JP5978887B2 - Propylene and linear butene production method - Google Patents

Description

  The present invention relates to a process for producing propylene and linear butene by contacting ethylene and / or ethanol with a catalyst.

Conventional methods for producing olefins such as propylene and linear butene (1-butene, trans-2-butene, cis-2-butene), which are useful as raw materials for butadiene production, include naphtha steam cracking and vacuum gas oil. The fluid catalytic cracking method is mentioned, and the naphtha steam cracking method is mainly implemented. However, in the steam cracking method, ethylene is produced in large quantities, and it is difficult to greatly change the production ratio of the target olefins such as propylene and linear butene, so it is difficult to cope with changes in the balance between supply and demand. there were. In addition, since the butenes obtained by the steam cracking method contain a large amount of isobutene, there is a problem that the load of separation and purification becomes large when obtaining linear butene.
Therefore, a method for producing propylene and linear butene using ethylene as a raw material is desired for the purpose of effectively using ethylene produced in large quantities.

As a method for producing propylene, a method for directly producing propylene from ethylene has been proposed.
In Patent Document 1, propylene is produced in a high yield by contacting with ethylene and / or ethanol using a zeolite modified so that the outer surface acid amount of the zeolite is 5% or less based on the total acid amount. Is obtained.

Patent Document 2 describes a method for producing propylene using a steam-treated medium pore diameter aluminosilicate.
On the other hand, as a method for producing butenes, for example, a method for producing butenes by dimerization of ethylene using a Ziegler-Natta catalyst is known (Non-patent Document 1).

International Publication 2010/128644 Pamphlet International Publication No. 2009/031445 Pamphlet

Catalysis Today 14, (1992) 28

However, conventionally, a method for efficiently producing propylene and linear butene simultaneously from ethylene as a raw material has not been known.
In the method described in Patent Document 1, butenes are by-produced together with propylene. However, although the production amount of propylene is sufficient, the production amount of butenes is very small, and the production of butenes is not practical.

In the method described in Patent Document 2, the propylene yield is around 30%, and the amount of propylene produced is low. The yield of butenes (total of butene isomers) calculated from the examples is about 15%, and the combined yield of propylene and butenes is around 40%. Furthermore, the proportion of linear butene in the butenes produced is also unclear. For this reason, neither propylene production nor linear butene production is practical.

Regarding the ethylene dimerization reaction described in Non-Patent Document 1, although 1-butene is obtained in good yield, propylene is not obtained at all, which is undesirable from the viewpoint of simultaneous production with propylene. Furthermore, since the Ziegler-Natta catalyst used is very sensitive to moisture, there is a problem that when ethylene obtained by a dehydration reaction of ethanol is used as a raw material, it is necessary to once purify ethylene.
An object of the present invention is to provide a production method capable of simultaneously producing propylene and linear butene in high yield from ethylene and / or ethanol.

  As a result of intensive studies in order to solve the above problems, the present inventors have determined that an aluminosilicate having an oxygen 8-membered ring or oxygen 9-membered ring structure as a catalyst to be contacted with ethylene and / or ethanol is subjected to silylation treatment. It was found that by using a steam-treated and / or heat-treated product, propylene and linear butene can be simultaneously produced in good yield, and the present invention has been achieved.

That is, the gist of the present invention is as follows.
[1] A process for producing propylene and linear butene by bringing ethylene and / or ethanol into contact with a catalyst, wherein the active component of the catalyst has an oxygen 8-membered ring structure or an oxygen 9-membered ring structure In addition, a method for producing propylene and linear butene, characterized by being subjected to silylation treatment, steam treatment and / or heat treatment,
[2] The method for producing propylene and linear butene according to the above [1], wherein the aluminosilicate has a CHA type structure,
[3] The method for producing propylene and linear butene according to the above [1] or [2], wherein the aluminosilicate is silylated before being steamed and / or heat treated,
[4] Ethylene and / or ethanol and catalyst are brought into contact with ethylene and / or ethanol at a conversion rate of 60% or more, and propylene and straight chain according to any one of [1] to [3] above The production method of chain butene.

  According to the present invention, propylene and linear butene can be simultaneously and efficiently produced using ethylene and / or ethanol as raw materials. Moreover, since the amount of isobutene by-produced can be suppressed and linear butene can be selectively produced, it is possible to greatly reduce the load in the process of separating and purifying linear butene and isobutene.

Hereinafter, typical embodiments for carrying out the present invention will be specifically described. However, the present invention is not limited to the following embodiments unless the gist of the present invention is exceeded, and within the scope of the gist. Various modifications can be made.
The production method of the present invention is a method of producing propylene and linear butene by bringing ethylene and / or ethanol into contact with a catalyst, wherein the active component of the catalyst is an oxygen 8-membered ring structure or an oxygen 9-membered ring structure And the aluminosilicate is subjected to silylation treatment, steam treatment and / or heat treatment.
Hereinafter, the components in the present invention will be described.

<Catalyst>
(1) Aluminosilicate having an oxygen 8-membered ring or oxygen 9-membered ring structure The catalyst in the present invention is an aluminosilicate having an 8-membered ring or 9-membered ring structure as a catalytically active component (hereinafter sometimes simply referred to as aluminosilicate). Is included.
Aluminosilicate is a crystalline oxide containing silicon and aluminum as constituent atoms. The aluminosilicate has a tetrahedral structure of TO ₄ units (the atom represented by T is an atom other than oxygen among atoms constituting the skeleton of an aluminosilicate, also called a central atom) and shares an oxygen atom. Connected three-dimensionally to form open regular micropores.
The oxygen 8-membered or 9-membered ring structure means that the pores of the aluminosilicate are ring structures composed of 8 or 9 TO ₄ units.

Aluminosilicate is a kind of zeolite formed containing silicon, aluminum, and oxygen, and its structure can be defined by the structural classification of the zeolite.
As an aluminosilicate in which the pore contains an oxygen 8-membered ring, specifically, expressed by a code defined by International Zeolite Association (IZA), for example, AEI, AFX, CAS, CHA, DDR, ERI, ESV, GIS, GOO, ITE, JBW, KFI, LEV, LTA, MER, MON, MTF, PAU, PHI, RHO, RTE, RTH, RWR, UFI and the like.

Specifically, the aluminosilicate in which the pore contains an oxygen 9-membered ring includes an oxygen 9-membered ring and an oxygen 9-membered ring such as LOV, NAT, RSN, etc. And those containing an oxygen 7-membered ring together with an oxygen 9-membered ring, such as STT.
The pore diameter of the aluminosilicate having an oxygen 8-membered ring or oxygen 9-membered ring structure varies depending on the structure, but is generally about 3 to 5 mm. Therefore, when used as a catalyst, depending on the size of the pore diameter, Since diffusion of branched olefins outside the pores is suppressed, linear butene can be obtained with high selectivity in addition to propylene.

  Among these, as the skeleton structure of the aluminosilicate in the present invention, AFX, CHA, DDR, ERI, KFI, LEV, LTA, RHO, RTH, and UFI are preferable, and CHA is more preferable. These structures are preferable because the framework density described later is small, so that pore clogging is unlikely to occur even when coking into the pores proceeds in the hydrocarbon conversion reaction.

CHA-type aluminosilicate is an aluminosilicate with a three-dimensional pore consisting of an 8-membered oxygen ring with a crystal structure equivalent to that of naturally occurring chabazite and a diameter of 3.8 × 3.8 mm. is there. Its structure is characterized by X-ray diffraction data.
The framework density of the aluminosilicate is not particularly limited, but the framework density is usually 18.0 T / nm ³ or less, preferably 17.0 T / nm ³ or less, usually 11.0 T / nm. ³ or more, preferably 12.0 T / nm ³ or more. It exists in the point which a pore obstruction | occlusion does not occur easily in the conversion reaction of hydrocarbon because it exists in the said range.

Here, the framework density (unit: T / nm ³ ) means the number of atoms (T atoms) other than oxygen forming a skeleton existing per unit volume (1 nm ³ ) of aluminosilicate, and this value is It depends on the structure of the aluminosilicate. The relationship between framework density and aluminosilicate structure is shown in ATLAS OF ZEOLITE FRAMEWORK TYPES Sixth Revised Edition 2007 ELSEVIER.

The SiO ₂ / Al ₂ O ₃ molar ratio of the aluminosilicate used in the present invention is not particularly limited, but is usually 5 or more, preferably 8 or more, more preferably 10 or more, and usually 1000 or less. , Preferably 300 or less, more preferably 200 or less, still more preferably 100 or less. The SiO ₂ / Al ₂ O ₃ molar ratio in the aluminosilicate is a value determined on the assumption that all Si atoms in the produced aluminosilicate are contained as SiO ₂ and Al atoms are contained as Al ₂ O ₃ . If the molar ratio is too high, the acid amount is small, so the ethylene conversion rate may decrease.If the molar ratio is too low, deactivation due to coke adhesion and accumulation is accelerated, and aluminum tends to escape from the skeleton. There are cases where the acid strength per acid point becomes weak.

  The method for producing an aluminosilicate used in the present invention is not particularly limited, and can be produced by a known method described in, for example, US Pat. No. 4,544,538 and JP-A 2011-102209. In general, it can be prepared by a hydrothermal synthesis method. In addition, after the hydrothermal synthesis, treatments such as ion exchange, dealumination treatment, impregnation, etc., and aluminosilicate composition changed can be used.

Specifically, the aluminosilicate is usually used in a proton type (hereinafter also referred to as H type), but a part thereof is exchanged with an alkali metal such as Na or K, or an alkaline earth metal such as Mg or Ca. It may be.
In the production method of the present invention, a product obtained by subjecting the aluminosilicate to silylation treatment, steam treatment and / or heat treatment is used. Hereinafter, these processing methods will be described.

(2) Silylation treatment The silylation treatment of aluminosilicate is a method in which the amount of acid on the outer surface is reduced by silylating the outer surface acid sites of aluminosilicate, or the pore diameter of the crystal opening is reduced. is there. The method of silylation is not particularly limited, and a known method can be used as appropriate. Specifically, liquid phase silylation using alkoxysilane, gas phase silylation using chlorosilane, or the like is performed. be able to. Hereinafter, silylation in the liquid phase will be specifically described.

<Silylating agent>
The silylating agent is not particularly limited as long as it is a molecule that can silylate the aluminosilicate surface and cannot silylate the pores of the aluminosilicate. Silicone, chlorosilane, alkoxysilane , Siloxane, silazane and the like can be used. Of these, a preferred silylating agent is alkoxysilane.

  Specific examples of silicone include dimethyl silicone, diethyl silicone, phenylmethyl silicone, methyl hydrogen silicone, ethyl hydrogen silicone, phenyl hydrogen silicone, methyl ethyl silicone, phenyl ethyl silicone, diphenyl silicone, methyl trifluoropropyl silicone, Ethyl trifluoropropyl silicone, tetrachlorophenyl methyl silicone, tetrachlorophenyl ethyl silicone, tetrachlorophenyl hydrogen silicone, tetrachlorophenyl silicone, methyl vinyl silicone, ethyl vinyl silicone and the like are used.

Specific examples of chlorosilane include tetrachlorosilane, trichlorosilane, trichloromethylsilane, dichlorodimethylsilane, chlorotrimethylsilane, trichloroethylsilane, dichlorodiethylsilane, and chlorotriethylsilane.
Specific examples of the alkoxysilane include tetramethoxysilane, tetraethoxysilane and the like; quaternary alkoxysilane, trimethoxymethylsilane, trimethoxyethylsilane, triethoxymethylsilane, triethoxyethylsilane and the like; tertiary alkoxy Silane, dimethoxydimethylsilane, dimethoxydiethylsilane, diethoxydimethylsilane, diethoxydiethylsilane, etc .; secondary alkoxysilane, methoxytrimethylsilane, methoxytriethylsilane, ethoxytrimethylsilane, ethoxytriethylsilane, etc.
Grade alkoxysilanes are used. A secondary or higher alkoxysilane is preferable, a tertiary or higher alkoxysilane is more preferable, and a quaternary alkoxysilane is more preferable.

Specific examples of siloxane include hexamethyldisiloxane, hexaethyldisiloxane, pentamethyldisiloxane, tetramethyldisiloxane, and the like, and hexamethyldisiloxane is preferred.
Specific examples of the silazane include hexamethyldisilazane, dipropyltetramethyldisilazane, diphenyltetramethyldisilazane, tetraphenyldimethyldisilazane, and the like, and hexamethyldisilazane is preferable.

<Solvent>
The solvent for the silylation in the liquid phase is not particularly limited, and an organic solvent such as hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane, benzene, toluene, xylene, or an aqueous solvent is used. Can be used. In the aqueous solvent system, an acidic aqueous solution to which an acid such as sulfuric acid or nitric acid is added can be used to promote the silylation reaction.

<Moisture content>
When silylation is performed in the liquid phase, a specific range of moisture may be imparted to the aluminosilicate to be subjected to the silylation treatment. The moisture contained in the aluminosilicate may be originally contained in the aluminosilicate, or may be adjusted to a specific range by artificially supplying moisture. Usually, the aluminosilicate is obtained by calcining a product obtained by hydrothermal synthesis, and further converting to an ammonium type and then calcining as necessary to convert to a proton type. Therefore, it is assumed that the water content of the aluminosilicate before silylation is usually very low, and it may be subjected to silylation treatment as it is, or water is supplied to the aluminosilicate so as to contain a specific water content. The amount may be adjusted and used (hereinafter sometimes referred to as humidity conditioning treatment).
In addition, the water content is not particularly limited, but is expressed in terms of wt% of the moisture content contained in the aluminosilicate with respect to the dry aluminosilicate weight, usually 30 wt% or less, preferably 25 wt% or less, The lower limit is 0% by weight in a completely dry state. When the upper limit is exceeded, pores are blocked by excessive silylation coating, and the catalytic activity tends to decrease.

<Humidity treatment method>
The humidity control method is not particularly limited as long as it can be adjusted to a predetermined moisture content. For example, humidity control can be performed by leaving aluminosilicate in an atmosphere having an appropriate relative humidity. Moreover, humidity control can also be performed by placing a container containing water in a desiccator and placing aluminosilicate in a saturated water vapor atmosphere and leaving it to stand. In some cases, humidity control can also be performed under conditions in which the water vapor pressure in the desiccator is adjusted by allowing a container containing a saturated aqueous solution of an inorganic salt such as ammonium chloride or ammonium sulfate to coexist. In addition, humidity can be controlled by circulating a gas having an appropriate water vapor pressure. In addition, in order to perform a more uniform humidity control, you may perform a humidity control process, mixing or stirring aluminosilicate.

<Reaction raw material composition>
The amount of the silylating agent relative to the aluminosilicate is not particularly limited, but is usually 0.001 mol or more, preferably 0.01 mol or more, more preferably 0.1 mol, per 1 mol of aluminosilicate. That's it. Moreover, it is 5 mol or less normally, Preferably it is 3 mol or less, More preferably, it is 1 mol or less. When the amount of the silylating agent is less than the lower limit, silylation becomes insufficient, and the effect of silylation may be reduced.
The silylating agent may be excessively laminated to block the pores. The amount of the silylating agent is expressed in terms of the number of moles of Si atoms contained in the silylating agent. In the case of a silylating agent having a plurality of Si atoms in the molecule, the total number of moles of Si atoms is converted to silylation. It will be treated as the number of moles of agent.

  The amount of the solvent relative to the aluminosilicate in the case of performing silylation in the liquid phase is not particularly limited, but is usually 1 g or more, preferably 3 g or more, more preferably 5 g or more with respect to 1 g of aluminosilicate. . Moreover, it is 100 g or less normally, Preferably it is 60 g or less, More preferably, it is 20 g or less. When the amount of the solvent relative to the aluminosilicate is less than the lower limit, stirring of the slurry may be insufficient, and when the amount exceeds the upper limit, productivity may be lowered.

  The concentration of the silylating agent in the hydrocarbon solvent when performing silylation in the liquid phase is not particularly limited, but is usually 0.01% by weight or more, preferably 0.5% by weight or more. Preferably it is 1 weight% or more. Moreover, it is 80 weight% or less normally, Preferably it is 60 weight% or less, More preferably, it is 40 weight% or less. If the silylating agent concentration is less than the lower limit, the reaction time tends to be long because the silylation rate decreases, and if the silylating agent concentration exceeds the upper limit, condensation between silylating agents in the solution tends to occur. Tend to be.

<Reaction conditions>
The temperature for the silylation treatment depends on the kind of the silylating agent and the solvent, but is not particularly limited, and is usually 20 ° C. or higher, preferably 40 ° C. or higher, more preferably 60 ° C. or higher. Moreover, it is 140 degrees C or less normally, Preferably it is 120 degrees C or less, More preferably, it is 100 degrees C or less. If the amount is less than the lower limit, the progress of silylation tends to be slow. If the amount exceeds the upper limit, moisture in the aluminosilicate pores is greatly lost, and the silylation efficiency may be lowered.

  The time required to raise the temperature to the silylation temperature after adding the silylating agent is not particularly limited, and the silylating agent may be added at the silylation temperature, but is usually 0.01 hours. As described above, preferably 0.05 hours or more, more preferably 0.1 hours or more, and there is no particular upper limit for the time required for temperature increase. When the silylation temperature is high, if the time required for the temperature rise is too short, the water discharge rate from the aluminosilicate pores increases, the hydrolysis and polymerization reaction of the silylating agent in the solution proceeds, and The silylation efficiency on the surface may decrease.

  The treatment time for silylation depends on the reaction temperature, but is usually 0.1 hour or longer, preferably 0.5 hour or longer, more preferably 1 hour or longer, as long as the performance of the catalyst is not impaired. There is no upper limit. If the treatment time is too short, sufficient silylation does not occur, and the decrease in the acid amount on the outer surface may be insufficient.

It is considered that the aluminosilicate is coated with the acid sites on the outer surface by the silylation treatment, and deactivates to reduce the outer surface acid amount. When the outer surface acid amount decreases, side reactions occurring on the outer surface of the aluminosilicate are suppressed. Specifically, raw material ethylene, propylene generated in the pores of aluminosilicate, and linear butene come into contact with acid sites on the outer surface of the aluminosilicate, thereby suppressing the formation of components other than the target product. It is considered effective. In addition, the silylation of the acid points on the outer surface also binds to the acid points that make up the pores, so the pore diameter at the outer surface opening is slightly reduced, suppressing the molecular diffusion outside the crystal. It is thought that there is also. Thereby, it is considered that generation of hydrocarbons having 5 or more carbon atoms, which are larger molecules, can be suppressed.
In the present invention, steam treatment (steaming) and / or heat treatment is performed on the silylated aluminosilicate.

(3) Steam Treatment The steam treatment method of aluminosilicate is not particularly limited, and specifically, a method of contacting water vapor or air containing steam and / or an inert gas, ethylene and / or ethanol. In addition, a method of contacting with a reaction atmosphere containing water vapor, a method of contacting with a reaction atmosphere generating water vapor, or the like may be mentioned. The reaction that generates water vapor is a reaction that generates water vapor by dehydration, such as the dehydration reaction of ethanol. Although the water vapor may partially exist as liquid water depending on the conditions, it is preferable that the whole be present in the state of water vapor in order to give the aluminosilicate a uniform water vapor treatment effect.

  The steaming temperature of the aluminosilicate is not particularly limited, but is usually 400 ° C or higher, preferably 500 ° C or higher, more preferably 550 ° C or higher. Moreover, it is 850 degrees C or less normally, Preferably it is 750 degrees C or less, More preferably, it is 700 degrees C or less. When the temperature is too low, the effect of the steam treatment is small, and the linear butene yield may be reduced. When the upper limit is exceeded, the structure of the aluminosilicate may be collapsed.

  The water vapor (steam) used for the water vapor treatment can be diluted with helium, nitrogen, air or the like. The water vapor concentration is not particularly limited, but is usually 3% by volume or more, preferably 5% by volume or more, more preferably 10% by volume or more, based on the total gas used when the aluminosilicate is treated. Is not particularly limited, and 100% by volume of water vapor can be used. When the water vapor concentration is lower than the above range, the effect of the water vapor treatment is small, and the water vapor treatment for achieving the desired linear butene yield may require a long treatment time.

The water vapor treatment time of the aluminosilicate is not particularly limited, but is usually 0.1 hour or longer, preferably 0.5 hour or longer, more preferably 1 hour or longer. Further, there is no upper limit of the treatment time as long as the catalyst activity is not significantly inhibited. The treatment time can be appropriately adjusted depending on the steam treatment temperature and the water vapor concentration.
In the aluminosilicate, the aluminum atoms forming the skeleton are desorbed by steam treatment (hereinafter simply referred to as dealumination), so that not only the outer surface acid amount of the crystal described later but also the acid amount of the entire crystal ( Hereinafter, the total acid amount) is considered to decrease.

As an effect of the water vapor treatment in the present invention, the generation of coke that inhibits the diffusion of molecules inside the pores of the aluminosilicate is suppressed by dealumination from the skeleton, thereby reducing the total acid amount. It is speculated that the improvement of diffusion promotes the production of linear butene, which is a molecule larger than propylene.
Note that, by strengthening the steam treatment, larger molecules can be produced, and the production amount of hydrocarbon molecules having a large number of carbon atoms such as pentene and hexene tends to increase. Therefore, in order to increase the yield of linear butene and increase the total yield with propylene, the yield of linear butene is improved and the amount of hydrocarbons having 5 or more carbon atoms is not increased. To appropriate steam treatment conditions.

  The steam treatment of the aluminosilicate may be performed in a state where organic substances are present inside the pores. The presence of organic substances inside the pores makes it possible to greatly reduce the acid points on the outer surface while preventing an extreme decrease in the acid points inside the pores, particularly when a strong steam treatment is performed. Although it does not specifically limit as an organic substance, The structure directing agent used at the time of the hydrothermal synthesis of aluminosilicate, the coke produced | generated by reaction, etc. are mentioned. These organic substances can be removed through a combustion process such as air firing after steaming the aluminosilicate after hydrothermal synthesis (hereinafter sometimes referred to as as-made aluminosilicate), or air or the like. By treating with steam diluted with an oxygen-containing gas, steam treatment can be performed while removing organic substances.

It is also possible to physically mix the aluminosilicate with a compound containing an alkaline earth metal before subjecting the aluminosilicate to steam treatment. By adding an alkaline earth metal, the strong acid point of the aluminosilicate may be neutralized and the production of coke generated at the strong acid point may be suppressed. Examples of the compound containing an alkaline earth metal include calcium carbonate, calcium hydroxide, and magnesium carbonate, among which calcium carbonate is preferable.
The amount of the compound containing an alkaline earth metal is preferably 0.5% by weight to 45% by weight with respect to the aluminosilicate. More preferably, it is 3 to 40% by weight.

(4) Heat treatment The method of heat-treating the aluminosilicate is not particularly limited, but specifically, before being subjected to the synthesis reaction of propylene and straight-chain butene, the temperature is high in an air and / or inert gas atmosphere. The method of processing, or the method of high-temperature processing in the mixed gas atmosphere containing ethylene and / or ethanol in the synthesis reaction of propylene and a linear butene etc. are mentioned.
The aluminosilicate is considered to have the same effect as the above-described steam treatment in that dealumination occurs by heat treatment and the total acid amount is reduced.

The heat treatment temperature is not particularly limited, but is usually 600 ° C. or higher, preferably 700 ° C. or higher, usually 1000 ° C. or lower, preferably 900 ° C. or lower. If the heat treatment temperature is too low, the effect of the heat treatment may be small, and the yield of linear butene may be reduced. If it is too high, the structure of the aluminosilicate may be collapsed and the catalytic activity may be reduced.
As the gas species used for the heat treatment, helium, nitrogen, air, or the like can be used.

The heat treatment time is not particularly limited, but is usually 0.1 hour or longer, preferably 0.5 hour or longer, and more preferably 1.0 hour or longer. Further, there is no upper limit of the treatment time as long as the catalyst activity is not significantly inhibited, and the treatment time can be appropriately adjusted depending on the heat treatment temperature.
Further, the heat treatment may be performed in a state where organic substances are present inside the pores, similarly to the steam treatment. When an inert gas such as helium or nitrogen is used, the organic substance may be carbonized by heat treatment, but can be removed by firing with air.

The aluminosilicate used in the present invention has been subjected to silylation treatment, steam treatment and / or heat treatment. The reason why performing both of these treatments is effective for the simultaneous production of propylene and linear butene is not clear, but is presumed as follows.
As described above, the effect of steam treatment and heat treatment is to reduce the total acid amount by dealumination from the skeleton, thereby suppressing the formation of coke, improving the molecular diffusion in the pores, and generating in the pores. Propylene and linear butene are considered to be easily diffused out of the pores.

  The silylation treatment is considered to be a modification to inactivate acid points on the outer surface and suppress side reactions that occur on the outer surface of the aluminosilicate, specifically to improve the selectivity of propylene. It is done. Steam treatment and heat treatment are thought to bring a certain amount of the same effect as silylation treatment, but silylation treatment that mainly acts on the outer surface acid sites has a greater effect of inactivating the outer surface acid sites. it is conceivable that. Therefore, it is considered that propylene and linear butene can be obtained in high yield by using a catalyst modified by a combination of silylation treatment, steam treatment and / or heat treatment.

The degree of silylation treatment and steam and / or heat treatment is appropriately adjusted according to the desired production ratio of propylene and linear butene. When it is desired to produce by increasing the linear butene ratio in the reaction product, it is desirable to relax the silylation treatment and perform the steam treatment under more severe conditions.
Since the yield of propylene and linear butene is determined by the degree of silylation and steam and / or heat treatment, the treatment conditions can be adjusted according to the structure of the aluminosilicate and the acid amount while actually confirming the reaction results. Good.

  Although the processing order is not limited, it is preferable to perform steam treatment and / or heat treatment after silylation treatment. In the silylation treatment, the coating efficiency of the acid surface on the outer surface tends to be higher when the amount of acid on the outer surface before steaming and / or heat treatment is higher, and this order is more suitable for isobutene in butenes. It is preferable at the point which can reduce the ratio of this, and the point which can suppress the production | generation of C5 or more hydrocarbons.

  The outer surface acid amount of the above-treated aluminosilicate used as a catalyst in the production method of the present invention is not particularly limited, but usually the total acid amount of the aluminosilicate crystals after the above treatment (hereinafter referred to as “aluminosilicate”). The total acid amount) is preferably 5% or less. The total acid amount of the crystal is the sum of the amount of acid points present in the pores of the crystal and the amount of acid points on the outer surface. When the amount of acid on the outer surface is too large, the selectivity of propylene and linear butene tends to decrease due to side reactions occurring at the acid points on the outer surface. This is presumably because the reaction proceeding at the outer surface acid sites generates hydrocarbons other than the target product. Further, it is presumed that the propylene and linear butene produced in the pores of the catalyst further react on the outer surface also contribute to the decrease in selectivity.

In addition to the silylation of the outer surface of the aluminosilicate, the method of reducing the acid amount on the outer surface includes steam treatment of the aluminosilicate, heat treatment of the aluminosilicate, and binder and aluminosilicate when forming the aluminosilicate. The method may be such that the outer surface acid sites are bonded, and after the silylation treatment, these methods can be additionally reduced.
In addition, about the value of the outer surface acid amount of the aluminosilicate used in this invention, and the total acid amount, it is the value measured by the method as described in international publication 2010/128644 pamphlet.

  The aluminosilicate that has been subjected to the above treatment may be used as it is as a catalyst in the reaction, or it may be used for the reaction by granulating / molding using a substance or binder that is inert to the reaction, or by mixing them. Also good. The aluminosilicate that has been subjected to the above treatment becomes an active component of the catalyst. Therefore, the aluminosilicate in the catalyst is sometimes referred to as a “catalytic active component”.

Examples of the substance or binder inert to the reaction include alumina or alumina sol, silica, silica sol, quartz, and a mixture thereof. When the amount of acid on the outer surface is reduced relative to the total amount of acid by molding, molding using silica as a binder is preferable.
When a binder having an acid point such as alumina is used, the total acid amount and the external surface acid amount are measured as a total value including the acid amount of the binder together with the acid amount of the aluminosilicate. The In that case, it is possible to determine the amount of acid derived from the binder by another method and subtract the value to determine the total amount of acid and the amount of outer surface acid that do not include the amount of acid derived from the binder. The method for determining the acid amount of the binder is not particularly limited. For example, in ²⁷ Al-NMR, the total acid amount of aluminosilicate is determined from the peak intensity of 4-coordinated Al derived from an aluminosilicate acid point, Examples include a method of subtracting from the total value of the total amount of aluminosilicate to be obtained and the acid amount derived from the binder.

(5) Propylene and linear butene production method In the present invention, propylene and linear butene are produced by bringing ethylene and / or ethanol into contact with a catalyst containing an aluminosilicate that has undergone the above treatment (hereinafter referred to as the present invention). This is referred to as a method for producing propylene and linear butene in the invention. Hereinafter, the manufacturing method will be described.

(5-1) Reaction method <Reaction raw material>
The raw material ethylene is not particularly limited. For example, ethylene produced by catalytic cracking or steam cracking from petroleum sources, ethylene obtained by performing Fischer-Tropsch synthesis using hydrogen / CO mixed gas obtained by gasification of coal as raw material, or ethane dehydrogenation or Ethylene obtained by oxidative dehydrogenation, ethylene obtained by metathesis reaction and homologation reaction, ethylene obtained by MTO (Methanol to Olefin) reaction, ethylene obtained by dehydration reaction of ethanol, ethylene obtained by oxidative coupling of methane, Ethylene obtained by other various known methods can be arbitrarily used. At this time, a state in which a compound other than ethylene resulting from various production methods is arbitrarily mixed may be used as it is, or purified ethylene may be used, but purified ethylene is preferable.

  Ethanol used for the raw material is not particularly limited. For example, those obtained by various known methods such as those produced by hydration reaction of ethylene, those produced from synthesis gas, and those produced by fermentation using plant-derived polysaccharides as raw materials are arbitrarily used. In this case, a compound in which a compound (particularly water) resulting from each production method is arbitrarily mixed may be used as it is, or purified ethanol may be used.

Ethanol is easily dehydrated and converted to ethylene by the acid sites present in the aluminosilicate. Therefore, ethanol may be directly introduced into the reactor as a raw material. Hereinafter, the production method using ethanol as a raw material will be handled in the same manner as the production method using ethylene as a raw material on the basis of ethylene converted by dehydration.
Moreover, when producing propylene and linear butene according to the present invention, olefin contained in the reactor outlet gas may be recycled to the reactor inlet. The olefin to be recycled is usually ethylene, but other olefins may be recycled. As the olefin to be a raw material, a lower olefin is preferable, and a branched chain olefin is not preferable because it is difficult to enter the pores of the aluminosilicate because of the molecular size. The lower olefin is preferably ethylene, but propylene or linear butene may be recycled depending on the desired production ratio of propylene and linear butene.

<Reactor>
In the method for producing propylene and linear butene of the present invention, propylene and linear butene are usually produced by contacting ethylene with a catalyst in a reactor. Although the form of the reactor to be used is not particularly limited, a continuous fixed bed reactor or a fluidized bed reactor is usually selected. Preferably, it is a fluidized bed reactor.

When packing the above-mentioned catalyst into the fluidized bed reactor, in order to suppress the temperature distribution of the catalyst layer to a small level, particles that are inert to the reaction such as quartz sand, alumina, silica, and silica-alumina are mixed with the catalyst. And may be filled. In this case, there is no particular limitation on the amount of granular material inert to the reaction such as quartz sand. In addition, it is preferable that a granular material is a particle size comparable as a catalyst from the surface of uniform mixing property with a catalyst.

<Diluent>
In the reactor, in addition to ethylene, helium, argon, nitrogen, carbon monoxide, carbon dioxide, hydrogen, water (steam), paraffins, hydrocarbons such as methane, aromatic compounds, and their Gases that are inert to the reaction, such as a mixture, can be present, but among these, it is preferable that hydrogen coexists.

(5-2) Reaction conditions <Substrate concentration>
There is no particular limitation on the concentration of ethylene (that is, the substrate concentration) in all the feed components fed to the reactor, but it is usually at least 5 mol%, usually at most 90 mol%, preferably at most 70 mol%. If the substrate concentration is less than the lower limit, the reaction rate decreases, so a large amount of catalyst is required, and the reactor tends to be too large. Moreover, when the said upper limit is exceeded, the production | generation of an aromatic compound and paraffin becomes remarkable, and there exists a tendency for the selectivity of a propylene and a linear butene to fall.
Therefore, it is preferable to dilute ethylene with the above-mentioned diluent as necessary so as to obtain such a substrate concentration.

<Space velocity>
The space velocity mentioned here is a flow rate (weight / hour) of ethylene as a reaction raw material per weight of the catalyst (catalytic active component). Here, the catalyst weight is the weight of an inactive component used for granulation / molding of the catalyst and a catalytically active component that does not contain a binder.
The space velocity is not particularly limited, but is usually 0.01 Hr ⁻¹ or more, preferably 0.1 Hr ⁻¹ or more, and usually 500 Hr ⁻¹ or less, preferably 100 Hr ⁻¹ or less. If the space velocity is less than the lower limit, the production of hydrocarbons having 5 or more carbon atoms, aromatic compounds, paraffins and the like tends to increase, and the selectivity for propylene and linear butene tends to decrease. On the other hand, when the upper limit is exceeded, unreacted ethylene tends to increase, and the yield of propylene and linear butene tends to decrease.

<Reaction temperature>
The reaction temperature is not particularly limited as long as ethylene is in contact with the catalyst to produce propylene and linear butene, but is usually 200 ° C. or higher, preferably 300 ° C. or higher, and usually 700 ° C. or lower. The temperature is preferably 600 ° C. or lower. When the reaction temperature is less than the lower limit, the reaction rate tends to be low, the amount of unreacted ethylene tends to increase, and the yield of propylene and linear butene tends to decrease. On the other hand, if the reaction temperature exceeds the upper limit, coke deposition becomes remarkable, the yields of propylene and linear butene tend to decrease, and the catalyst life tends to be shortened. Moreover, since the increase in the amount of coke produced decreases the molecular diffusion in the pores of the aluminosilicate, the ratio of propylene / linear butene tends to increase, and the linear butene yield tends to decrease.

<Reaction pressure>
The reaction pressure is not particularly limited, but is usually 1 kPa (absolute pressure, the same applies hereinafter) or more, preferably 50 kPa or more, more preferably 100 kPa or more. Moreover, it is 3 MPa or less normally, Preferably it is 1 MPa or less, More preferably, it is 0.7 MPa or less. When the reaction pressure is less than the lower limit, the reaction rate tends to decrease, and when the upper limit is exceeded, the amount of undesired by-products such as paraffins increases, and the selectivity for propylene and linear butene tends to decrease. There is.

<Catalyst regeneration>
The catalyst subjected to the reaction can be regenerated and used. Specifically, a catalyst having a reduced ethylene conversion can be regenerated using various known catalyst regeneration methods.
The regeneration method is not particularly limited. Specifically, for example, the regeneration can be performed using air, nitrogen, water vapor, hydrogen, or the like, and the regeneration is preferably performed using hydrogen (for example, Japanese Patent Application Laid-Open No. 2011-2011). Can be reproduced in accordance with the method described in Japanese Patent No. -78962.

<Conversion rate>
In the production method of the present invention, the conversion rate of ethylene is not particularly limited, but the conversion rate is usually 60% or more, preferably 65% or more, more preferably 70% or more.
In the present invention, propylene and linear butene can be produced in a high yield by reacting so that the conversion rate of ethylene is 60% or more, and can be produced at a higher linear butene / propylene ratio. it can. The higher the ethylene conversion, the higher the linear butene / propylene ratio tends to be. On the other hand, the upper limit of the ethylene conversion is not particularly limited, but is usually less than 100%, preferably 98% or less, more preferably 95% or less, and still more preferably 90% or less. When the conversion rate is around 100%, the amount of by-products such as paraffins increases, and the selectivity for propylene and linear butene tends to decrease.

Usually, since the conversion rate of ethylene tends to decrease as the reaction time elapses, the catalyst that has been reacted for a certain period of time needs to be subjected to regeneration treatment. The method for operating in the above ethylene conversion range is not particularly limited.
For example, when the reaction is carried out in a fixed bed reactor, a plurality of reactors are provided in parallel, and when the ethylene conversion rate falls from the above preferred range, the contact between the catalyst and the reaction raw material is stopped. The catalyst is subjected to a regeneration step. In a fixed bed reactor, the reaction time and the regeneration time are appropriately adjusted, that is, the time for switching between the reaction step and the regeneration step in the operation is appropriately adjusted, thereby continuously operating at the ethylene conversion rate in the above preferred range. can do.

  When the reaction is carried out in a fluidized bed reactor, a catalyst regenerator is attached to the reactor, the catalyst extracted from the reactor is continuously sent to the regenerator, and the catalyst regenerated in the regenerator is removed. The reaction is preferably carried out while continuously returning to the reactor. By appropriately adjusting the residence time of the catalyst in the reactor and the residence time in the regenerator, the catalyst can be continuously operated at an ethylene conversion rate in the above preferred range.

Moreover, as a method for maintaining a high ethylene conversion rate for a long time, there is a method for suppressing coke accumulation in the catalyst by reacting ethylene in a hydrogen atmosphere described in JP-A-2011-79818.
The conversion rate is a value calculated by the following formula.
Ethylene conversion (%) = [[Reactor inlet ethylene (mol / Hr) −Reactor outlet ethylene (mol / Hr)] / Reactor inlet ethylene (mol / Hr)] × 100
Since ethanol is easily dehydrated and converted to ethylene when it comes into contact with the catalyst, when ethanol is used as a raw material in the present invention, it is considered that all of the supplied ethanol has been converted to ethylene at the reactor inlet. By treating it as inlet ethylene (mol / Hr), the ethylene conversion rate is calculated from the above formula.

<Selectivity>
The selectivity in this specification is a value calculated by the following equations. In each of the following formulas, “derived carbon flow rate (mol / Hr)” of propylene, butene, C5 +, paraffin or aromatic hydrocarbon means the molar flow rate of carbon atoms constituting each hydrocarbon. Paraffin is the sum of paraffins having 1 to 4 carbon atoms, aromatic compounds are the sum of benzene, toluene and xylene, and C5 + is the sum of hydrocarbons having 5 or more carbon atoms excluding the aromatic compounds.

Propylene selectivity (%) = [reactor outlet propylene-derived carbon molar flow rate (mol / Hr) / [reactor outlet total carbon molar flow rate (mol / Hr) −reactor outlet ethylene-derived carbon molar flow rate (mol / Hr)] ] × 100
Butene selectivity (%) = [reactor outlet butene-derived carbon molar flow rate (mol / Hr) / [reactor outlet total carbon molar flow rate (mol / Hr) −reactor outlet ethylene-derived carbon molar flow rate (mol / Hr)] ] × 100
C5 + selectivity (%) = [reactor outlet C5 + derived carbon molar flow rate (mol / Hr) / [
Reactor outlet total carbon molar flow rate (mol / Hr) −reactor outlet ethylene-derived carbon molar flow rate (mol / Hr)]] × 100
Paraffin selectivity (%) = [reactor outlet paraffin-derived carbon molar flow rate (mol / Hr) / [reactor outlet total carbon molar flow rate (mol / Hr) −reactor outlet ethylene-derived carbon molar flow rate (mol / Hr)] ] × 100
Aromatic compound selectivity (%) = [reactor outlet aromatic compound-derived carbon molar flow rate (mol / Hr) / [reactor outlet total carbon molar flow rate (mol / Hr) −reactor outlet ethylene-derived carbon molar flow rate (mol) / Hr)]] × 100

The ratio of each isomer in butenes is calculated by the following formulas.
1-butene ratio (%) = [reactor outlet 1-butene-derived carbon molar flow rate (mol / Hr) / reactor outlet butene-derived carbon molar flow rate (mol / Hr)] × 100
trans-2-butene ratio (%) = [reactor outlet trans-2-butene-derived carbon molar flow rate (mol / Hr) / reactor outlet butene-derived carbon molar flow rate (mol / Hr)] × 100
cis-2-butene ratio (%) = [reactor outlet cis-2-butene-derived carbon molar flow rate (mol / Hr) / reactor outlet butene-derived carbon molar flow rate (mol / Hr)] × 100
Isobutene ratio (%) = [reactor outlet isobutene-derived carbon molar flow rate (mol / Hr) / reactor outlet butene-derived carbon molar flow rate (mol / Hr)] × 100
The yield in the present specification is determined by the product of the ethylene conversion rate and the selectivity of each component produced. Specifically, the propylene yield and the linear butene yield are represented by the following formulas, respectively. Is done. The linear butene selectivity here is represented by the product of the butene selectivity and the sum of the ratios of 1-butene, trans-2-butene and cis-2-butene in butenes.

Propylene yield (%) = ethylene conversion (%) × propylene selectivity (%) / 100
Linear Butene Yield (%) = Ethylene Conversion (%) × Linear Butene Selectivity (%) / 100
Linear butene selectivity (%) = butene selectivity (%) × [1-butene ratio + trans-2-butene ratio + cis-2-butene ratio (%)] / 100

(5-3) Reaction product As the reactor outlet gas (reactor effluent), a mixed gas containing propylene and linear butene, unreacted ethylene, by-products, and a diluent, which is a reaction product, is obtained. It is done. The total concentration of propylene and linear butene in the mixed gas is usually 1% by weight or more, preferably 2% by weight or more, and usually 95% by weight or less, preferably 80% by weight or less.
The mixed gas usually contains ethylene, but it is preferable that at least a part of the ethylene in the mixed gas is recycled to the reactor and reused as a reaction raw material.
Examples of by-products include olefins having 5 or more carbon atoms, paraffins, and aromatic compounds.

Propylene obtained by the production method of the present invention can produce polypropylene by polymerizing it. The method for polymerizing propylene is not particularly limited, but the propylene obtained by the present invention can be directly used as a raw material monomer by introducing it into a polymerization reactor. Moreover, the propylene obtained by this invention can be utilized also as a raw material of propylene derivative products through the various reaction mentioned later besides a polypropylene. For example, acrylonitrile can be produced by ammonia oxidation, acrolein, acrylic acid and acrylate esters by selective oxidation, normal butyl alcohol by oxo reaction, propylene oxide, propylene glycol, etc. by selective oxidation. Propylene can produce acetone by the Wacker reaction, and methyl isobutyl ketone can be produced from the obtained acetone. Further, methyl methacrylate can be produced from acetone via acetone cyanohydrin. Propylene can produce isopropyl alcohol by a hydration reaction. Propylene can be produced by reacting with benzene, and can be used to produce phenol, bisphenol A, or polycarbonate resin using cumene as a raw material.

  The linear butene obtained by the production method of the present invention can produce butadiene by dehydrogenation. Furthermore, butadiene can produce polybutadiene (BR) by homopolymerization, styrene butadiene rubber (SBR) by polymerization with styrene, acrylonitrile-styrene-butadiene resin (ABS resin) by polymerization of acrylonitrile and styrene, and the like. Linear butene can also be used as a raw material for other butene derivatives. For example, linear butene can produce methyl ethyl ketone through sec-butyl alcohol by the indirect hydration method and subsequent dehydrogenation reaction. 1-butene can produce polybutene-1 by polymerization, amyl alcohol or the like by oxo reaction.

The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
(Preparation Example 1)
59.2 g of 25% by weight N, N, N-trimethyl-1-adamantanammonium hydroxide aqueous solution and 145.6 g of 1M sodium hydroxide aqueous solution were successively dissolved in 371 g of water, and then aluminum hydroxide (in terms of aluminum oxide) (50 to 57% by weight) was added and stirred, and then fumed silica 42.1 g was added as a silica source and stirred for 2 hours. Further, 2% by weight of CHA-type aluminosilicate was added as a seed crystal to the weight of the added fumed silica, and further stirred. Next, this gel was charged into a 1000 ml autoclave, and hydrothermal synthesis was performed at 160 ° C. for 42 hours while stirring at 150 rpm under an autogenous pressure. The product was filtered, washed with water and dried.

The aluminosilicate after hydrothermal synthesis (as-made aluminosilicate) was dried and then calcined at 580 ° C. for 6 hours under air flow to obtain a sodium-type aluminosilicate. The aluminosilicate was ion-exchanged twice at 80 ° C. for 1 hour with a 1M ammonium nitrate aqueous solution, dried at 100 ° C. and then calcined at 500 ° C. for 6 hours in an air stream to obtain a proton type aluminosilicate A. .
The aluminosilicate obtained above was a CHA type H type aluminosilicate, and the SiO ₂ / Al ₂ O ₃ ratio was 14 (molar ratio). Moreover, the primary particle diameter of the aluminosilicate was about 100 nm by the measurement of the scanning electron microscope.

(Preparation Example 2)
Dissolve 5.92 kg of 25% by weight N, N, N-trimethyl-1-adamantanammonium hydroxide aqueous solution and 0.56 kg of sodium hydroxide sequentially in 51.0 kg of water, then aluminum hydroxide (in terms of aluminum oxide) After adding 0.534 kg, the mixture was stirred for 2 hours after adding 4.22 kg of fumed silica as a silica source. Further, 2% by weight of CHA-type aluminosilicate was added as a seed crystal to the weight of the added fumed silica, and further stirred. Next, this gel was charged into a 100 l autoclave, and hydrothermal synthesis was performed at 160 ° C. for 48 hours while stirring at 180 rpm under an autogenous pressure. The product was filtered, washed with water and dried.

The as-made aluminosilicate after drying was converted to the proton type by the same treatment method as in Preparation Example 1 to obtain proton-type aluminosilicate B.
The aluminosilicate obtained above was a CHA type H type aluminosilicate, and the SiO ₂ / Al ₂ O ₃ ratio was 24 (molar ratio). Moreover, the primary particle diameter of the aluminosilicate was about 50 nm by the measurement of the scanning electron microscope.

(Preparation Example 3)
3.93 g of sodium hydroxide and 47.3 g of 25% by weight N, N, N-trimethyl-1-adamantanammonium hydroxide aqueous solution were sequentially dissolved in 89.6 g of water, and then aluminum hydroxide (in terms of aluminum oxide) After adding 4.27 g and mixing, 111 g of colloidal silica SI-30 (SiO ₂ 30 wt%, Na 0.3 wt%, manufactured by JGC Catalysts and Chemicals Co., Ltd.) is sufficiently added as a silica source. Stir. Further, 10% by weight of CHA type aluminosilicate was added as a seed crystal to the added SiO ₂ and further stirred. Next, this gel was charged into a 1000 ml autoclave, and hydrothermal synthesis was performed at 160 ° C. for 42 hours while stirring at 200 rpm under a self-pressure. The product was filtered, washed with water and dried.

The as-made aluminosilicate after drying was converted to the proton type by the same treatment method as in Preparation Example 1 to obtain proton type aluminosilicate C.
The aluminosilicate obtained above was a CHA type H type aluminosilicate, and the SiO ₂ / Al ₂ O ₃ ratio was 22 (molar ratio). Moreover, the primary particle diameter of the aluminosilicate was about 20-60 nm by the measurement of the scanning electron microscope.

(Preparation Example 4)
Dissolve 2.09 g of sodium hydroxide and 47.3 g of 25% by weight N, N, N-trimethyl-1-adamantanammonium hydroxide aqueous solution successively in 89.6 g of water, then aluminum hydroxide (in terms of aluminum oxide) After adding 4.27 g and mixing, 111 g of colloidal silica SI-30 (SiO ₂ 30 wt%, Na 0.3 wt%, manufactured by JGC Catalysts and Chemicals Co., Ltd.) is sufficiently added as a silica source. Stir. Further, 10% by weight of CHA type aluminosilicate was added as a seed crystal to the added SiO ₂ and further stirred. Next, this gel was charged into a 1000 ml autoclave, and hydrothermal synthesis was performed at 160 ° C. for 20 hours while stirring at 250 rpm under an autogenous pressure. The product was filtered, washed with water and dried.

The as-made aluminosilicate after drying was converted to the proton type by the same treatment method as in Preparation Example 1 to obtain proton-type aluminosilicate D.
The aluminosilicate obtained above was a CHA type H type aluminosilicate, and the SiO ₂ / Al ₂ O ₃ ratio was 26 (molar ratio). Moreover, the primary particle diameter of the aluminosilicate was about 50 nm by the measurement of the scanning electron microscope.

Example 1
(Preparation of catalyst)
To 10 g of aluminosilicate A obtained in Preparation Example 1, 100 ml of hexamethyldisiloxane as a solvent and 25 ml of tetraethoxysilane as a silylating agent were added, and heat treatment was performed at 100 ° C. for 6 hours while stirring. After completion of the reaction, the solid and liquid were separated by filtration, and the solid content was dried at 100 ° C. After drying, calcination was carried out at 550 ° C. for 6 hours under air flow to obtain a silylated aluminosilicate.
Next, 1 g of silylated aluminosilicate was treated at 600 ° C. for 5 hours under the flow of 50% steam (steam / nitrogen = 50/50) to obtain a silylation-treated and steam-treated catalyst.

(reaction)
Using the catalyst obtained above, a reaction for synthesizing propylene and linear butene was performed using ethylene as a raw material. For the reaction, a normal pressure fixed bed flow reactor was used, and a quartz reaction tube having an inner diameter of 6 mm was filled with a mixture of the catalyst 100 mg and quartz sand 400 mg. Ethylene and nitrogen were fed to the reactor so that the space velocity of ethylene was 0.36Hr ⁻¹ , 30% by volume of ethylene and 70% by volume of nitrogen, and synthesis of propylene and linear butene was performed at 350 ° C. and 0.1 MPa. The reaction was carried out. In order to compare the reaction results of this reaction, the reaction was carried out for a time when the conversion rate of ethylene was about 80%, and then the product was analyzed by gas chromatography. The reaction results are shown in Table 1.

(Example 2)
The aluminosilicate B obtained in Preparation Example 2 was subjected to a silylation treatment in the same manner as in Example 1, and was treated in the same manner except that the treatment time for the steam treatment was 2 hours. A catalyst was obtained.
The obtained catalyst was charged into the same reactor as in Example 1, and a synthesis reaction of propylene and linear butene was performed under the same reaction conditions. The reaction results are shown in Table 1.

(Example 3)
25 ml of toluene as a solvent and 6.3 ml of tetraethoxysilane as a silylating agent were added to 2.5 g of aluminosilicate C obtained in Preparation Example 3, and the mixture was treated at room temperature for 2 hours with stirring. After completion of the reaction, the solid and liquid were separated by filtration, and the solid content was dried at 100 ° C. After drying, calcination was carried out at 550 ° C. for 6 hours under air flow to obtain a silylated aluminosilicate. Subsequently, it processed similarly to the steaming process of Example 1, and obtained the silylation process and the steam-processed catalyst.
This catalyst was charged into the same reactor as in Example 1, and a synthesis reaction of propylene and linear butene was performed under the same reaction conditions. The reaction results are shown in Table 1.

Example 4
The aluminosilicate C obtained in Preparation Example 3 was subjected to silylation treatment in the same manner as in Example 3, and 1 g of silylated aluminosilicate was treated at 800 ° C. under nitrogen flow for 6 hours, whereby silylation treatment and A heat-treated catalyst was obtained.
This catalyst was charged into the same reactor as in Example 1, and a synthesis reaction of propylene and linear butene was performed under the same reaction conditions. The reaction results are shown in Table 1.

(Comparative Example 1)
To 2.0 g of aluminosilicate D obtained in Preparation Example 4, a moisture conditioning treatment was performed so that the water content was 21% by weight, and 20 ml of toluene as a solvent and 5 ml of tetraethoxysilane as a silylating agent were added. Heating was performed for 4 hours at 70 ° C. with stirring. After completion of the reaction, the solid-liquid was separated by filtration, and the solid content was dried at 100 ° C. to obtain a silylated aluminosilicate catalyst.
This catalyst was charged into the same reactor as in Example 1, and a synthesis reaction of propylene and linear butene was performed under the same reaction conditions. The reaction results are shown in Table 1.

  Comparative Example 1 is a result obtained when a CHA type aluminosilicate which is an 8-membered ring is contacted with ethylene using aluminosilicate subjected to silylation as a catalyst. The propylene yield was 68.5%, but the linear butene yield was 3.2%, and the linear butene yield was very low. On the other hand, Examples 1 to 3 are cases where CHA type aluminosilicate subjected to both silylation treatment and steam treatment was used as a catalyst. In this case, the propylene yield from ethylene was 45% or more, and A chain butene yield of 15% or more was obtained. In Example 4, heat treatment was performed instead of the water vapor treatment in Example 3. From this, it can be seen that both propylene and linear butene can be obtained in high yield simultaneously by subjecting the aluminosilicate to both steam treatment and heat treatment in addition to silylation.

  The production method of the present invention provides a method for producing propylene and linear butene at the same time in a high yield. In addition, since by-product of inbutene can be suppressed and linear butene can be selectively produced, the load of separation and purification of linear butene from butenes can be greatly reduced.

Claims (4)

A method for producing propylene and linear butene by bringing ethylene and / or ethanol into contact with a catalyst, wherein the active component of the catalyst is silylated to an aluminosilicate having an oxygen 8-membered ring structure or an oxygen 9-membered ring structure. A process for producing propylene and straight-chain butene , wherein the heat treatment temperature is 600 ° C. or higher and 1000 ° C. or lower .   The method for producing propylene and linear butene according to claim 1, wherein the aluminosilicate has a CHA type structure.   The method for producing propylene and linear butene according to claim 1 or 2, wherein the aluminosilicate is subjected to silylation treatment before being subjected to steam treatment and / or heat treatment.   The method for producing propylene and linear butene according to any one of claims 1 to 3, wherein the conversion of ethylene and / or ethanol is 60% or more, and ethylene and / or ethanol and the catalyst are brought into contact with each other. .