Process for producing indane and hydrindane

Abstract

A production method for indan and hydrindane, the method comprising: a reaction step for introducing a raw material composition containing tetrahydroindene into a continuous reaction vessel that includes a solid catalyst including platinum to bring the raw material composition into contact with the solid catalyst under a 150-350°C condition, thereby obtaining a reaction product containing indan and hydrindane, wherein the amount (mol / min) of hydrogen molecules is at most five times the amount (mol / min) of tetrahydroindene, and the amount (mol / min) of oxygen molecules is at most 0.1 times the amount (mol / min) of tetrahydroindene.

Description

Technical Field

[0001] The present invention relates to a method for producing indane and hydrindane.

Background Art

[0002] Indane is known as a useful substance as a synthetic raw material for pharmaceuticals, a raw material for metallocene catalysts, etc. As a method for producing indane, for example, a method for producing indane by dehydrogenation reaction of tetrahydroindene is known (for example, Patent Document 1).

[0003] Further, hydrindane has excellent solubility and is suitably used for applications such as solvents for paints and cleaning agents. As a method for producing hydrindane, for example, a method for producing hydrindane by hydrogenation reaction of tetrahydroindene is known (for example, Patent Document 2).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present invention is to provide a method for producing indane and hydrindane that can efficiently produce both indane and hydrindane simultaneously.

Means for Solving the Problems

[0006] The present inventors have found that both indane and hydrindane can be efficiently produced from a raw material composition containing 3a,4,7,7a-tetrahydroindene under specific catalysts and specific reaction conditions, and have completed the present invention.

[0007] One aspect of the present invention relates to a method for producing indane and hydrindane, which comprises introducing a raw material composition containing 3a,4,7,7a-tetrahydroindene into a continuous reactor containing a solid catalyst containing platinum, and bringing the above raw material composition into contact with the above solid catalyst under the conditions of 150 to 350 ° C to obtain a reaction product containing indane and hydrindane.

[0008] In the above production method, the amount (mol / min) of hydrogen molecules introduced into the continuous reactor per unit time is 5 times or less with respect to the amount (mol / min) of 3a,4,7,7a-tetrahydroindene introduced into the continuous reactor per unit time. Further, in the above production method, the amount (mol / min) of oxygen molecules introduced into the continuous reactor per unit time is 0.1 times or less with respect to the amount (mol / min) of 3a,4,7,7a-tetrahydroindene introduced into the continuous reactor per unit time.

[0009] In one aspect, the above reaction step may be a step of bringing the above raw material composition into contact with the above solid catalyst under the conditions of 0.1 to 5.0 MPaG.

[0010] In one aspect, the above solid catalyst may contain a carrier and a supported metal supported on the carrier, the above carrier may contain aluminum, and the above supported metal may contain platinum.

[0011] In one aspect, the proportion of the above platinum in the above supported metal may be 80% by mass or more.

[0012] In one aspect, the above platinum may be supported on the above carrier using a platinum source containing no chlorine atom.

[0013] In one aspect, the content of 3a,4,7,7a-tetrahydroindene in the above raw material composition may be 5% by mass or more.

[0014] In one aspect, the content C of hydrindane in the reaction product 2 and the content C of indane relative to 1 The mass ratio (C 1 / C 2 ) may be 1.0 or more and 4.5 or less.

[0015] In one aspect, the reaction product may further contain 3a,4,7,7a-tetrahydroindene, and a part of the reaction product may be reused as the raw material composition in the reaction step.

[0016] The production method according to one aspect may further include a raw material synthesis step of reacting butadiene with at least one selected from the group consisting of cyclopentadiene and dicyclopentadiene to obtain 3a,4,7,7a-tetrahydroindene.

Advantages of the Invention

[0017] According to the present invention, there is provided a method for producing indane and hydrindane, which can efficiently produce indane and hydrindane simultaneously.

Embodiments for Carrying Out the Invention

[0018] Hereinafter, preferred embodiments of the present invention will be described in detail.

[0019] The method for producing indane and hydrindane according to the present embodiment introduces a raw material composition containing 3a,4,7,7a-tetrahydroindene (hereinafter, also simply referred to as "THI") into a continuous reactor containing a solid catalyst containing platinum, and contacts the raw material composition with the solid catalyst under the conditions of 150 to 350°C to obtain a reaction product containing indane and hydrindane, and includes a reaction step.

[0020] In the production method of this embodiment, the amount of hydrogen molecules (mol / min) introduced into the continuous reactor per unit time is 5 times or less with respect to the amount of THI (mol / min) introduced into the continuous reactor per unit time. Further, in the production method of this embodiment, the amount of hydrogen molecules (mol / min) introduced into the continuous reactor per unit time is 0.1 times or less with respect to the amount of THI (mol / min) introduced into the continuous reactor per unit time.

[0021] According to the production method of this embodiment, indane and hydrindane can be efficiently produced simultaneously.

[0022] In the production method of this embodiment, by adopting a specific solid catalyst and specific reaction conditions, the reaction of THI in the continuous reactor proceeds efficiently, and both indane and hydrindane can be obtained in a well-balanced manner.

[0023] Hereinafter, the solid catalyst in this embodiment will be described in detail.

[0024] The solid catalyst may be, for example, a catalyst containing a carrier and a supported metal supported on the carrier. At this time, the solid catalyst preferably contains platinum as the supported metal.

[0025] The carrier is preferably a carrier containing aluminum, and more preferably an inorganic oxide carrier containing aluminum. The carrier may contain alumina (Al 2 O 3 ), may contain alumina and oxides of other elements, or may contain composite oxides of aluminum and other elements. Examples of other elements include silicon (Si), magnesium (Mg), tin (Sn), lead (Pb), zinc (Zn), selenium (Se), iron (Fe), indium (In), etc. Among these, silicon (Si), magnesium (Mg), and tin (Sn) are preferably used. As alumina, γ-alumina is particularly preferred.

[0026] The specific surface area of the carrier may be, for example, 20 m 2 / g or more, preferably 100 m 2 / g or more, more preferably 150 m 2 / g or more. Thereby, the catalytic activity tends to be further improved. Also, the specific surface area of the carrier may be, for example, 500 m 2 / g or less, preferably 400 m 2 / g or less, more preferably 300 m 2 / g or less. Thereby, the strength and moldability of the carrier tend to be further improved. In this specification, the specific surface area of the carrier is measured with a BET specific surface area meter using the nitrogen adsorption method.

[0027] In the solid catalyst, the supported metal supported on the carrier only needs to contain platinum, and may further contain other metals other than platinum. Examples of other metals include Pd, Re, Sn, Fe, Zn, Co, Ni, Ga, In, Mn, etc.

[0028] It is preferable that the supported metal of the solid catalyst is mainly platinum. Specifically, the ratio of platinum in the supported metal may be, for example, 70 mass% or more, preferably 80 mass% or more, more preferably 90 mass% or more, and may be 95 mass% or more, 97 mass% or more, 99 mass% or more, or 99.5 mass% or more.

[0029] From the viewpoint of further improving the catalytic activity, the content of the supported metal in the solid catalyst may be, for example, 0.1 mass% or more, preferably 0.2 mass% or more, and may be 0.5 mass% or more, 1 mass% or more, or 1.5 mass% or more. Also, from the viewpoint of better economy, the content of the supported metal in the solid catalyst may be, for example, 10 mass% or less, preferably 8 mass% or less, more preferably 6 mass% or less, still more preferably 4 mass% or less, and may be 2 mass% or less or 1 mass% or less.

[0030] The suitable range of the platinum content in the solid catalyst may be the same as the suitable range of the content of the supported metal.

[0031] The solid catalyst may be one in which a supported metal is supported on a carrier using a metal source. The metal source is preferably a metal source that does not contain chlorine atoms. Thereby, corrosion of the apparatus is suppressed, and indane and hydrindane can be produced more efficiently.

[0032] Examples of the metal source (platinum source) for supporting platinum include tetraammineplatinum(II) nitrate ([Pt(NH 3 ) 4 (NO 3 ) 2 ), dinitrodiammineplatinum(II) (Pt(NO 2 ) 2 (NH 3 ) 2 ), tetraammineplatinum(II) hydroxide ([Pt(NH 3 ) 4 (OH) 2 ), hexaammineplatinum(IV) hydroxide ([Pt(NH 3 ) 6 (OH) 4 ), hexaammineplatinum(IV) nitrate ([Pt(NH 3 ) 6 )(NO 3 ) 4 , tetraammineplatinum(II) acetate ([Pt(NH 3 ) 4 (CH 3 COO) 2 ) and the like. Among these, as the platinum source, tetraammineplatinum(II) nitrate ([Pt(NH 3 ) 4 (NO 3 ) 2 ), dinitrodiammineplatinum(II) (Pt(NO 2 ) 2 (NH 3 ) 2 ), and tetraammineplatinum(II) hydroxide ([Pt(NH 3 ) 4 (OH) 2 ) are particularly preferred.

[0033] The method for supporting the supported metal is not particularly limited, and for example, known supporting methods such as an impregnation method, a deposition method, a coprecipitation method, a kneading method, an ion exchange method, and a pore filling method can be used.

[0034] The shape of the solid catalyst is not particularly limited and can be appropriately selected according to the shape of the reactor and the like. The shape of the solid catalyst may be, for example, pellet-shaped, granular, honeycomb-shaped, sponge-shaped, or the like.

[0035] As the solid catalyst, one that has been subjected to a reduction treatment as a pretreatment may be used. The reduction treatment can be carried out, for example, by holding the solid catalyst at 100 to 700 ° C in the presence of a reducing gas. The holding time may be, for example, 10 minutes to 20 hours. Examples of the reducing gas include hydrogen and carbon monoxide. By using the reduced solid catalyst, the induction period at the initial stage of the reaction can be shortened. The induction period refers to a state in which there are few supported metals in the solid catalyst in an active state and the catalytic activity is low.

[0036] Next, the reaction step in the present embodiment will be described in detail.

[0037] In the production method of the present embodiment, in the reaction step, a raw material composition containing THI is introduced into a continuous reactor containing a solid catalyst containing platinum, and the raw material composition is brought into contact with the solid catalyst under the conditions of 150 to 350 ° C. As a result, a hydrogen transfer reaction between THIs occurs, and a reaction product containing indane and hydrindane is obtained.

[0038] The raw material composition may further contain other components other than THI. Examples of other components include alkanes, olefins, aromatic compounds, and hydrides of THI.

[0039] From the viewpoints of excellent reactivity and economy, the content of THI in the raw material composition is, for example, 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and may be 10% by mass or more, 30% by mass or more, 50% by mass or more, 70% by mass or more, 90% by mass or more, 95% by mass or more, or even 100% by mass.

[0040] The continuous reactor may be any reactor capable of continuous reaction. Examples of the continuous reactor include a tubular reactor and a continuous stirred tank reactor.

[0041] The reaction mode of the reaction step is not particularly limited, and may be, for example, a fixed bed type, a moving bed type or a fluidized bed type. Among these, from the viewpoint of equipment cost, the fixed bed type is preferred.

[0042] In the reaction step, the temperature (reaction temperature) when the raw material composition is brought into contact with the solid catalyst is 150 °C or higher, preferably 170 °C or higher, more preferably 190 °C or higher, and still more preferably 200 °C or higher. When the reaction temperature is low, the reaction tends to proceed with difficulty. Also, the reaction temperature is 350 °C or lower, preferably 320 °C or lower, more preferably 300 °C or lower, and still more preferably 290 °C or lower. When the reaction temperature is high, the catalyst deterioration tends to proceed easily. The reaction temperature can also be said to be the temperature inside the reactor.

[0043] In the reaction step, the pressure (reaction pressure) when the raw material composition is brought into contact with the solid catalyst may be, for example, 0.01 MPaG or higher, preferably 0.05 MPaG or higher, more preferably 0.1 MPaG or higher, and may be 0.7 GMPa or higher or 0.9 MPaG or higher, from the viewpoint of improving the reactivity. Also, the reaction pressure may be, for example, 9.0 MPaG or lower, preferably 7.0 MPaG or lower, more preferably 5.0 MPaG or lower, and still more preferably 3.0 MPaG or lower, from the viewpoint of better economy.

[0044] The conditions inside the reactor are preferably such that THI becomes a liquid. That is, the reaction step is preferably a step of bringing a liquid raw material composition into contact with a solid catalyst.

[0045] In the reaction step, WHSV may be, for example, 0.1 h -1 or higher, preferably 0.5 h -1 or higher, more preferably 1.0 h -1More preferably, it is 3.0 h or more -1 or more. Further, from the viewpoint of further improving the reactivity, the WHSV may be, for example, 30 h -1 or less, preferably 20 h -1 or less, more preferably 10 h -1 or less, and still more preferably 5.0 h -1 or less. The WHSV represents the weight ratio of the supply amount per unit time of the raw material composition to the solid catalyst filled in the reactor.

[0046] In the reaction step, hydrogen gas, oxygen gas, air, an inert gas, etc. may be introduced into the continuous reactor together with the raw material composition.

[0047] In the reaction step, the amount of hydrogen molecules (mol / min) introduced into the continuous reactor per unit time is 5 times or less with respect to the amount of THI (mol / min) introduced into the continuous reactor per unit time. In other words, the amount C of THI introduced into the continuous reactor per unit time 0 (mol / min), the amount C of hydrogen molecules introduced into the continuous reactor per unit time H2 (mol / min) ratio (C H2 / C 0 ) is 5 or less. In the production method of the present embodiment, indane and hydrindane are generated by the hydrogen transfer reaction between THIs, so the introduction of hydrogen into the continuous reactor is not necessarily required. If the introduction amount of hydrogen gas is too large, the yield of indane may be significantly reduced.

[0048] The ratio (C H2 / C 0 ) is preferably 3 or less, more preferably 1 or less, still more preferably 0.5 or less, even more preferably 0.1 or less, and may be 0.

[0049] In the reaction step, the amount of oxygen molecules (mol / min) introduced into the continuous reactor per unit time is 0.1 times or less with respect to the amount of THI (mol / min) introduced into the continuous reactor per unit time. In other words, the amount C of THI introduced into the continuous reactor per unit time0 The amount C of oxygen molecules introduced into the continuous reactor per unit time with respect to (mol / min). O2 The ratio (C O2 / C 0 ) is 0.1 or less. In the production method of the present embodiment, since indane and hydrindane are generated by the hydrogen transfer reaction between THIs, introduction of oxygen into the continuous reactor is not necessary. When oxygen is introduced, the total yield of indane and hydrindane decreases.

[0050] The ratio (C O2 / C 0 ) is preferably 0.05 or less, more preferably 0.01 or less, and may be 0.

[0051] In the reaction step, a reaction product containing indane and hydrindane generated by the reaction of THI is obtained. Further, the generated hydrindane may contain a cis form and a trans form.

[0052] In the reaction step, the conversion rate of THI may be, for example, 70% or more, preferably 80% or more, more preferably 85% or more, still more preferably 95% or more, and may be 97% or more, 98% or more, 99% or more, or even 100%.

[0053] In the reaction step, the total selectivity of indane and hydrindane may be, for example, 10 mol% or more, preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 90 mol% or more, and may be 100 mol%. Note that the total selectivity of indane and hydrindane can be obtained from the ratio of the total yield of indane and hydrindane to the conversion rate of THI.

[0054] The mass ratio (C 2 of the content C of indane to the content C 1 of hydrindane in the reaction product (C 1 / C 2) may be, for example, 0.5 or more, preferably 0.7 or more, more preferably 1.0 or more, still more preferably 1.3 or more, 1.5 or more, or 2.0 or more. Also, the mass ratio (C 1 / C 2 ) may be, for example, 5 or less, preferably 4.7 or less, more preferably 4.5 or less, still more preferably 4.3 or less, and even more preferably 4 or less.

[0055] A part of the reaction product may be reused as a part of the raw material composition in the reaction step. Thereby, the raw material composition is diluted, the heat generation by the hydrogen transfer reaction is suppressed, the catalyst deterioration due to rapid heat generation is suppressed, and the production efficiency of indane and hydrindane in the whole process may be improved.

[0056] The production method of the present embodiment may further include a raw material synthesis step of reacting butadiene with at least one selected from the group consisting of cyclopentadiene and dicyclopentadiene to obtain THI.

[0057] As described above, the preferred embodiments of the present invention have been described, but the present invention is not limited to the above embodiments.

Examples

[0058] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[0059] (Example 1) To commercially available γ-alumina (manufactured by Sumitomo Chemical Co., Ltd.), an aqueous solution of sodium stannate (manufactured by Kishida Chemical Co., Ltd., Na 2 SnO 3 ·3H 2 O) was mixed. The obtained mixture was dried at 130°C for 12 hours, then calcined at 550°C for 3 hours, and washed with ion-exchanged water. This washing operation was repeated 3 times to prepare a carrier. The tin oxide (SnO 2 ) content of the obtained carrier was 30% by mass. To this carrier, a dinitrodiammineplatinum(II) nitrate solution (manufactured by Tanaka Precious Metals Industry Co., Ltd., [Pt(NH 3) 2 (NO 2 ) 2 / HNO 3 ) was used to impregnate and support platinum so that the platinum content became 3.0% by mass. The obtained platinum-supported material was dried at 130 °C overnight and then calcined at 550 °C for 3 hours. Further, the obtained calcined product was impregnated and supported with potassium using an aqueous potassium carbonate solution (manufactured by FUJIFILM Wako Pure Chemical Corporation, K 2 CO 3 ) so that the potassium content became 0.3% by mass. The obtained potassium-supported material was dried at 130 °C overnight and then calcined at 550 °C for 3 hours to obtain catalyst CAT-1.

[0060] 1.0 g of catalyst CAT-1 was filled into a tubular reactor, and the reaction tube was connected to a fixed-bed flow-type reactor. After the reaction tube was heated to 300 °C at normal pressure, hydrogen was passed through at 50 mL / min for 60 minutes while maintaining the temperature to perform pre-treatment of the catalyst. Next, a raw material composition containing THI was introduced into the reaction tube together with nitrogen gas or hydrogen gas as necessary, and the reaction was carried out under the conditions of temperature, pressure, and WHSV shown in Table 2.

[0061] When a predetermined time had elapsed since the start of the reaction (when the raw material composition was introduced), the reaction product was sampled and analyzed using a gas chromatograph equipped with a flame ionization detector (GC-2014, FID-GC, column HP-1, manufactured by Shimadzu Corporation). Based on the analysis results using the above gas chromatograph, each component (unit: mass%) of the collected reaction product was quantified. From the number of moles of THI, indane, and hydrindane, the conversion rate of THI, and the yields of indane and hydrindane at the time when a predetermined time had elapsed were calculated. The conversion rate of THI is defined by the following formula (1), the yield of indane is defined by formula (2), and the yield of hydrindane is defined by formula (3). TC = {1 - (t1 / t0)} × 100 (1) I = {(i1 - i0) / t0} × 100 (2) H = {(h1 - h0) / t0} × 100 (3) In the formula, TC represents the conversion rate (%) of THI, I represents the yield (%) of indane, H represents the yield (%) of hydrindane, t0 represents the number of moles of THI in the raw material composition, t1 represents the number of moles of THI in the reaction product, i1 represents the number of moles of indane in the reaction product, i0 represents the number of moles of indane in the raw material composition, h1 represents the number of moles of hydrindane in the reaction product, and h0 represents the number of moles of hydrindane in the raw material composition.

[0062] The composition of the catalyst is shown in Table 1. The reaction conditions and measurement results are shown in Table 2.

[0063] (Example 2) Using the same catalyst as in Example 1, indane and hydrindane were produced in the same manner as in Example 1, except that the reaction conditions were changed as described in Table 2. The results are shown in Table 2.

[0064] (Example 3) Using the same catalyst as in Example 1, indane and hydrindane were produced in the same manner as in Example 1, except that the reaction conditions were changed as described in Table 2. The results are shown in Table 2.

[0065] (Example 4) Zeolite H-MFI (SiO 2 / Al 2 O 3 = 1500) manufactured by Tosoh Corporation was impregnated and supported with platinum using a dinitrodiammineplatinum(II) nitrate solution (manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., [Pt(NH 3 ) 2 (NO 2 ) 2 / HNO 3 ) so that the platinum content became 1.0 mass%. The obtained platinum-supported material was dried at 130 °C overnight and then calcined at 550 °C for 3 hours to obtain CAT-2.

[0066] Using CAT-2 as the catalyst, indane and hydrindane were produced in the same manner as in Example 1, except that the reaction conditions were the conditions described in Table 3. The results are shown in Table 3.

[0067] (Example 5) 20.0 g of commercially available γ-alumina (Neo Bead manufactured by Mizusawa Chemical Industry Co., Ltd.) and an aqueous solution prepared by dissolving 25.1 g of magnesium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd., Mg(NO 3 ) 2 ·6H 2 O) in 150 ml of water were mixed. The resulting mixture was stirred at 50 °C for 180 minutes, and then water was removed under reduced pressure using an evaporator. Thereafter, the obtained mixture was dried at 130 °C overnight, calcined at 550 °C for 3 hours, and subsequently calcined at 800 °C for 3 hours. The obtained calcined product and an aqueous solution prepared by dissolving 25.1 g of magnesium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd., Mg(NO 3 ) 2 ·6H 2 O) in 150 ml of water were mixed, stirred at 50 °C for 180 minutes, and then water was removed under reduced pressure using an evaporator. Thereafter, the obtained mixture was dried at 130 °C overnight, calcined at 550 °C for 3 hours, and subsequently calcined at 800 °C for 3 hours. Thereby, an alumina-magnesia carrier having a spinel-type structure was obtained. The obtained alumina-magnesia carrier was subjected to X-ray diffraction measurement (X-ray source: CuKα, apparatus: RINT 2500 manufactured by Rigaku Corporation), and diffraction peaks derived from Mg spinel were confirmed at 2θ = 36.9, 44.8, 59.4, 65.3 deg. This Mg spinel carrier was impregnated with platinum using a dinitrodiammineplatinum(II) nitrate solution (manufactured by Tanaka Kikinzoku Kogyo K.K., [Pt(NH 3 ) 2 (NO 2 ) 2 / HNO 3 ) so that the platinum content became 0.5 mass%, and the obtained platinum-supported product was dried at 130 °C overnight and then calcined at 550 °C for 3 hours to obtain CAT-3.

[0068] Using CAT-3 as a catalyst, indane and hydrindane were produced in the same manner as in Example 1 except that the reaction conditions were changed as shown in Table 3. The results are shown in Table 3.

[0069] (Example 6) Using 0.5% Pt / alumina spheres (CAT-4) manufactured by N.E. Chemcat Corporation as the catalyst, indane and hydrindane were produced in the same manner as in Example 1, except that the reaction conditions were changed as described in Table 3. The results are shown in Table 3.

[0070] (Example 7) Using 0.5% Pt / alumina pellets (CAT-5) manufactured by N.E. Chemcat Corporation as the catalyst, indane and hydrindane were produced in the same manner as in Example 1, except that the reaction conditions were changed as described in Table 3. The results are shown in Table 3.

[0071] (Example 8) Dinitrodiammineplatinum(II) nitrate solution (manufactured by Tanaka Precious Metals Industry Co., Ltd., [Pt(NH 3 ) 2 (NO 2 ) 2 / HNO 3 ) was used to impregnate and support platinum on commercially available γ-alumina (manufactured by Sumitomo Chemical Co., Ltd.) so that the platinum content became 0.5% by mass. The obtained platinum-supported material was dried at 130°C overnight and then calcined at 550°C for 3 hours to obtain CAT-6.

[0072] Using CAT-6 as the catalyst, indane and hydrindane were produced in the same manner as in Example 1, except that the reaction conditions were changed as described in Table 4. The results are shown in Table 4.

[0073] (Example 9) Using the same catalyst CAT-6 as in Example 8, indane and hydrindane were produced in the same manner as in Example 1, except that the reaction conditions were changed as described in Table 4. The results are shown in Table 4.

[0074] (Example 10) Using the same catalyst CAT-6 as in Example 8, indane and hydrindane were produced in the same manner as in Example 1, except that the reaction conditions were changed as described in Table 4. The results are shown in Table 4.

[0075] (Example 11) Using the same catalyst CAT-6 as in Example 8, indane and hydrindane were produced in the same manner as in Example 1 except that the reaction conditions were changed as described in Table 5. The raw material composition was a composition containing 10% by mass of THI, 63% by mass of indane, and 21% by mass of hydrindane. The results are shown in Table 5.

[0076] (Example 12) Using the same catalyst CAT-6 as in Example 8, indane and hydrindane were produced in the same manner as in Example 1 except that the reaction conditions were changed as described in Table 5. The initial raw material composition was a composition containing 10% by mass of THI, 61% by mass of indane, and 27% by mass of hydrindane. Also, while maintaining the THI concentration of the raw material composition at 10% by mass, a part of the obtained reaction product was recycled as the raw material composition to carry out the reaction. Therefore, as the reaction proceeded, the composition of the raw material composition changed, and the raw material composition at 1900 h was a composition containing 10% by mass of THI, 53% by mass of indane, and 16% by mass of hydrindane. The results are shown in Table 5.

[0077] (Comparative Example 1) Using the same catalyst CAT-1 as in Example 1, indane and hydrindane were produced in the same manner as in Example 1 except that the reaction conditions were changed as described in Table 6. The results are shown in Table 6.

[0078] (Comparative Example 2) Using the same catalyst CAT-1 as in Example 1, indane and hydrindane were produced in the same manner as in Example 1 except that the reaction conditions were changed as described in Table 6. The results are shown in Table 6.

[0079] (Comparative Example 3) Indane and hydrindane were produced in the same manner as in Example 1 except that no catalyst was used and the reaction conditions were changed as described in Table 6. The results are shown in Table 6.

[0080] (Comparative Example 4) Zeolite H-MFI manufactured by Tosoh Corporation (SiO 2 / Al 2 O3 Using a reaction temperature of 1500) as catalyst CAT-7, indane and hydrindane were produced in the same manner as in Example 1, except that the reaction conditions were changed as described in Table 6. The results are shown in Table 6.

[0081]

Table 1

[0082]

Table 2

[0083]

Table 3

[0084]

Table 4

[0085]

Table 5

[0086]

Table 6

Claims

1. A raw material composition containing 3a,4,7,7a-tetrahydroindene is introduced into a continuous reactor containing a solid catalyst containing platinum, and the raw material composition is brought into contact with the solid catalyst under conditions of 150 to 350°C to obtain a reaction product containing indane and hydrindane, and the amount of hydrogen molecules (mol / min) introduced into the continuous reactor per unit time is 1 time or less with respect to the amount of 3a,4,7,7a-tetrahydroindene (mol / min) introduced into the continuous reactor per unit time, the amount of oxygen molecules (mol / min) introduced into the continuous reactor per unit time is 0.01 time or less with respect to the amount of 3a,4,7,7a-tetrahydroindene (mol / min) introduced into the continuous reactor per unit time, the solid catalyst contains a carrier and a supported metal supported on the carrier, a method for producing indane and hydrindane, wherein the carrier contains aluminum and the supported metal contains platinum.

2. In the reaction step, the raw material composition is brought into contact with the solid catalyst under conditions of 0.1 to 5.0 MPaG. The production method according to claim 1.

3. The ratio of platinum in the supported metal is 80% by mass or more. The production method according to claim 1.

4. The platinum is supported on the carrier using a platinum source that does not contain chlorine atoms. The production method according to any one of claims 1 to 3.

5. The content of 3a,4,7,7a-tetrahydroindene in the raw material composition is 5% by mass or more. The production method according to any one of claims 1 to 4.

6. The content C of hydrindane in the reaction product ２ to the content C of indane １ The mass ratio of (C １ / C ２ ) is 1.0 or more and 4.5 or less. The production method according to any one of claims 1 to 5

7. the reaction product further contains 3a,4,7,7a-tetrahydroindene, and a part of the reaction product is reused as the raw material composition in the reaction step. The production method according to any one of claims 1 to 6.

8. The production method according to any one of claims 1 to 7, further comprising a raw material synthesis step of reacting butadiene with at least one selected from the group consisting of cyclopentadiene and dicyclopentadiene to obtain 3a,4,7,7a-tetrahydroindene.

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