Catalyst for production of hydrocarbons and method of producing hydrocarbons

Abstract

A catalyst is provided for production of hydrocarbons including monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and aliphatic hydrocarbons having a carbon number of 3 to 4 from feedstock in which a 10 vol % distillation temperature is 140° C. or higher and a 90 vol % distillation temperature is 380° C. or lower. The catalyst includes crystalline aluminosilicate including large-pore zeolite having a 12-membered ring structure.

Claims

1. A catalyst for production of hydrocarbons including monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and aliphatic hydrocarbons having a carbon number of 3 to 4 from feedstock in which a 10 vol % distillation temperature is 140° C. or higher and a 90 vol % distillation temperature is 380° C. or lower, the catalyst comprising phosphorus, a crystalline aluminosilicate comprising a large-pore BEA-type zeolite having a 12-membered ring structure, and a binder; wherein an amount of phosphorus with respect to the total weight of the catalyst is 0.1 by mass to 10% by mass, wherein an amount of phosphorus supported on the crystalline aluminosilicate is 0.1% by mass or more and 5.0% by mass or less based on 100% by mass of a total mass of the crystalline aluminosilicate, and wherein when the catalyst is subjected to a hydrothermal treatment at a treatment temperature of 650° C., a treatment time of 6 hours, and 100% by mass of vapor, a sum of a yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 is 30% by mass or more and a yield of the aliphatic hydrocarbons having a carbon number of 3 to 4 is 14% by mass or more.

2. The catalyst for production of hydrocarbons according to claim 1, wherein the amount of phosphorus supported on the crystalline aluminosilicate is 0.2% by mass or more and 3.0% by mass or less.

3. The catalyst for production of hydrocarbons according to claim 1, further comprising boron; wherein an amount of boron supported on the crystalline aluminosilicate is 0.1% by mass or more and 5.0% by mass or less based on 100% by mass of the crystalline aluminosilicate.

4. The catalyst for production of hydrocarbons according to claim 1, further comprising one or more element selected from gallium and zinc.

5. The catalyst for production of hydrocarbons according to claim 4, wherein an amount of gallium and/or zinc is 0.01% by mass or more and 5.0% by mass or less based on 100% by mass of the crystalline aluminosilicate.

Description

EXAMPLES

(1) Hereinafter, the embodiment will be described in detail on the basis of examples and comparative examples, but this embodiment is not limited to these examples.

(2) (Preparation of BEA-Type Zeolite)

(3) BEA-type zeolite was prepared as described below according to a hydrothermal synthesis method in the related art.

(4) 59.1 g of a silicic acid (SiO.sub.2: 89% by mass) was dissolved in 202 g of tetraethylammonium hydroxide aqueous solution (40% by mass) to prepare a first solution. This solution was added to a second solution that was prepared by dissolving 0.74 g of Al-pellets and 2.69 g of sodium hydroxide in 17.7 g of water.

(5) The two solutions were mixed, thereby obtaining a reaction mixture having a composition (in terms of molar ratio of oxides) of 2.4 Na.sub.2O-20.0 (TEA).sub.2-Al.sub.2O.sub.3-64.0 SiO.sub.2-612 H.sub.2O. This reaction mixture was placed in a 0.3 L autoclave, and was heated at 150° C. for 6 days. The obtained product was separated from the mother liquor and the separated product was cleaned with distilled water. From a result of X-ray diffraction analysis (apparatus model: Rigaku RINT-2500V) on the product, BEA-type zeolite was confirmed from XRD patterns.

(6) Then, after being subjected to ion-exchange using ammonium nitrate aqueous solution (30% by mass), the BEA-type zeolite was baked at 550° C. for 3 hours, whereby proton-type BEA zeolite was obtained.

Example 1

(7) The proton-type BEA zeolite, which was prepared as the catalyst, was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated catalyst 1 was obtained.

(8) Feedstock having properties shown in Table 1 and the catalyst were made to come into contact and react with each other under conditions of a reaction temperature of 550° C. and a reaction pressure of 0 MPaG by using a flow type reaction unit in which 10 ml of the catalyst 1 was filled in a reactor thereof. At this time, nitrogen as a diluting agent was introduced in order for the contact time between the feedstock and the catalyst to be 6.4 seconds. Under these conditions, reaction was carried out for 30 minutes, and thereby monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and aliphatic hydrocarbons having a carbon number of 3 to 4 were prepared. Then, composition analysis of the product was performed by an FID gas chromatography instrument that was directly connected to the reaction unit and the yields of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 were measured. From this measurement, the sum of the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 was 44% by mass, and that of the aliphatic hydrocarbons having a carbon number of 3 to 4 was 21% by mass. Measurement results are shown in Table 2.

(9) TABLE-US-00001 TABLE 1 Analysis Properties of raw material method Density (@15° C.) g/cm 0.906 JIS K 2249 Kinetic viscosity (@30° C.) mm.sup.2/s 3.640 JIS K 2283 Distillation Initial distillation ° C. 175.5 JIS K 2254 properties point 10 vol % distillation ° C. 224.5 temperature 50 vol % distillation ° C. 274.0 temperature 90 vol % distillation ° C. 349.5 temperature End point ° C. 376.0 Compositional Saturated portion % by 35 JPI-5S-49 analysis volume Olefin portion % by 8 volume Total aromatic % by 57 portion volume Monocyclic aromatic % by 23 portion volume Bicyclic aromatic % by 25 portion volume Tricyclic or more % by 9 aromatic portion volume

Example 2

(10) 120 g of BEA-type zeolite was impregnated with 120 g of gallium nitrate aqueous solution in order for 0.2% by mass (on the basis of 100% by mass of the total mass of the crystalline aluminosilicate) of gallium to be supported, and then the resultant product was dried at 120° C. Then, the resultant dried product was baked under a stream of air at a high temperature of 780° C. for 3 hours, whereby gallium-supporting crystalline aluminosilicate was obtained. This gallium-supporting crystalline aluminosilicate was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated catalyst 2 was obtained.

(11) In addition, the yields of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 were measured by using the catalyst 2 in place of the catalyst 1 in Example 1. From this measurement, the sum of the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 was 37% by mass, and that of the aliphatic hydrocarbons having a carbon number of 3 to 4 was 17% by mass. Measurement results are shown in Table 2.

Example 3

(12) 120 g of BEA-type zeolite was impregnated with 120 g of gallium nitrate aqueous solution in order for 0.4% by mass (on the basis of 100% by mass of the total mass of the crystalline aluminosilicate) of gallium to be supported, and then the resultant product was dried at 120° C. Then, the resultant dried product was baked under a stream of air at a high temperature of 780° C. for 3 hours, whereby gallium-supporting crystalline aluminosilicate was obtained. This gallium-supporting crystalline aluminosilicate was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated catalyst 3 was obtained.

(13) In addition, the yields of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 were measured by using the catalyst 3 in place of the catalyst 1 in Example 1. From this measurement, the sum of the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 was 34% by mass, and that of the aliphatic hydrocarbons having a carbon number of 3 to 4 was 14% by mass. Measurement results are shown in Table 2.

Comparative Example 1

(14) 120 g of MFI-type zeolite was impregnated with 120 g of gallium nitrate aqueous solution in order for 0.4% by mass (on the basis of 100% by mass of the total mass of the crystalline aluminosilicate) of gallium to be supported, and then the resultant product was dried at 120° C. Then, the resultant dried product was baked under a stream of air at a high temperature of 780° C. for 3 hours, whereby gallium-supporting crystalline aluminosilicate was obtained. This gallium-supporting crystalline aluminosilicate was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated catalyst 4 was obtained.

(15) In addition, the yields of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 were measured by using the catalyst 4 in place of the catalyst 1 in Example 1. From this measurement, the sum of the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 was 41% by mass, and that of the aliphatic hydrocarbons having a carbon number of 3 to 4 was 1% by mass. Measurement results are shown in Table 2.

Comparative Example 2

(16) 120 g of MFI-type zeolite was impregnated with 120 g of gallium nitrate aqueous solution in order for 1.6% by mass (on the basis of 100% by mass of the total mass of the crystalline aluminosilicate) of gallium to be supported, and then the resultant product was dried at 120° C. Then, the resultant dried product was baked under a stream of air at a high temperature of 780° C. for 3 hours, whereby gallium-supporting crystalline aluminosilicate was obtained. This gallium-supporting crystalline aluminosilicate was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated catalyst 5 was obtained.

(17) In addition, the yields of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 were measured by using the catalyst 5 in place of the catalyst 1 in Example 1. From this measurement, the sum of the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 was 35% by mass, and that of the aliphatic hydrocarbons having a carbon number of 3 to 4 was 1% by mass. Measurement results are shown in Table 2.

(18) TABLE-US-00002 TABLE 2 Comparative Comparative Example 1 Example 2 Example 3 Example 1 Example 2 Kind of zeolite BEA BEA BEA MFI MFI Content of gallium (% by mass) 0 0.2 0.4 0.4 1.6 Sum of yield of monocyclic aromatic 44 37 34 41 35 hydrocarbons having a carbon number of 6 to 8 and aliphatic hydrocarbons having a carbon number of 3 to 4 (% by mass) Yield of aliphatic hydrocarbons having a 21 17 14 1 1 carbon number of 3 to 4 (% by mass)

(19) (Results)

(20) In Examples 1 to 3 in which the catalysts 1 to 3 containing the large-pore zeolite were used, the sum of the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 was high, and the yield of the aliphatic hydrocarbons having a carbon number of 3 to 4 was high.

(21) Conversely, in comparative examples 1 and 2 in which the catalysts 4 and 5 containing the intermediate-pore zeolite and not containing the large-pore zeolite were used, the yield of the aliphatic hydrocarbons having a carbon number of 3 to 4 was low.

Examples 4, 5, and 6

(22) In addition, the yields of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 were measured in the same manner as Example 1 except that the reaction temperature in Example 1 was changed to 450° C. (Example 4), 500° C. (Example 5), and 600° C. (Example 6), respectively. The sum of the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 was 44% by mass in Example 4, 51% by mass in Example 5, and 32% by mass in Example 6, respectively and of the aliphatic hydrocarbons having a carbon number of 3 to 4 was 24% by mass in Example 4, 30% by mass in Example 5, and 9% by mass in Example 6, respectively. Measurement results are shown in Table 3.

Examples 7 and 8

(23) In addition, the yields of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 were measured in the same manner as Example 2 except that the reaction temperature in Example 2 was changed to 500° C. (Example 7) and 600° C. (Example 8), respectively. The sum of the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 was 40% by mass in Example 7 and 28% by mass in Example 8, respectively, and of the aliphatic hydrocarbons having a carbon number of 3 to 4 was 23% by mass in Example 7 and 6% by mass in Example 8, respectively. Measurement results are shown in Table 3.

Examples 9 and 10

(24) In addition, the yields of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 were measured in the same manner as Example 1 except that the reaction temperature in Example 3 was changed to 500° C. (Example 9) and 600° C. (Example 10), respectively. The sum of the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 was 37% by mass in Example 9 and 24% by mass in Example 10, respectively, and of the aliphatic hydrocarbon having a carbon number of 3 to 4 was 20% by mass in Example 9 and 6% by mass in Example 10, respectively. Measurement results are shown in Table 3.

(25) TABLE-US-00003 TABLE 3 Example 4 Example 5 Example 1 Example 6 Example 7 Example 2 Example 8 Example 9 Example 3 Example 10 Reaction temperature 450 500 550 600 500 550 600 500 550 600 (° C.) Sum of yield of 44 51 44 32 40 37 28 37 34 24 monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and aliphatic hydrocarbons having a carbon number of 3 to 4 (% by mass) Yield of aliphatic 24 30 21 9 23 17 6 20 14 6 hydrocarbons having a carbon number of 3 to 4 (% by mass)

(26) (Results)

(27) As shown in Table 3, even in the case of using any catalyst, when the reaction temperature is in a range of 450 to 600° C., it can be seen that the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 may be obtained with high yield.

Example 11

(28) 120 g of BEA-type zeolite was impregnated with 120 g of zinc nitrate aqueous solution in order for 0.4% by mass (on the basis of 100% by mass of the total mass of the crystalline aluminosilicate) of zinc to be supported, and then the resultant product was dried at 120° C. Then, the resultant dried product was baked under a stream of air at a high temperature of 780° C. for 3 hours, whereby zinc-supporting crystalline aluminosilicate was obtained. This zinc-supporting crystalline aluminosilicate was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated catalyst 6 was obtained.

(29) In addition, the yields of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 were measured by using the catalyst 6 in place of the catalyst 1 in Example 1. From this measurement, the sum of the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 was 35% by mass, and that of the aliphatic hydrocarbons having a carbon number of 3 to 4 was 12% by mass. Measurement results are shown in Table 4.

(30) (Results)

(31) In Example 11 in which the catalyst 6 containing the large-pore zeolite and supporting gallium was used, similarly to Example 3 in which the catalyst supporting gallium was used, the sum of the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 was high, and the yield of the aliphatic hydrocarbons having a carbon number of 3 to 4 was high.

(32) TABLE-US-00004 TABLE 4 Example Example 3 11 Kind of zeolite BEA BEA Kind of supported metal Gallium Zinc Content of zinc or gallium (% by mass) 0.4 0.4 Sum of yield of monocyclic aromatic 34 35 hydrocarbons having a carbon number of 6 to 8 and aliphatic hydrocarbons having a carbon number of 3 to 4 (% by mass) Sum of yield of aliphatic hydrocarbons having a 14 12 carbon number of 3 to 4 (% by mass)

Example 12

(33) The catalyst 1 was subjected to a hydrothermal treatment under an environment of a treatment temperature of 650° C., a treatment time of 6 hours, and 100% by mass of vapor to obtain a pseudo-degraded catalyst 1 that was hydrothermally degraded in a pseudo manner.

(34) The feedstock was subjected to reaction similarly to Example 1 except that the pseudo-degraded catalyst 1 was used in place of the catalyst 1, and composition analysis of the obtained product was performed to evaluate the catalyst activity after the hydrothermal degradation. In the case of using the pseudo-degraded catalyst 1, the sum of the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 was 15% by mass and that of the aliphatic hydrocarbons having a carbon number of 3 to 4 was 10% by mass. Evaluation results are shown in Table 5.

Example 13

(35) 120 g of BEA-type zeolite was impregnated with 120 g of diammonium hydrogen phosphate aqueous solution in order for 2.0% by mass (on the basis of 100% by mass of the total mass of the crystalline aluminosilicate) of phosphorus to be supported, and then the resultant product was dried at 120° C. Then, the resultant dried product was baked under a stream of air at a high temperature of 780° C. for 3 hours, whereby phosphorus-supporting crystalline aluminosilicate was obtained. This phosphorus-supporting crystalline aluminosilicate was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated catalyst 7 was obtained.

(36) In addition, the catalyst 7 was subjected to a hydrothermal treatment under an environment of a treatment temperature of 650° C., a treatment time of 6 hours, and 100% by mass of vapor to obtain a pseudo-degraded catalyst 7 that was hydrothermally degraded in a pseudo manner.

(37) The feedstock was subjected to reaction similarly to Example 1 except that the pseudo-degraded catalyst 7 was used in place of the catalyst 1, and composition analysis of the obtained product was performed to evaluate the catalyst activity after the hydrothermal degradation. In the case of using the pseudo-degraded catalyst 7, the sum of the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 was 30% by mass and that of the aliphatic hydrocarbons having a carbon number of 3 to 4 was 14% by mass. Evaluation results are shown in Table 5.

(38) (Preparation of FAU-Type Zeolite)

(39) FAU-type zeolite was prepared as described below according to a hydrothermal synthesis method in the related art.

(40) 3 g of sodium aluminate containing 30.0% by mass of Na.sub.2O, 44.1% by mass of Al.sub.2O.sub.3, and 25.9% by mass of H.sub.2O, and 16.4 g of sodium hydroxide containing 77.5% by mass of Na.sub.2O were dissolved in 131 ml of deionized water. This resultant solution was added to 74.5 g of aqueous colloidal silica sol containing 29.5% by mass of silica, and these two solutions were mixed, thereby obtaining a reaction mixture having a composition (in terms of molar ratio of oxides) of 16.9 Na.sub.2O—Al.sub.2O.sub.3-28.2 SiO.sub.2-808 H.sub.2O. This mixture was mixed and stirred until it reached a uniform state, and this reaction mixture was placed in a 0.3 L autoclave, and was heated at 120° C. for 3 hours. The obtained product was separated from the mother liquor and the separated product was cleaned with distilled water. From a result of X-ray diffraction analysis (apparatus model: Rigaku RINT-2500V) on the product, FAU-type zeolite (Y-type zeolite) was confirmed from XRD patterns.

(41) Then, after being subjected to ion-exchange using ammonium nitrate aqueous solution (30% by mass), the FAU-type zeolite was baked at 550° C. for 3 hours, whereby proton-type FAU zeolite was obtained. Then, this FAU-type zeolite was treated under vapor at a temperature of 650° C. to stabilize this zeolite, whereby stabilized proton-type FAU zeolite (USY zeolite) was prepared.

Example 14

(42) The proton-type FAU zeolite that was prepared as the catalyst was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated catalyst 8 was obtained.

(43) In addition, the catalyst 8 was subjected to a hydrothermal treatment under an environment of a treatment temperature of 650° C., a treatment time of 6 hours, and 100% by mass of vapor to obtain a pseudo-degraded catalyst 8 that was hydrothermally degraded in a pseudo manner.

(44) The feedstock was subjected to reaction similarly to Example 1 except that the pseudo-degraded catalyst 8 was used in place of the catalyst 1, and composition analysis of the obtained product was performed to evaluate the catalyst activity after the hydrothermal degradation. In the case of using the pseudo-degraded catalyst 8, the sum of the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 was 13% by mass and that of the aliphatic hydrocarbons having a carbon number of 3 to 4 was 9% by mass. Evaluation results are shown in Table 5.

Example 15

(45) 120 g of FAU-type zeolite was impregnated with 120 g of diammonium hydrogen phosphate aqueous solution in order for 2.0% by mass (on the basis of 100% by mass of the total mass of the crystalline aluminosilicate) of phosphorus to be supported, and then the resultant product was dried at 120° C. Then, the resultant dried product was baked under a stream of air at a high temperature of 780° C. for 3 hours, whereby phosphorus-supporting crystalline aluminosilicate was obtained. This phosphorus-supporting crystalline aluminosilicate was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated catalyst 9 was obtained.

(46) In addition, the catalyst 9 was subjected to a hydrothermal treatment under an environment of a treatment temperature of 650° C., a treatment time of 6 hours, and 100% by mass of vapor to obtain a pseudo-degraded catalyst 9 that was hydrothermally degraded in a pseudo manner.

(47) The feedstock was subjected to reaction similarly to Example 1 except that the pseudo-degraded catalyst 9 was used in place of the catalyst 1, and composition analysis of the obtained product was performed to evaluate the catalyst activity after the hydrothermal degradation. In the case of using the pseudo-degraded catalyst 9, the sum of the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 was 29% by mass and that of the aliphatic hydrocarbons having a carbon number of 3 to 4 was 10% by mass. Evaluation results are shown in Table 5.

(48) (Preparation of MOR-Type Zeolite)

(49) MOR-type zeolite was prepared as described below according to a hydrothermal synthesis method in the related art. 2.7 g of sodium aluminate containing 30.0% by mass of Na.sub.2O, 44.1% by mass of Al.sub.2O.sub.3, and 25.9% by mass of H.sub.2O, and 6.3 g of sodium hydroxide were dissolved in 200 ml of deionized water. This resultant solution was added to 241 cc of aqueous colloidal silica sol containing 27.8% by mass of silica, thereby obtaining a reaction mixture having a composition (in terms of molar ratio of oxides) of 1.9 Na.sub.2O—Al.sub.2O.sub.3-13 SiO.sub.2. This mixture was mixed and stirred until it reached a uniform state, and this reaction mixture was placed in a 0.3 L autoclave, and was heated at 150° C. for 8 hours. The obtained product was separated from the mother liquor and the separated product was cleaned with distilled water. From a result of X-ray diffraction analysis (apparatus model: Rigaku RINT-2500V) on the product, MOR-type zeolite was confirmed from XRD patterns.

(50) Then, after being subjected to ion-exchange using ammonium nitrate aqueous solution (30% by mass), the MOR-type zeolite was baked at 550° C. for 3 hours, whereby proton-type MOR zeolite was obtained. Then, this MOR zeolite was treated under vapor at a temperature of 650° C. to stabilize this zeolite, whereby stabilized proton-type MOR zeolite was prepared.

Example 16

(51) The proton-type MOR zeolite that was prepared as the catalyst was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated catalyst 10 was obtained.

(52) In addition, the catalyst 10 was subjected to a hydrothermal treatment under an environment of a treatment temperature of 650° C., a treatment time of 6 hours, and 100% by mass of vapor to obtain a pseudo-degraded catalyst 10 that was hydrothermally degraded in a pseudo manner.

(53) The feedstock was subjected to reaction similarly to Example 1 except that the pseudo-degraded catalyst 10 was used in place of the catalyst 1, and composition analysis of the obtained product was performed to evaluate the catalyst activity after the hydrothermal degradation. In the case of using the pseudo-degraded catalyst 10, the sum of the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 was 14% by mass and that of the aliphatic hydrocarbons having a carbon number of 3 to 4 was 10% by mass. Evaluation results are shown in Table 5.

Example 17

(54) 120 g of MOR-type zeolite was impregnated with 120 g of phosphoric acid aqueous solution in order for 2.0% by mass (on the basis of 100% by mass of the total mass of the crystalline aluminosilicate) of phosphorus to be supported, and then the resultant product was dried at 120° C. Then, the resultant dried product was baked under a stream of air at a high temperature of 780° C. for 3 hours, whereby phosphorus-supporting crystalline aluminosilicate was obtained. This phosphorus-supporting crystalline aluminosilicate was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated catalyst 11 was obtained.

(55) In addition, the catalyst 11 was subjected to a hydrothermal treatment under an environment of a treatment temperature of 650° C., a treatment time of 6 hours, and 100% by mass of vapor to obtain a pseudo-degraded catalyst 11 that was hydrothermally degraded in a pseudo manner.

(56) The feedstock was subjected to reaction similarly to Example 1 except that the pseudo-degraded catalyst 11 was used in place of the catalyst 1, and composition analysis of the obtained product was performed to evaluate the catalyst activity after the hydrothermal degradation. In the case of using the pseudo-degraded catalyst 11, the sum of the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 was 30% by mass and that of the aliphatic hydrocarbons having a carbon number of 3 to 4 was 11% by mass. Evaluation results are shown in Table 5.

(57) TABLE-US-00005 TABLE 5 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Catalyst Pseudo-degraded Pseudo-degraded Pseudo-degraded Pseudo-degraded Pseudo-degraded Pseudo-degraded catalyst 1 catalyst 7 catalyst 8 catalyst 9 catalyst 10 catalyst 11 Kind of Zeolite BEA BEA FAU FAU MOR MOR Amount of  0  2 0  2  0  2 phosphorus Sum of yield of 15 30 13  29 14 30 monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and aliphatic hydrocarbons having a carbon number of 3 to 4 (% by mass) Yield of aliphatic 10 14 9 10 10 11 hydrocarbons having a carbon number of 3 to 4 (% by mass)

(58) (Results)

(59) Even in the case of using the catalyst containing the MOR-type zeolite or the FAU-type zeolite, which is a large-pore zeolite, substantially the same effect as the case of using the catalyst containing the BEA-type zeolite was exhibited.

(60) Furthermore, when phosphorus was incorporated in the catalyst, even after the pseudo-degradation, the sum of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4, and the aliphatic hydrocarbons having a carbon number of 3 to 4 were obtained with high yield.

INDUSTRIAL APPLICABILITY

(61) According to the catalyst for production of hydrocarbons of the invention, monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and aliphatic hydrocarbons having a carbon number of 3 to 4 may be produced with high efficiency from feedstock in which a 10 vol % distillation temperature is 140° C. or higher and a 90 vol % distillation temperature is 380° C. or lower.