the obtained liquid product was low. Moreover, when the catalyst composition of Reference Example 2 was used, the octane number of the gasoline fraction of the obtained liquid product was high, but the gas component selectivity (CH ₄ selectivity, CO ₂ selectivity, C 2 -C4 selectivity) was higher than C5 + selectivity, and the liquid fraction could not be produced efficiently, which was not preferable.

Claims (5)

It contains one or more metals that are active in the Fischer-Tropsch reaction, manganese carbonate, and H-ZSM-5 , which is a zeolite showing a solid acid, and the content of the zeolite relative to the catalyst composition is 30 mass % To 65% by mass of a catalyst composition for producing hydrocarbons from a gas mainly composed of hydrogen and carbon monoxide,
(A) Research method octane number of 80-93,
(B) Motor method octane number of 74 to 83,
(C) The aromatic ratio is 3% by volume or more and less than 30% by volume,
(D) The proportion of olefins is 70% by volume or less,
(E) Oxygen content is 0.5 mass% or less,
(F) A method for producing a gasoline substrate, comprising producing a gasoline substrate having a benzene content of 0.5% by volume or less and (g) a sulfur content of 0.5 ppm by mass or less. The gasoline base is
(H) 10% by volume distillation temperature (T10) is 25.0-40.0 ° C, 50% by volume distillation temperature (T50) is 90.0-125.0 ° C, and 90% by volume distillation. The temperature (T90) is 160.0-180.0 ° C,
The method for producing a gasoline base material according to claim 1, wherein It contains one or more metals that are active in the Fischer-Tropsch reaction, manganese carbonate, and H-ZSM-5 , which is a zeolite showing a solid acid, and the content of the zeolite relative to the catalyst composition is 30 mass A gasoline fraction of a product obtained from a gas mainly composed of hydrogen and carbon monoxide using a catalyst composition for producing hydrocarbons that is not less than 65% and not more than 65% by mass;
(A) Research method octane number of 80-93,
(B) Motor method octane number of 74 to 83,
(C) The aromatic ratio is 3% by volume or more and less than 30% by volume,
(D) The proportion of olefins is 70% by volume or less,
(E) Oxygen content is 0.5 mass% or less,
(F) benzene is 0.5 volume% or less ,
(G) the sulfur content is 0.5 mass ppm or less, and
(H) 10% by volume distillation temperature (T10) is 25.0-40.0 ° C, 50% by volume distillation temperature (T50) is 90.0-125.0 ° C, and 90% by volume distillation. Temperature (T90) is 160.0-180.0 ° C
The gasoline base material characterized by being. Wherein the catalyst composition comprises a Fischer-Tropsch synthesis catalyst containing one or more metals and manganese carbonate showing the activity in the Fischer-Tropsch reaction, according to claim 3, characterized by containing a zeolite showing a solid acid Gasoline base material. The gasoline base material according to claim 3 or 4 , wherein the metal is ruthenium.