Title of the invention: Porous molded product and its production method, α-olefin dimer catalyst and its production method, and α-olefin dimer production method.
Technical field
[0001]
　The present invention relates to a porous molded product and a method for producing the same, a catalyst for dimerizing α-olefin and a method for producing the same, and a method for producing an α-olefin dimer.
Background technology
[0002]
　Α-olefin dimers represented by 4-methyl-1-pentene (including α-olefin codimers; the same applies hereinafter) are used as monomers for producing polyolefins. Many basic catalysts have been conventionally proposed as catalysts for producing a corresponding dimer by a dimerization reaction of α-olefin (including a codimerization reaction of α-olefin; the same applies hereinafter). In particular, a catalyst in which an alkali metal is supported on a carrier containing an anhydrous potassium compound as a main component is often used.
[0003]
　With respect to these catalysts, research is being continuously conducted to further improve the catalytic activity and the availability of the target substance (hereinafter, also referred to as "selectivity"). Moreover, since the catalyst life is not sufficient even if the initial activity is high, research for extending the catalyst life is being continued.
　Further, by adjusting the physical characteristics of the anhydrous potassium compound used or the physical characteristics of the carrier, improvement of catalytic activity, improvement of selectivity, and improvement of catalyst life have been promoted (see, for example, Patent Documents 1 to 6).
　In Patent Document 7, as a molded product used as a carrier for an α-olefin dimerization catalyst, a porous molded product (porous molded product) in which the size of the pore volume is adjusted to a specific range is produced. The method is disclosed. It is disclosed that when the molded product is used as a carrier for a catalyst for α-olefin dimerization, the reaction selectivity is higher than that of a known catalyst.
　Further, Patent Document 8 discloses that a mixture of potassium carbonate and silica / alumina is used as a carrier of a catalyst for α-olefin dimerization, and Non-Patent Document 1 discloses a substance in which the surface of zeolite is coated with potassium carbonate. Is disclosed to be used.
[0004]
　　Patent Document 1: Japanese Patent Application
　　Laid-Open No. 58-114737 Patent Document 2: Japanese Patent Application Laid-Open No. 3-42043
　　Patent Document 3: Japanese Patent Application Laid-Open No. 7-22927
　　Patent Document 4: Japanese Patent Application Laid-Open No. 2006-326418
　　Patent Document 5: Special Publication Kai 2008-149275 Japanese
　　Patent Document 6: US Patent No. 5081094
　　Patent Document 7: International Publication No. 2015/093378
　　Patent Document 8: European Patent No. 474087
[0005]
　　Non-Patent Document 1: Chem. Eng. Technol. 17 1995 354
Outline of the invention
Problems to be solved by the invention
[0006]
　The present inventors have conducted various studies on catalysts represented by the above patent documents. As a result, the catalysts disclosed in Patent Documents 1 to 5 have a certain degree of improvement in improving the catalytic activity or selectivity, but the catalyst carrier collapses in a long-term reaction (hereinafter, "pulverization"). It has become clear that it tends to be difficult to continue operation. The present inventors have stated that the catalyst carrier may have a strong tendency to pulverize, especially in an embodiment requiring a reaction in a liquid phase such as obtaining 3-methyl-1-pentene from ethylene and 1-butene. I found it.
　The catalyst using the carrier containing potassium hydrogen carbonate disclosed in Patent Document 6 is in the form of powder and is not suitable for industrial production. Further, although Patent Document 6 discloses that the carrier may be molded into pellets or the like, potassium hydrogen carbonate is dissolved because water is used for molding, and filling into the molding die cannot be performed smoothly. It was presumed that the physical properties of the molded product would be non-uniform.
　Further, in producing a porous molded product, it is more desirable that the size of the pores can be adjusted. More specifically, it may be required to produce a porous molded product having a larger pore diameter than the porous molded product obtained by the method described in Patent Document 7. Further, it is considered that a preferable requirement is that the manufacturing method has a shape that is easy to control.
　Patent Document 8 and Non-Patent Document 1 do not describe molded articles using the above mixture or substance, and it is difficult to recognize their industrial usefulness.
[0007]
　Therefore, one embodiment according to the present disclosure provides a porous molded product having excellent pulverization inhibitory properties in the α-olefin dimerization reaction.
　Further, one embodiment according to the present disclosure is a method for producing a porous molded body having excellent powdering inhibitory property in an α-olefin dimerization reaction, a catalyst for α-olefin dimerization using the porous molded body, and its production. Provided are a method and a method for producing an α-olefin dimer using the catalyst.
Means to solve problems
[0008]
　The disclosure includes the following embodiments:
<1> The 　above-mentioned alkali metal carbonate or alkali metal
　containing a porous molded body (X) satisfying the following requirements (x-1) to (x-3) and an alkali metal carbonate or alkali metal hydrogen
carbonate. The content of hydrogen carbonate is in the range of 1 part by mass to 230 parts by mass with respect to 100 parts by mass of the porous molded body (X). Requirement (x-1): The pore volume in the range of 0.01 μm to 100 μm in pore diameter is 0.10 mL / g to 1.00 mL / g.
　Requirement (x-2): The median pore diameter of pores having a pore diameter in the range of 0.01 μm to 100 μm is more than 0.01 μm and not more than 10.0 μm.
　Requirement (x-3): The crushing strength is 0.7 kgf to 15.0 kgf.
<2> The porous molded product (Y) according to <1>, wherein the porous molded product (X) further satisfies the following requirement (x-4).
　Requirement (x-4): Includes oxides of metal or rare earth elements and at least one compound selected from the group consisting of composite oxides thereof, zeolites, activated carbons, and SiC.
<3> The alkali metal carbonate or alkali metal hydrogen carbonate is Na 2 CO 3 , NaHCO 3 , K 2 CO 3 , and KHCO. The porous molded article (Y) according to <1> or <2>, which is at least one compound selected from the group consisting of 3 .
<4> The pore volume of the porous molded body (Y) in the range of 0.01 μm to 100 μm is 0.10 mL / g to 0.80 mL / g, <1> to < The porous molded body (Y) according to any one of 3>.
<5> The porous molded product (Y) according to any one of <1> to <4>, wherein the porous molded product (X) is a molded product of Al 2 O 3 .
<6> A catalyst for α-olefin dimerization, which carries the alkali metal (D) of the porous molded product (Y) according to any one of <1> to <5>.
<7> α, which comprises a step of supporting an alkali metal (D) on the porous molded body (Y) according to any one of <1> to <5> to obtain a catalyst for α-olefin dimerization. -A method for producing a catalyst for olefin dimerization.
<8> Production of an α-olefin dimer comprising a step of dimerizing an α-olefin to obtain an α-olefin dimer in the presence of the α-olefin dimer catalyst according to <6>. Method.
<9> An alkali metal carbonate or alkali metal bicarbonate is added to the porous molded body (X) that satisfies the following requirements (x-1) to (x-3), and 100 parts by mass of the porous molded body (X). A step of obtaining a support by supporting the support in the range of 1 part by mass to 230 parts by mass, and a step
　of heat-treating the support at 100 ° C. to 500 ° C. to obtain a porous molded body (Y).
A method for producing a porous molded product (Y).
　Requirement (x-1): The pore volume in the range of 0.01 μm to 100 μm in pore diameter is 0.10 mL / g to 1.00 mL / g.
　Requirement (x-2): The median pore diameter of pores having a pore diameter in the range of 0.01 μm to 100 μm is more than 0.01 μm and not more than 10.0 μm.
　Requirement (x-3): The crushing strength is 0.7 kgf to 15.0 kgf.
<10> The method for producing a porous molded product (Y) according to <9>, wherein the porous molded product (X) further satisfies the following requirement (x-4).
　Requirement (x-4): Includes oxides of metal or rare earth elements and at least one compound selected from the group consisting of composite oxides thereof, zeolites, activated carbons, and SiC.
<11> The alkali metal carbonate or alkali metal hydrogen carbonate is at least one compound selected from the group consisting of Na 2 CO 3 , NaHCO 3 , K 2 CO 3 , and KHCO 3. <9> Alternatively, the method for producing the porous molded product (Y) according to <10>.
<12> The porous molded product (X) is Al 2 O 3The method for producing a porous molded product (Y) according to any one of <9> to <11>, which is the molded product of the above.
<13> The method for producing a porous molded product (Y) according to any one of <9> to <12>, wherein the step of obtaining the carrier is a step of supporting the carrier by an impregnation method to obtain the carrier. ..
Effect of the invention
[0009]
　According to one embodiment of the present disclosure, there is provided a porous molded article having excellent pulverization inhibitory properties in the α-olefin dimerization reaction.
　Further, according to one embodiment of the present disclosure, a method for producing a porous molded body having excellent powdering inhibitory property in an α-olefin dimerization reaction, a catalyst for α-olefin dimerization using the porous molded body, and a catalyst for dimerization of α-olefin. A method for producing the α-olefin dimer using the catalyst and a method for producing an α-olefin dimer using the catalyst are provided.
Mode for carrying out the invention
[0010]
　In the present specification, the numerical range represented by using "-" means a range including the numerical values ​​before and after "-" as the minimum value and the maximum value, respectively. In the numerical range described stepwise in the present specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. Further, in the numerical range described in the present specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
　In the present specification, the combination of preferred embodiments is a more preferred embodiment.
　Further, the unit of crushing strength [kgf] in the present specification can be converted to [N] by the relational expression of 1 kgf = 9.8N.
　In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. Is done.
[0011]
<< Porous molded body (Y) >>
　The porous molded body (Y) according to the present disclosure includes a porous molded body (X) satisfying the following requirements (x-1) to (x-3) and an alkali metal. It contains a carbonate or an alkali metal hydrogen carbonate (hereinafter, also referred to as a "specific compound"), and the content of the alkali metal carbonate or the alkali metal hydrogen carbonate is the same as the porous molded product (X) 100. The range is from 1 part by mass to 230 parts by mass with respect to the mass part.
　Since the porous molded product (Y) according to the present disclosure has the above-mentioned structure, it is excellent in suppressing pulverization in the α-olefin dimerization reaction (hereinafter, also referred to as “excellent in suppressing pulverization”). That is, the excellent pulverization inhibitory property means that the porous molded product (Y) is difficult to be pulverized even when it is used in the α-olefin dimerization reaction.
　The reason for this is not clear, but it is presumed as follows. However, this disclosure is not limited to the following reasons.
[0012]
　As a result of examination by the present inventors, the content of the porous molded product (X) satisfying the requirements (x-1) to (x-3) is contained in the porous molded product (X) and the specific compound. In the porous molded body (Y) containing a specific compound in a specific range, the porous molded body (X) serves as a core, and the porous molded body (X) and the specific compound are compounded. It has been found that even when the α-olefin dimerization reaction is carried out using the porous molded product (Y) according to the present disclosure, the porous molded product (Y) is difficult to be pulverized during the reaction.
　The porous molded product (X) included in the porous molded product (Y) according to the present disclosure satisfies the requirements (x-1) to (x-3) and contains, for example, an oxide such as a specific metal. The above-mentioned metal oxide component is not only a component having excellent strength, but is also considered to have substantially no function related to the reaction as a catalyst. Therefore, the influence on the structure due to the catalytic reaction (for example, It may be difficult to be deformed, hard to be destroyed, etc.). Therefore, it is presumed that the porous molded product (Y) according to the present disclosure is more difficult to pulverize than before, especially in the above-mentioned α-olefin codimerization reaction.
　Further, when a conventional Na-supported potassium carbonate catalyst is used for the dimerization reaction of α-olefin, it is presumed that the catalyst is pulverized by the progress of the dimerization reaction inside the catalyst.
　On the other hand, since the porous molded body (Y) according to the present disclosure has the above-mentioned configuration, the alkali metal (D) carrier (catalyst for α-olefin dimerization) of the porous molded body (Y) described later will be described. The present inventors also consider that when this is used in the dimerization reaction of α-olefin, the reaction point is difficult to be formed even inside the porous molded body (Y), and therefore the pulverization inhibitory property is excellent.
　Further, in the method for producing a porous molded product (Y) according to the present disclosure, by having the above steps, a specific compound can be easily carried on the porous molded product (X), and further, the specific compound can be a porous molded product (X). Since the structure can be firmly adhered to X), the obtained porous molded product (Y) is different from the conventional porous molded product produced by tableting a specific compound using graphite or the like as a lubricant. In comparison, it is presumed that the porous molded product (Y) is suppressed from being pulverized during the α-olefin dimerization reaction.
　Hereinafter, each component constituting the porous molded product (Y) according to the present disclosure, the porous molded product (X) used in the method for producing the porous molded product (Y) according to the present disclosure, and a specific compound will be described. To do.
[0013]

　The porous molded product (Y) according to the present disclosure is a porous molded product (X) that satisfies the following requirements (x-1) to (x-3) (hereinafter, simply "porous". It is also referred to as "quality molded product (X)").
Requirement (x-1): The pore volume in the range of 0.01 μm to 100 μm in pore diameter is 0.10 mL / g to 1.00 mL / g.
Requirement (x-2): The median pore diameter of pores having a pore diameter in the range of 0.01 μm to 100 μm is more than 0.01 μm and not more than 10.0 μm.
Requirement (x-3): The crushing strength is 0.7 kgf to 15.0 kgf.
　The porous molded product (Y) according to the present disclosure is a porous molded product using the porous molded product (X) satisfying the requirements (x-1) to (x-3) as a carrier from the viewpoint of suppressing pulverization. It is preferable that the carrier (X) is supported by a specific compound described later. The carrier is difficult to pulverize even when the porous molded product (Y) is used for the α-olefin dimerization reaction.
　Hereinafter, each requirement satisfied by the porous molded product (X) will be described.
[0014]
(X-1) Pore volume The pore volume
　(hereinafter, simply referred to as “pore diameter (X)”) of the porous molded product (X) is in the range of 0.01 μm to 100 μm (hereinafter, referred to as “pore diameter (X)”). , Simply referred to as “pore volume (X)”) is 0 from the viewpoint of improving the reaction selectivity when the obtained porous molded product (Y) is applied to the carrier of the α-olefin dimerization catalyst. It is .10 mL / g to 1.00 mL / g, preferably 0.20 mL / g to 0.80 mL / g, and more preferably 0.26 mL / g to 0.77 mL / g.
　In the present specification, the “pore volume” refers to the total volume of all pores having a pore diameter (X) in the range of 0.01 μm to 100 μm.
　The pore volume (X) can be adjusted, for example, depending on the type of raw material of the porous molded product used and the molding method or conditions.
　The pore volume (X) and pore diameter (X) can be determined from the pore distribution measured by the mercury intrusion method. Further, in the present specification, the pore volume means that the pore diameter (X) (hereinafter, also referred to as “pore diameter (X)”) is in the range of 0.01 μm to 100 μm unless otherwise specified. It means the value of the pore volume.
　The method for measuring the pore volume in the present disclosure is 50, which is a pressure range of 1.0 psi (6894.76 Pa) to 33,000 psi (2275.27 × 10 3 Pa), using Micrometrics Co., Ltd., model number: Auto Pore IV). The relationship between each pore diameter and the pore volume can be determined by measuring from a point to 100 points and measuring the amount of mercury pressed into the pores.
　The above-mentioned measuring method is a measuring method based on the principle that the pore diameter into which mercury is press-fitted is determined by the pressure of mercury due to the characteristics of mercury. The pore volume in the pore diameter range, which will be described later, can also be obtained from the measured values ​​of the pore diameter and the pore volume measured in the same manner.
[0015]
(X-2) Median pore diameter
　porous median pore diameter of the pore pore diameter (X) is in the range of 0.01 [mu] m ~ 100 [mu] m of the molded article (X) is obtained porous molded body (Y) From the viewpoint of improving the reaction selectivity when applied to the carrier of the α-olefin dimerization catalyst, it is more than 0.01 μm and 10.0 μm or less, preferably 0.10 μm or more and 10.0 μm or less.
　In the present specification, the median pore diameter (X) refers to a pore diameter in which the pore diameter (X) (pore diameter (X)) is in the range of 0.01 μm to 100 μm, measured by a mercury intrusion method, and falls within the above range. When a certain pore diameter with a cumulative total of 50% is divided into two, it means that the large side (large diameter side) and the small side (small diameter side) have the same number of pore diameters.
　The method for measuring the median pore size (X) is described in the section of Examples.
[0016]
(X-3) Crushing strength The crushing strength of the
　porous molded product (X) is 0.7 kgf to 15.0 kgf, preferably 1.0 kgf or more, and more preferably 1.5 kgf or more.
　Here, the crushing strength indicates the strength in the radial direction of the porous molded product.
　The shape of the porous molded body (X) is not particularly limited, and examples thereof include a tablet shape, a noodle shape, a columnar shape (pellet shape), a convex shape, a ring shape, a spherical shape, and the like. In each case, there is a direction corresponding to the radial direction, but in the case of a porous molded body having a shape without a direction corresponding to the radial direction, the strength in the weakest direction is defined as the crushing strength.
　The crushing strength is generally known as a physical property indicating the pressure resistance of the granulated product, and usually, one molded body having a shape such as a pellet shape or a tablet shape is added in the body direction (major axis direction). It measures the force when crushing and crushing.
　JIS Z8841 (1993) "Granulated product-strength test method" stipulates the test method.
[0017]
(X-4) Composition The
　porous molded product (X) is also referred to as an oxide of a metal or rare earth element (hereinafter, also simply referred to as “oxide”) and a composite oxide thereof (hereinafter, simply referred to as “composite oxide”). It is preferable to contain at least one compound selected from the group consisting of zeolite, activated carbon, and SiC.
　The above compounds may be used alone or in combination of two or more.
　Examples of the metal include Al, Si, Ti, Zr, Ca, Sr, Ba, Na, K, Cs, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Ru, Rh, Pd. , Ag, Cd, W, Ir, Pt, Au and the like.
　Examples of rare earth elements include scandium (Sc), yttrium (Y), and lanthanoids.
　From the viewpoint of preparing the porous molded product (Y) and using it as a catalyst for α-olefin dimerization, the porous molded product (X) preferably contains a metal oxide and a composite oxide, and Al. , Si, Ti, Zr, Mn, Co, Ni, Cu, Zn, Mo, W, Ca, Sr, Ba, Na, K or Cs oxides and composite oxides thereof are more preferably contained. It is more preferable to contain an oxide of Si, Ti or Zr, particularly preferably to contain Al 2 O 3, and it is particularly preferable that the porous molded body (X) is an Al 2 O 3 molded body.
　The oxide, composite oxide, zeolite, activated carbon, or SiC contained in the porous molded body (Y) was supported by, for example, impregnating water with the porous molded body (Y). It can be confirmed by dissolving a specific compound in water, removing it, drying it, and then identifying it by X-ray fluorescence (XRD), X-ray fluorescence analysis (XRF), or high-frequency induction coupled plasma (ICP) emission analysis. .. Of course, the pore shape and the like can also be measured by using the mercury press-fitting method.
[0018]
　The content of at least one compound selected from the group consisting of the above oxides, composite oxides, zeolites, activated carbon, and SiC is 70% by mass to 100% by mass with respect to the total mass of the porous molded body (X). It is preferably contained in the range of mass%, and more preferably in the range of 80% by mass to 100% by mass.
[0019]
　The size and shape of the porous molded product (X) are not particularly limited. The shape of the porous molded product (X) can be selected depending on the conditions of the molding apparatus and the like, and can be any of tablet-shaped, noodle-shaped, columnar (pellet-shaped), convex, ring-shaped, and spherical. ..
　As the molding apparatus used for forming the porous molded product (X), a commercially available one can be used, and an apparatus having an optimum scale can be appropriately selected according to the production amount.
[0020]
　When the shape of the porous molded body (X) is, for example, a columnar shape, it can usually be molded into a size of 2 mm to 5 mm in diameter and 2 mm to 7 mm in height.
　When the porous molded body (X) is columnar, if the size of the porous molded body (X) is within the above range, for example, for α-olefin dimerization after heat treatment of the porous molded body (X). When applied as a catalyst carrier, the diffusion of raw materials and reaction products in the α-olefin dimerization reaction system tends to be good, and the reaction activity and reaction selectivity of the α-olefin dimerization reaction tend to be improved.
[0021]
　The porous molded product (X) satisfying the above requirements (x-1) to (x-2) can be prepared by using a known method. For example, it may be prepared by a method of making the surface of the porous molded product (X) uneven due to a change in density by heat-treating the above metal oxide or the like in a specific temperature range to undergo crystal transition. Further, by using the same method, the porous molded body (X) can be controlled to various shapes and sizes.
　Further, this heat treatment activates a functional group structure such as an acid point (sometimes referred to as an "active site") on the surface of the porous molded product (X), and the porous molded product (X) will be described later. It is considered that it becomes easy to firmly support the specific compound. From that point of view, the above heat treatment is preferable. Further, the surface of the heat-treated porous molded product (X) often has a large specific surface area. This is also considered to be one of the reasons why it is easy to firmly support the specific compound on the porous molded product (X).
　The shape of the porous molded product (X) may be formed before the specific compound is supported, and the shape of the porous molded product (X) is formed while the specific compound is supported on the porous molded product (X). You may. From the viewpoint of firmly supporting the specific compound, it is preferable to form the porous molded product (X) before supporting the specific compound. On the other hand, when the shape of the porous molded product (X) is formed while the specific compound is supported on the porous molded product (X), the condition that the desired shape can be formed by the porous molded product (X) alone is set in advance. It is preferable to confirm it.
　The preferred temperature range for performing the heat treatment is 1,000 ° C to 1,300 ° C. The lower limit of the more preferable temperature range is 1,050 ° C., more preferably 1,100 ° C.
　The above temperature range is a preferable temperature range from the viewpoint of activation of the above acid points, formation of a porous structure, and maintenance.
[0022]
　Further, as the porous molded product (X), a commercially available product may be used, and examples of the commercially available product include alumina SA5102, SA3132, and SA31132 (above, product number). These can be obtained from Saint-Gobain Co., Ltd.
[0023]

　The porous molded product (Y) according to the present disclosure contains an alkali metal carbonate or an alkali metal hydrogen carbonate (specific compound).
　The porous molded product (Y) containing the specific compound is excellent in the pulverization inhibitory property in the α-olefin dimerization reaction.
　From the viewpoint of pulverization inhibitory property, the specific compound is preferably a carrier supported on the porous molded product (X) as a carrier.
　For example, from the viewpoint of thermal stability, particular compounds, Na 2 CO 3 , NaHCO 3 , K 2 CO 3 , and KHCO 3 is preferably at least one compound selected from the group consisting of, K 2 CO 3 It is more preferably at least one compound selected from the group consisting of and Na 2 CO 3, and even more preferably K 2 CO 3 .
　The specific compound may be used alone or in combination of two or more.
[0024]
　The content of the specific compound is in the range of 1 part by mass to 230 parts by mass with respect to 100 parts by mass of the porous molded product (X).
　When the content of the specific compound is in the above range, sufficient catalytic performance can be exhibited when the porous molded product (Y) according to the present disclosure is used as an olefin dimerization catalyst.
　From the above viewpoint, the content of the specific compound is preferably in the range of 3 parts by mass to 150 parts by mass with respect to 100 parts by mass of the porous molded body (X), and is in the range of 5 parts by mass to 100 parts by mass. It is more preferably 10 parts by mass to 50 parts by mass.
[0025]
(Y-1) Pore volume The pore volume of the
　porous molded product (Y) (hereinafter, also simply referred to as “pore volume (Y)”) is obtained by dimerizing the porous molded product (Y) into α-olefin. From the viewpoint of improving the reaction selectivity when applied to the carrier of the catalyst, it is preferably 0.10 mL / g to 0.80 mL / g, and more preferably 0.15 mL / g to 0.80 mL / g. ..
　The pore volume (Y) can be adjusted, for example, by changing the amount of the specific compound to be supported, the supporting method, and the supporting conditions.
　The pore volume (Y) and pore diameter (pore diameter) (hereinafter, also referred to as "pore diameter (Y) (pore diameter (Y)") are pore distributions measured by the mercury intrusion method. The pore volume (Y) means the value of the pore volume in which the pore diameter (Y) (pore diameter (Y)) is in the range of 0.01 μm to 100 μm. Pore volume (Y). The measuring method of is described in the section of Examples.
[0026]
(Y-2) Median pore diameter
　median pore diameter of the porous compact (Y) (hereinafter, simply referred to as "median pore diameter (Y)".), The porous molded body (Y) alpha-olefin dimerization From the viewpoint of improving the reaction selectivity when applied to the carrier of the catalyst for use, it preferably exceeds 0.01 μm, and more preferably 0.15 μm or more. The upper limit of the median pore diameter is preferably 10.0 μm. For the median pore diameter (Y), the pore diameter in the range of 0.01 μm to 100 μm is measured, and the total pore diameter in the above range is 50%. When divided into, it means the pore diameter (D50) in which the large side (large diameter side) and the small side (small diameter side) have the same number. The method for measuring the median pore size (Y) is described in the section of Examples.
[0027]
(Y-3) Crushing strength The crushing strength of the
　porous molded product (Y) is preferably 0.7 kgf or more, more preferably 1.0 kgf or more, and further preferably 1.5 kgf or more. The upper limit is preferably 15.0 kgf.
　The crushing strength of the porous molded body (Y) is synonymous with the crushing strength of the porous molded body (X) described above, and the crushing strength can be obtained by the same method as that of the porous molded body (X). it can.
[0028]
　The porous molded product (Y) according to the present disclosure can be suitably used for the α-olefin dimerization catalyst according to the present disclosure described later.
[0029]
<< Production method of porous molded product (Y) >>
　The method for producing the porous molded product (Y) according to the present disclosure is a porous molded product (x-1) to (x-3) satisfying the above requirements (x-1) to (x-3). An alkali metal carbonate or an alkali metal hydrogen carbonate (specific compound) is supported on X) in the range of 1 part by mass to 230 parts by mass with respect to 100 parts by mass of the porous molded product (X). (Hereinafter, also referred to as “supporting step”) and a step of heat-treating the carried material at 100 ° C. to 500 ° C. to obtain a porous molded product (Y) (hereinafter, also referred to as “heat treatment step”). ) And.
　The porous molded product (Y) obtained by the method for producing the porous molded product (Y) according to the present disclosure has a structure in which the porous molded product (X) and the specific compound are in close contact with each other. Even when the molded product (Y) is used as a catalyst for the α-olefin dimerization reaction, it is difficult to pulverize, so that the α-olefin dimerization reaction can be continued for a long period of time.
　The porous molded body (X) used in the method for producing the porous molded body (Y) according to the present disclosure, and the alkali metal carbonate or alkali metal hydrogen carbonate are the porous molded body (Y) according to the present disclosure described above. ), And the alkali metal carbonate or the alkali metal hydrogen carbonate, and the preferred embodiment is also the same.
Hereinafter, each step of the method for producing the porous molded product (Y) according to the present disclosure will be described.
[0030]
In the
　supporting step, a specific compound is supported on the porous molded product (X) in the range of 1 part by mass to 230 parts by mass with respect to 100 parts by mass of the porous molded product (X). Is the process of obtaining.
　The amount of the specific compound supported on the porous molded body (X) (hereinafter, also referred to as “supported amount”) is determined from the viewpoint of obtaining a structure in which the porous molded body (X) and the specific compound are in close contact with each other. It is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and further preferably 10 or more parts with respect to 100 parts by mass of the body (X). From the same viewpoint, the amount of the specific compound carried in the porous molded body (X) is preferably 200 parts by mass or less, more preferably 150 parts by mass, with respect to 100 parts by mass of the porous molded body (X). It is less than or equal to, more preferably 100 parts by mass or less, and particularly preferably 50 parts by mass.
[0031]
　In the supporting step, the specific compound may be used after being dissolved or dispersed in a solvent, but it is preferably used after being dissolved in a solvent from the viewpoint of obtaining a high supporting rate. The solvent is preferably water.
　When the specific compound is dissolved in water and used, the concentration of the aqueous solution of the specific compound is preferably 10% by mass to 50% by mass, preferably 30% by mass to 50% by mass, from the viewpoint of obtaining a high carrying ratio. More preferably.
[0032]
　Various methods can be adopted as a method for supporting the specific compound on the porous molded product (X) (hereinafter, also referred to as “supporting method”).
　Examples of the supporting method include a vapor deposition method, a sputtering method, a chemical vapor deposition method (CVD method), an impregnation method and the like.
　From the viewpoint of dissolving the specific compound in water, the impregnation method is preferable as the supporting method.
　The impregnation method is not particularly limited, and may be, for example, a method in which an aqueous solution of a specific compound is stirred to impregnate the porous molded body (X), and the aqueous solution of the specific compound is left to stand without stirring. A method of impregnating the porous molded body (X) may be used. Moreover, you may use these methods in combination.
[0033]
　When the supporting step in the method for producing the porous molded product (Y) is a step of supporting a specific compound by an impregnation method to obtain a carrier, the supporting step has a predetermined concentration from the viewpoint of obtaining a high loading rate. It is preferable that the step is to impregnate the porous molded product (X) with the aqueous solution of the specific compound adjusted to.
[0034]
　When the aqueous solution of the specific compound is allowed to stand and impregnated into the porous molded product (X), the standing time is such that the aqueous solution of the specific compound is placed in the pores (that is, the inner surface of the pores) of the porous molded product (X). From the viewpoint of sufficient diffusion, it is preferably 1 hour or longer, more preferably 3 hours or longer, and further preferably 5 hours or longer. The upper limit of the standing time is preferably 24 hours from the viewpoint of manufacturing suitability.
[0035]
　In the method for producing a porous molded product (Y) according to the present disclosure, from the viewpoint of obtaining a high loading ratio, in the above-mentioned supporting step, the porous molded product (X) is impregnated with a specific compound, and then the carrier is supported. It is preferable to have a step of taking out the specific compound from the aqueous solution (hereinafter, also referred to as “step of recovering the carrier”).
　The method for removing the carrier from the aqueous solution of the specific compound is not particularly limited, and for example, a method of evaporating water by evaporation to dryness, a method of recovering the carrier from the aqueous solution of the specific compound using a sieve, or the like. There may be. When the carrier is recovered from the aqueous solution of the specific compound using a sieve, the carrier can be easily taken out with lower energy than, for example, in the case of evaporation to dryness.
[0036]
The
　heat treatment step is a step of heat-treating the carrier at 100 ° C. to 500 ° C. to obtain a porous molded product (Y).
　By heat-treating the carrier within the above temperature range, the carrier can be sufficiently dried. Further, when the specific compound supported on the carrier is at least one compound selected from the group consisting of NaHCO 3 and KHCO 3 , these compounds are thermally decomposed to generate a gas such as water vapor. , A porous molded product (Y) having a pore volume suitable for a catalyst can be obtained.
　The temperature of the heat treatment step is 100 ° C. to 500 ° C., preferably 150 ° C. to 450 ° C., and more preferably 180 ° C. to 400 ° C. under atmospheric pressure.
　The temperature of the heat treatment can be arbitrarily set depending on the type of the specific compound.
[0037]
　As described above, the porous molded product (Y) produced by the production method according to the present disclosure is excellent in strength and shape uniformity, and is therefore suitable as a catalyst carrier, particularly as a carrier for a catalyst for α-olefin dimerization. is there.
　Although (Y) obtained by the production method according to the present disclosure is preferably used as a carrier for the α-olefin dimerization catalyst, it may be used as a catalyst carrier other than the carrier for the α-olefin dimerization catalyst. ..
[0038]
<< α-Olefin Dimerization Catalyst >>
　The α-olefin dimerization catalyst according to the present disclosure is a catalyst in which an alkali metal (D) is supported on a porous molded body (Y) according to the present disclosure. That is, the α-olefin dimerization catalyst according to the present disclosure is a carrier of the porous molded product (Y) and the alkali metal (D).
[0039]
　Examples of the alkali metal (D) include lithium, sodium, potassium and the like, but from the viewpoint of catalytic activity, sodium, potassium or a mixture of sodium and potassium is preferable. Here, the alkali metal (D) indicates a zero-valent metal that has not been ionized. When the purity of the alkali metal is 90% or more, the alkali metal (D) may contain a component other than the alkali metal, but is preferably substantially not contained.
　In the present disclosure, "substantially free" means that the content is less than 1% by mass, preferably less than 0.1% by mass. The purity of the alkali metal indicates the mass fraction of the alkali metal in the α-olefin dimerization catalyst.
　Examples of the components other than the alkali metal include various oxides or hydroxides of metal elements other than Group 1 elements of the periodic table, metal elements other than Group 1 elements of the periodic table, and the like.
The alkali metal (D) may be used alone or in combination of two or more.
[0040]
　The content of the alkali metal (D) in the α-olefin dimerization catalyst (that is, the carrying ratio of the alkali metal (D)) is different from that of the alkali metal (D) and the carrier (that is, the porous molded body (Y)). When the total mass of the above is 100% by mass, it is usually in the range of 0.5% by mass to 15% by mass, preferably in the range of 1% by mass to 13% by mass.
[0041]
<< Method for producing α-olefin dimerization catalyst >> In the method for producing an
　α-olefin dimerization catalyst according to the present disclosure, an alkali metal (D) is supported on a porous molded product (Y) according to the present disclosure. This comprises a step of obtaining a catalyst for α-olefin dimerization.
　Since the method for producing an α-olefin dimerization catalyst according to the present disclosure includes the above steps, an α-olefin dimerization catalyst having excellent pulverization inhibitory properties can be obtained. Further, since it has the above steps, it is easy to obtain a catalyst for α-olefin dimerization having excellent reaction selectivity in the α-olefin dimerization reaction.
[0042]
　In the method for producing a catalyst for α-olefin dimerization, various known supporting methods may be adopted as a method for supporting the alkali metal (D) on the porous molded body (Y) according to the present disclosure.
　The temperature during the loading treatment is usually in the range of 150 ° C. to 400 ° C. under atmospheric pressure. From the viewpoint of obtaining a catalyst having excellent catalytic activity, catalyst life, and selectivity for α-olefin dimerization products, the temperature during the supporting treatment is preferably in the range of 200 ° C. to 350 ° C., preferably 200 ° C. to 350 ° C. The range of 300 ° C. is more preferable. The atmosphere at the time of the supporting treatment may be a reducing atmosphere or an inert atmosphere as long as it is not a water and oxidizing atmosphere. In consideration of safety and economy, it is preferable to carry out the support treatment in a nitrogen atmosphere.
[0043]
　In order to uniformly support the alkali metal (D) during the supporting treatment, the porous molded body (Y) and the alkali metal (D) are vibrated, rotated, or stirred to be supported on the porous molded body (Y). Is preferable.
　It is known that the alkali metal (D) undergoes an exchange reaction with the alkali metal contained in the carrier when it comes into contact with the carrier (porous molded body (Y)) under heating.
[0044]
　The method for producing the α-olefin dimerization catalyst preferably further includes a step of preparing the porous molded product (Y).
　Examples of the step of preparing the porous molded product (Y) include each step of the method for producing the porous molded product (Y), and the preferred embodiment is also the same.
[0045]
　The porous molded product (Y) obtained by the method for producing the porous molded product (Y) according to the present disclosure has a pore diameter adjusted to be larger than that of the molded product produced by the prior art. Is obtained. Further, since the carrying ratio of the alkali metal (D) and the catalytic activity are correlated, it is possible to support a larger amount of the alkali metal (D) in the porous molded body in which the pore diameter is adjusted to be larger. The α-olefin dimerization catalyst according to the disclosure can carry out an α-olefin dimerization reaction with higher activity.
　In general, as the catalytic activity increases, the load on the carrier increases, and the disintegration (pulverization) of the catalyst carrier (porous molded body (Y)) tends to increase. ), Since the strength (for example, the crushing strength in the radial direction) is secured, it is considered that the α-olefin dimerization catalyst is unlikely to disintegrate (pulverize).
[0046]
　When observing the surface of the porous molded product (Y) according to the present disclosure, it may be relatively easy to distinguish between the color derived from the porous molded product (X) and the color derived from the specific compound.
　The color tone of the surface of the porous molded product (Y) according to the present disclosure generally shows a blackish color tone, which is a color derived from a specific compound. Further, as the surface color of the porous molded product (Y) according to the present disclosure, it is preferable that the proportion of the color derived from this specific compound is high from the viewpoint of pulverization inhibitory property.
[0047]
　The evaluation of the surface color of the porous molded product (Y) according to the present disclosure can be judged by the index (CI) occupied by the color derived from the specific compound.
　In the present specification, the index (CI) (hereinafter, also referred to as “index (CI)”) occupied by the color derived from the specific compound can be obtained as follows.
　As described above, the specific compound (X) is substantially in the form of particles.
　Adjust the magnification so that 1:50 or more porous compacts (Y) fit in the field of view, take a picture of the porous compacts (Y) with a digital camera, and select any 50 porous compacts (Y) from the image. Select the porous molded product (Y).
　2: Next, regarding the 50 porous molded products (Y), (i) almost the entire surface of the porous molded product (Y) exhibits a color derived from a specific compound, (ii) porous. It is classified into three types: one in which the surface of the molded product (Y) is partially colored, and (iii) one in which the surface of the porous molded product (Y) is almost uncolored.
　3: The porous molded products (Y) classified into (i) to (iii) are given the following scores, and the total score is used as an index (CI).
[0048]
　2 points: Almost the entire surface of the porous molded product (Y) exhibits a color derived from a specific compound.
　1 point: The surface of the porous molded product (Y) is partially colored.
　0 point: The surface of the porous molded product (Y) is almost uncolored.
[0049]
　Therefore, when all 50 porous molded articles (Y) exhibit a color derived from a specific compound, the index (CI) is 100 points, and the surface of the porous molded article is almost uncolored (that is, that is). If the specific compound is not supported), the score is 0.
[0050]
　The index (CI) is preferably 100 ≧ index (CI) ≧ 20 from the viewpoint of pulverization inhibitory property.
[0051]
　The preferred lower limit of the index (CI) value is 30, more preferably 40, and even more preferably 45. On the other hand, the preferred upper limit of the index (CI) value is 95, more preferably 92.
　From the viewpoint of pulverization inhibitory property, the (CI) value is preferably 30 to 95, preferably 40 to 92, and more preferably 45 to 92.
　When the size (size) of the porous molded product (Y) is small, the index (CI) value can be obtained by photographing with a suitable device such as an optical microscope instead of a digital camera.
[0052]
<< Method for producing α-olefin dimer >>
　The method for producing an α-olefin dimer according to the present disclosure is a dimerization reaction of α-olefin in the presence of the α-olefin dimerization catalyst according to the present disclosure. To obtain a dimer of α-olefin by carrying out the above.
　Since the method for producing an α-olefin dimer has the above steps, the α-olefin dimerization reaction is carried out in the presence of a catalyst for α-olefin dimerization having excellent pulverization inhibitory properties, so that α-olefin dimerization is carried out. The α-olefin dimer can be obtained in a high yield with excellent selectivity for the product.
[0053]
　Specific examples of the α-olefin used in the method for producing an α-olefin dimer include lower α-olefins such as ethylene, propylene, 1-butene, isobutylene and 1-pentene.
　The method for producing an α-olefin dimer is to carry out the α-olefin dimerization reaction in the presence of the above-mentioned α-olefin dimerization catalyst to dimerize propylene among the lower α-olefin dimerization reactions. 4-Methyl-1-pentene according to the above and 3-methyl-1-pentene obtained by codimerization of 1-butene and ethylene in high yield, according to the
　method for producing an α-olefin dimer according to the present disclosure. Then, since the α-olefin dimerization catalyst having excellent pulverization inhibitory property according to the present disclosure is used, a stable high yield of 4-methyl-1-pentene, 3-methyl-1-pentene, etc. over a long period of time Can be manufactured at.
[0054]
　In the method for producing an α-olefin dimer according to the present disclosure, the reaction temperature in the dimerization reaction of α-olefin is usually 0 ° C. to 300 ° C., preferably 50 ° C. to 200 ° C.
　The reaction pressure is usually normal pressure, that is, about 0.1 MPa to 19.6 MPa (200 kg / cm 2- G), preferably 1.96 MPa to 14.7 MPa (20 kg / cm 2- G to 150 kg). It is in the range of / cm 2- G).
　The state of α-olefin in the dimerization reaction of α-olefin varies depending on the dimerization reaction conditions and the type of α-olefin used, but can generally be in a liquid phase state, a gas phase state or a supercritical state.
　Further, the dimerization reaction of α-olefin can be carried out by a fixed bed method or a fluidized bed method, and among them, the fixed bed method is preferable. When performing the dimerization reaction in a fixed bed system, the liquid hourly space velocity of the α- olefin (LHSV) is usually 0.1 hr -1 ~ 10 hr -1 is preferably 0.5 hr -1 ~ 5 hr -1 in the range of is there.
　The unreacted α-olefin and the dimerized anti-product are separated from the mixture after the completion of the dimerization reaction according to a conventional method, and the unreacted α-olefin is recycled and reused in the dimerization reaction.
Example
[0055]
　Hereinafter, embodiments of the present disclosure will be specifically described with reference to Examples, but the raw materials, amounts used, proportions, treatment contents, treatment procedures, etc. shown in the following Examples deviate from the purpose of the embodiments of the present disclosure. Unless otherwise specified, it can be changed as appropriate. Therefore, the embodiments of the present disclosure are not limited to these examples.
[0056]
[Measurement of pore volume (X) and (Y), and median pore diameter (X) and (Y)] As described
　above, a mercury porosimeter (manufactured by Micrometrics, model number: Auto Pole IV) is used. The pore volume (mL / g) of the pores having a pore diameter (that is, the pore diameter) in the range of 0.01 μm to 100 μm was measured by the mercury intrusion method. Further, the pore diameter in the above range was measured, and the median pore diameter (μm) was calculated from the measured value.
[0057]
[Measurement of crushing strength of porous molded body] Porous medium using a
　digital hardness tester (manufactured by Fujiwara Seisakusho, model number: KHT-40N) according to the method described in JIS Z8841 (1993) "Granulated product-strength test method". The crushing strength (kgf) in the radial direction of the molded body (that is, the body direction (longitudinal direction) of the columnar molded body) was measured.
　The principle of measuring the fracture strength is that a cylindrical porous molded body to be measured is placed on a stationary sample table, and a movable pressure surface is lowered from above at a constant speed to form a columnar shape. This is to measure the strength when it is pressed against the porous molded body of No. 1 and broken.
[0058]
(Example 1)
[Porous molded body (X1)] As the
　porous molded body (X1), Al 2 O 3 manufactured by Saint-Gobain Co., Ltd. (Product number: SA5102, diameter 3.0 mm, height 2 mm to 7 mm, thin A pore volume of 0.26 mL / g, a median pore diameter of 1.17 μm, and a crushing strength of 9.4 kgf) were used.
[0059]
[Production of Porous Molded Body (Y1)]
　57.5 g of the porous molded product (X1) was impregnated with 100 g of a 30 mass% K 2 CO 3 aqueous solution and allowed to stand at room temperature (25 ° C.) for 5 hours. Then, the porous molded product (X1) is taken out from the K 2 CO 3 aqueous solution using a sieve (opening diameter: 710 μm), heat-treated in dry air at 300 ° C. for 2 hours in an electric furnace, and the porous molded product (X1) is subjected to heat treatment. ) A porous molded body (Y1) in which 10 parts by mass of K 2 CO 3 was supported with respect to 100 parts by mass was obtained.
　Table 1 shows the pore volume, median pore diameter, and radial crush strength of the obtained porous molded product (Y1).
[0060]
[Preparation of α-olefin dimerization catalyst (Z1)]
　98.0 parts by mass of the porous molded product (Y1) obtained above was dried in a nitrogen stream at 300 ° C. for 2 hours, and then under a nitrogen atmosphere stream. , 2.0 parts by mass of sodium was added, and the mixture was stirred at 280 ° C. for 3.5 hours to prepare a catalyst for α-olefin dimerization (Z1).
[0061]
　Since no adhesion of the added sodium was observed on the supporting container, it was judged that the entire amount of sodium was supported on the porous molded product (Y1). At this time, the sodium content (that is, the sodium carrying ratio) in the α-olefin dimerization catalyst (Z1) was 2.0% by mass.
[0062]
[Evaluation]
-Pulsation inhibitory property: Pulverization rate-
[Dimmation reaction of ethylene and 1-butene]
　2.5 g of α-olefin dimerization catalyst (Z1) obtained by the above preparation method is used as a single-tube reaction. It is filled in a vessel (diameter 18 mm), and a mixed solution of ethylene and 1-butene is continuously supplied to the catalyst layer at a reactor internal temperature of 80 ° C., a reaction pressure of 9.3 MPa, and a flow rate of 7.2 g / h. A synthetic reaction of 3-methyl-1-pentene (hereinafter abbreviated as 3MP-1) was carried out by a dimerization reaction with -butene. After the flow reaction was carried out for 140 hours, the α-olefin dimerization catalyst (Z1) was taken out from the reactor and the weight was measured.
　After that, all of the removed α-olefin dimerization catalyst (Z1) was placed on the upper part of a net sieve having a mesh size of 500 μm, and the powder mass passed through the sieve (pass) was manually sifted from inside the reactor. The pulverization rate of the catalyst was calculated by dividing by the weight of the α-olefin dimerization catalyst (Z1) taken out. The results are shown in Table 1.
[0063]
(Example 2)
[Porous molded body (X2)] As the
　porous molded body (X2), Al 2 O 3 manufactured by Saint-Gobain Co., Ltd. (Product number: SA3132, diameter 3.0 mm, height 2 mm to 7 mm, thin A pore volume of 0.55 mL / g, a median pore diameter of 0.87 μm, and a crushing strength of 1.5 kgf) were used.
[0064]
[Production of Porous Molded Body (Y2)]
　30.9 g of the porous molded product (X2) was impregnated with 100 g of a 40% by mass K 2 CO 3 aqueous solution and allowed to stand at room temperature for 5 hours. Then, the porous molded product (X2) was taken out from the K 2 CO 3 aqueous solution using a sieve (opening diameter: 710 μm), and heat-treated in dry air at 300 ° C. for 2 hours in an electric furnace to perform the porous molded product (X2). A porous molded body (Y2) in which 32 parts by mass of K 2 CO 3 was supported with respect to 100 parts by mass was obtained.
　Table 1 shows the pore volume, median pore diameter, and radial crush strength of the obtained porous molded product (Y2).
[0065]
[Preparation of catalyst for α-olefin dimerization (Z2)]
　90.0 parts by mass of the porous molded product (Y2) was dried in a nitrogen stream at 300 ° C. for 2 hours, and then sodium 10. 0 parts by mass was added, and the mixture was stirred at 280 ° C. for 3.5 hours to prepare a catalyst for α-olefin dimerization (Z2).
[0066]
　Since no adhesion of the added sodium was observed on the supporting container, it was judged that the entire amount of sodium was supported on the porous molded product (Y2). At this time, the sodium content (that is, the sodium support ratio) in the α-olefin dimerization catalyst (Z2) was 10.0% by mass.
　Using the obtained α-olefin dimerization catalyst (Z2), the α-olefin dimerization reaction was carried out in the same manner as in Example 1 for evaluation. The results are shown in Table 1.
[0067]
(Example 3)
[Porous molded body (X3)] As the
　porous molded body (X3), Al 2 O 3 manufactured by Saint-Gobain Co., Ltd. (Product number: SA31132, diameter 3.0 mm, height 2 mm to 7 mm, thin A pore volume of 0.77 mL / g, a median pore diameter of 0.15 μm, and a crushing strength of 3.5 kgf) were used.
[0068]
Production of porous compact (Y3)]
　porous shaped body (X3) 26.8 g, 50 wt% K 2 CO 3 impregnated with an aqueous solution 100 g, and allowed to stand at room temperature for 5 hours. Then, the porous molded body (X3) is taken out from the K 2 CO 3 aqueous solution using a sieve, and heat-treated in dry air at 300 ° C. for 2 hours in an electric furnace with respect to 100 parts by mass of the porous molded body (X3). A porous molded body (Y3) carrying 68 parts by mass of K 2 CO 3 was obtained.
　Table 1 shows the pore volume, median pore diameter, and radial crush strength of the obtained porous molded product (Y3).
[0069]
[Preparation of catalyst for α-olefin dimerization (Z3)]
　96.5 parts by mass of the porous molded product (Y3) was dried in a nitrogen stream at 300 ° C. for 2 hours, and then sodium 3. 5 parts by mass was added, and the mixture was stirred at 280 ° C. for 3.5 hours to prepare a catalyst for α-olefin dimerization (Z3).
[0070]
　Since no adhesion of the added sodium to the supporting container was observed, it was judged that the entire amount of sodium was supported on the porous molded product. At this time, the sodium content (that is, the sodium support ratio) in the α-olefin dimerization catalyst (Z3) was 3.5% by mass. Using the obtained α-olefin dimerization catalyst (Z3), the α-olefin dimerization reaction was carried out in the same manner as in Example 1 for evaluation. The results are shown in Table 1.
[0071]
(Example 4)
[Porous molded body (X4)] As the
　porous molded body (X4), Al 2 O 3 manufactured by Saint-Gobain Co., Ltd. (Product number: SA31132, diameter 3.0 mm, height 2 mm to 7 mm, thin A pore volume of 0.77 mL / g, a median pore diameter of 0.15 μm, and a crushing strength of 3.5 kgf) were used.
[0072]
[Production of Porous Molded Body (Y4)]
　26.9 g of the porous molded product (X4) was impregnated with 100 g of a 30 mass% K 2 CO 3 aqueous solution and allowed to stand at room temperature for 5 hours. Then, the porous molded body (X4) is taken out from the K 2 CO 3 aqueous solution using a sieve, and heat-treated in dry air at 300 ° C. for 2 hours in an electric furnace with respect to 100 parts by mass of the porous molded body (X4). A porous molded body (Y4) carrying 35 parts by mass of K 2 CO 3 was obtained.
　Table 1 shows the pore volume, median pore diameter, and radial crush strength of the obtained porous molded product (Y4).
[0073]
[Preparation of catalyst for α-olefin dimerization (Z4)]
　87.0 parts by mass of the porous molded product (Y4) was dried in a nitrogen stream at 300 ° C. for 2 hours, and then sodium 13. 0 parts by mass was added, and the mixture was stirred at 280 ° C. for 3.5 hours to prepare a catalyst for α-olefin dimerization (Z4).
[0074]
　Since no adhesion of the added sodium to the supporting container was observed, it was judged that the entire amount of sodium was supported on the porous molded product. At this time, the sodium content (that is, the sodium support ratio) in the α-olefin dimerization catalyst (Z4) was 13.0% by mass. Using the obtained α-olefin dimerization catalyst (Z4), the α-olefin dimerization reaction was carried out in the same manner as in Example 1 for evaluation. The results are shown in Table 1.
[0075]
(Comparative Example 1)
[Adjustment of Tableting Mold (T1)]
　100 parts by mass of K 2 CO 3 (manufactured by Asahi Glass Co., Ltd., purity 99%) and 0.9 parts by mass of graphite (purity 98%, median) A diameter (d50) of 7 μm and a specific surface area of ​​150 m 2 / g measured by the BET method ) are uniformly mixed, and the compaction strength is controlled to be 1.7 g / mL, and the mixture is locked in dry air. A graphite compact (T1) was obtained by heat-treating at 300 ° C. for 2 hours.
　Table 1 shows the pore volume, median pore diameter, and radial crush strength of the obtained tableted compact (T1).
[0076]
[Preparation of α-olefin dimerization catalyst (T1)] In
　Example 3, α was formed in the same manner as in Example 3 except that a tableting compact (T1) was used instead of the porous compact (Y3). -A catalyst for olefin dimerization (T1) was prepared. The sodium content (that is, the sodium support ratio) in the α-olefin dimerization catalyst (T1) is shown in Table 1.
　Using the obtained α-olefin dimerization catalyst (T1), the α-olefin dimerization reaction was carried out in the same manner as in Example 1 for evaluation. The results are shown in Table 1.
[0077]
[table 1]

[0078]
　As shown in Table 1, the requirement (x-1) ~ porous compact satisfying (x-4) and (X), Na 2 CO 3 , NaHCO 3 , K 2 CO 3 , and KHCO 3 the group consisting of Examples 1 to 4 containing at least one compound selected from the above, and the content of the compound is in the range of 1 part by mass to 230 parts by mass with respect to 100 parts by mass of the porous molded product (X). The porous molded product (Y) of No. 1 was excellent in suppressing pulverization in the α-olefin dimerization reaction even when it was used in the α-olefin dimerization reaction.
　On the other hand, the tableting molded product (T1) of Comparative Example 1, which does not contain the porous molded product (X) satisfying the above requirements (x-1) to (x-4), was used in the α-olefin dimerization reaction. In the case, pulverization by α-olefin dimerization reaction was confirmed.
[0079]
(Example 5)
[Porous molded product (X5)] As the
　porous molded product (X5), Al 2 O 3 manufactured by Coralvan Co., Ltd. (Product number: SA31132, diameter 3.0 mm, height 2 mm to 7 mm, thin Pore ​​volume 0.77 mL / g, median pore diameter 0.15 μm, crush strength 3.5 kgf) baked at 1,200 ° C. for 5 hours (pore volume 0.69 mL / g, median pore diameter 0) .52 μm and crush strength 3.7 kgf) were used.
[0080]
[Production of Porous Molded Body (Y5)]
　300 g of the porous molded product (X5) was impregnated with 500 g of a 30% by mass K 2 CO 3 aqueous solution and allowed to stand at room temperature for 5 hours. Then, the porous molded body (X5) is taken out from the K 2 CO 3 aqueous solution using a sieve, and heat-treated in dry air at 300 ° C. for 2 hours in an electric furnace with respect to 100 parts by mass of the porous molded body (X5). A porous molded body (Y5) carrying 28 parts by mass of K 2 CO 3 was obtained.
[0081]
[Preparation of catalyst for α-olefin dimerization (Z5)]
　87.0 parts by mass of the porous molded product (Y5) was dried in a nitrogen stream at 300 ° C. for 2 hours, and then sodium 13. 0 parts by mass was added, and the mixture was stirred at 280 ° C. for 3.5 hours to prepare a catalyst for α-olefin dimerization (Z5).
[0082]
　Since no adhesion of the added sodium to the supporting container was observed, it was judged that the entire amount of sodium was supported on the porous molded product. The loading ratio at this time was 13.0% by mass. Using the obtained α-olefin dimerization catalyst (Z5), the α-olefin dimerization reaction was carried out in the same manner as in Example 1. The results are shown in Table 2.
[0083]
(Example 6)
[Porous molded product (X6)] As the
　porous molded product (X6), Al 2 O 3 manufactured by Coralvan Co., Ltd. (Product number: SA31132, diameter 3.0 mm, height 2 mm to 7 mm, thin A pore volume of 0.77 mL / g, a median pore diameter of 0.15 μm, and a crushing strength of 3.5 kgf) was calcined at 1,200 ° C. for 5 hours (pore volume of 0.69 mL / g, median pore diameter of 0. 52 μm and crush strength 3.7 kgf) were used.
[0084]
Production of porous compact (Y6)]
　porous shaped body (X6) 32.8 g, 25 wt% K 2 CO 3 impregnated with an aqueous solution 100 g, and allowed to stand at room temperature for 5 hours. Then, the porous molded body (X6) is taken out from the K 2 CO 3 aqueous solution using a sieve, and heat-treated in dry air at 300 ° C. for 2 hours in an electric furnace with respect to 100 parts by mass of the porous molded body (X6). A porous molded body (Y6) carrying 24 parts by mass of K 2 CO 3 was obtained.
[0085]
[Preparation of catalyst for α-olefin dimerization (Z6)]
　87.0 parts by mass of the porous molded product (Y6) was dried in a nitrogen stream at 300 ° C. for 2 hours, and then sodium 13. 0 parts by mass was added, and the mixture was stirred at 280 ° C. for 3.5 hours to prepare a catalyst for α-olefin dimerization (Z6).
[0086]
　Since no adhesion of the added sodium to the supporting container was observed, it was judged that the entire amount of sodium was supported on the porous molded product. The loading ratio at this time was 13.0% by mass. Using the obtained α-olefin dimerization catalyst (Z6), the α-olefin dimerization reaction was carried out in the same manner as in Example 1 for evaluation. The results are shown in Table 2.
[0087]
(Example 7)
[Preparation of catalyst for α-olefin dimerization (Z7)]
　84.0 parts by mass of the porous molded body (Y6) was dried in a nitrogen stream at 300 ° C. for 2 hours, and then a nitrogen atmosphere stream. Below, 16.0 parts by mass of sodium was added, and the mixture was stirred at 280 ° C. for 3.5 hours to prepare a catalyst for α-olefin dimerization (Z6).
[0088]
　Since no adhesion of the added sodium to the supporting container was observed, it was judged that the entire amount of sodium was supported on the porous molded product. The loading ratio at this time was 16.0% by mass. Using the obtained α-olefin dimerization catalyst (Z7), the α-olefin dimerization reaction was carried out in the same manner as in Example 1 for evaluation. The results are shown in Table 2.
[0089]
(Example 8)
　3.8 g of the α-olefin dimerization catalyst (Z6) prepared in Example 6 was filled in a single-tube reactor (diameter 18 mm), the temperature inside the reactor was 140 ° C., and the reaction pressure was 9.8 MPa. , Propylene was continuously supplied to the catalyst layer at a propylene flow rate of 4 g / h, and 4-methyl-1-pentene (hereinafter abbreviated as 4MP-1) was obtained by a dimerization reaction of propylene. A distribution reaction was carried out and the production of 4MP-1 was confirmed. The α-olefin dimerization catalyst (Z6) was taken out from the reactor and weighed. Then, all of the removed α-olefin dimerization catalyst (Z6) was placed on the upper part of a 500 μm net sieve and sieved manually. The pulverization rate of the catalyst was calculated by dividing the mass of the powder of the catalyst (Z6) that passed the sieve by the weight of the catalyst (Z6) taken out from the reactor. The pulverization rate of the α-olefin dimerization catalyst (Z6) was 0%.
[0090]
-Evaluation of the surface color
　of the porous molded body (Y) -The porous molded body (Y6) in Examples 5 to 8 described above is obtained from any 50 photographs taken with a digital camera according to the method described above. The index (CI) of the obtained porous molded product (Y6) was determined based on the above method. The results are shown in Table 2. The index (CI) in Example 8 was 98.
[0091]
[Table 2]

[0092]
　As shown in Table 2, it can be seen that the porous molded product (Y) and the α-olefin dimerization catalyst according to the present disclosure in Examples 5 to 7 are excellent in pulverization inhibitory property.
　Based on the above, the porous molded product (Y) and its production method, the α-olefin dimer catalyst and its production method, and the α-olefin dimer production method according to the present disclosure are described in the α-olefin dimerization reaction. It is excellent in suppressing pulverization in.
[0093]
　The disclosure of Japanese Patent Application No. 2018-066083, filed March 29, 2018, is incorporated herein by reference in its entirety.
　All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Is incorporated herein by reference.
The scope of the claims
[Claim 1]
　The porous molded body (X) satisfying the following requirements (x-1) to (x-3) and an
　alkali metal carbonate or alkali metal hydrogen carbonate are contained, and the
　alkali metal carbonate or alkali metal hydrogen carbonate is contained. The content of the salt is in the range of 1 part by mass to 230 parts by mass with respect to 100 parts by mass of the porous molded body (X).
　Requirement (x-1): The pore volume in the range of 0.01 μm to 100 μm in pore diameter is 0.10 mL / g to 1.00 mL / g.
　Requirement (x-2): The median pore diameter of pores having a pore diameter in the range of 0.01 μm to 100 μm is more than 0.01 μm and not more than 10.0 μm.
　Requirement (x-3): The crushing strength is 0.7 kgf to 15.0 kgf.
[Claim 2]
　The porous molded product (Y) according to claim 1, wherein the porous molded product (X) further satisfies the following requirement (x-4).
　Requirement (x-4): Includes oxides of metal or rare earth elements and at least one compound selected from the group consisting of composite oxides thereof, zeolites, activated carbons, and SiC.
[Claim 3]
Claim 1 or claim, 　wherein the alkali metal carbonate or alkali metal hydrogen carbonate is at least one compound selected from the group consisting of Na 2 CO 3 , NaHCO 3 , K 2 CO 3 , and KHCO 3. 2. The porous molded body (Y) according to 2.
[Claim 4]
　Claims 1 to 3, wherein the pore diameter of the porous molded body (Y) is in the range of 0.01 μm to 100 μm, and the pore volume is 0.10 mL / g to 0.80 mL / g. The porous molded body (Y) according to any one item.
[Claim 5]
The porous molded product (Y) according to any one of claims 1 to 4, 　wherein the porous molded product (X) is a molded product of Al 2 O 3 .
[Claim 6]
　A catalyst for α-olefin dimerization, which carries the alkali metal (D) of the porous molded product (Y) according to any one of claims 1 to 5.
[Claim 7]
　Α-olefin dimer comprising a step of supporting an alkali metal (D) on the porous molded body (Y) according to any one of claims 1 to 5 to obtain a catalyst for α-olefin dimerization. A method for producing a catalyst for quantification.
[Claim 8]
　A method for producing an α-olefin dimer, which comprises a step of dimerizing an α-olefin in the presence of the α-olefin dimer catalyst according to claim 6 to obtain an α-olefin dimer.
[Claim 9]
　An alkali metal carbonate or an alkali metal hydrogen carbonate is added to a porous molded product (X) that satisfies the following requirements (x-1) to (x-3) with respect to 100 parts by mass of the porous molded product (X). It
　comprises a step of obtaining a support by supporting the support in the range of 1 part by mass to 230 parts by mass, and a step of heat-treating the support at 100 ° C. to 500 ° C. to obtain a porous molded product (Y)
. A method for producing a porous molded product (Y).
　Requirement (x-1): The pore volume in the range of 0.01 μm to 100 μm in pore diameter is 0.10 mL / g to 1.00 mL / g.
　Requirement (x-2): The median pore diameter of pores having a pore diameter in the range of 0.01 μm to 100 μm is more than 0.01 μm and not more than 10.0 μm.
　Requirement (x-3): The crushing strength is 0.7 kgf to 15.0 kgf.
[Claim 10]
　The method for producing a porous molded product (Y) according to claim 9, wherein the porous molded product (X) further satisfies the following requirement (x-4).
　Requirement (x-4): Includes oxides of metal or rare earth elements and at least one compound selected from the group consisting of composite oxides thereof, zeolites, activated carbons, and SiC.
[Claim 11]
9 or claim, 　wherein the alkali metal carbonate or alkali metal hydrogen carbonate is at least one compound selected from the group consisting of Na 2 CO 3 , NaHCO 3 , K 2 CO 3 , and KHCO 3. 10. The method for producing a porous molded body (Y) according to 10.
[Claim 12]
　The method for producing a porous molded body (Y) according to any one of claims 9 to 11, wherein the porous molded body (X) is a molded body of Al 2 O 3 .
[Claim 13]
　The method for producing a porous molded product (Y) according to any one of claims 9 to 12, wherein the step of obtaining the carrier is a step of supporting the carrier by an impregnation method to obtain the carrier.