Catalyst for dehydrogenation of propane for preparing propylene and preparation method thereof

Abstract

The invention discloses a catalyst, which is carried by an AlSn-SBA-15 molecular sieve with SnAl double metal-containing framework, for dehydrogenation of propane for preparing propylene. In the catalyst, the AlSn-SBA-15 molecular sieve with SnAl double metal-containing framework is used as a carrier, platinum-group element metal is used as a main catalyst, IVA-group, IA-group or IIA-group element metal is used as an auxiliary agent, and high-temperature-resistant inorganic oxide is used for forming an adhesive. A multi-step dipping method is used in the preparation of the catalyst, namely the alkaline metal auxiliary agent is dipped, so that the acidity and alkalinity of the catalyst and the types of cations in pores of the molecular sieve are effectively modulated by cation exchange technology, and the platinum-group element metal is dipped. The catalyst has superior anti-carbon deposit performance, high propane conversion rate under the reaction conditions of high temperature and low pressure, propylene selectivity and reaction stability.

Description

technical field

[0001] The invention relates to a catalyst for propane dehydrogenation to propylene, which is supported by AlSn-SBA-15 molecular sieves containing Sn and Al bimetals in the skeleton, and a preparation method thereof, which is suitable for gas-solid catalytic reactions and belongs to the technical field of industrial catalysis catalyst preparation technology. Background technique

[0002] As an important organic chemical raw material, propylene can be used in large quantities in the production of acrylonitrile, propylene oxide, butanol, octanol, isopropanol, cumene, acrylic acid, carbonyl alcohol and nonyl alcohol in addition to polypropylene. Chemical products such as phenol. Propylene mainly comes from by-products or co-productions such as naphtha cracking and refinery FCC processes, accounting for about 90% of propylene sources. Since the 1990s, with the gradual increase in the consumption of propylene, the traditional propylene production has been unable...

Examples

Embodiment 1

[0022] Sn-SBA-15 (the content of Sn is 1.0wt%) containing Sn in the skeleton was prepared by hydrothermal synthesis method. Dry at 60-150°C for 3-12h, roast at 500-650°C for 3-8h, then stir in 5wt% aluminum isopropoxide in n-hexane solution at room temperature for 6-12h, suction filter, wash with n-hexane, 60- Drying at 150°C for 3-12 hours, calcining at 500-650°C for 3-8 hours, and cooling to obtain an AlSn-SBA-15 molecular sieve carrier (with an Al content of 2.2 wt%).

[0023] At 60-100°C, impregnate the AlSn-SBA-15 molecular sieve carrier into NaCl aqueous solution for 2-8 hours, and after drying at 120°C for 3-5 hours, at 60-100°C, impregnate the above carrier into H 2 PtCl 6 Aqueous solution of 2~8h, after drying at 60~150℃ for 3~24h, add 20wt% Al 2 o 3 Binder and 1-15wt% scallop powder, while adding 1-10wt% dilute HNO 3 Aqueous solution, extrusion molding.

[0024] Then dry at 60-150°C for 2-24 hours, roast in air at 400-600°C for 3-10 hours, and reduce in hydrogen...

Embodiment 2

[0028]Sn-SBA-15 (the content of Sn is 0.3wt%) containing Sn in the skeleton was prepared by hydrothermal synthesis method. Dry at 60-150°C for 3-12h, roast at 500-650°C for 3-8h, then stir in 1wt% aluminum isopropoxide in n-hexane solution at room temperature for 6-12h, suction filter, wash with n-hexane, 60- Drying at 150°C for 3-12 hours, calcining at 500-650°C for 3-8 hours, and cooling to obtain an AlSn-SBA-15 molecular sieve carrier (with an Al content of 0.4 wt%).

[0029] At 60-100°C, impregnate the AlSn-SBA-15 molecular sieve carrier into MgCl 2 Aqueous solution for 2 to 8 hours, after drying at 120°C for 3 to 5 hours, at 60 to 100°C, impregnate the above carrier into H 2 PtCl 6 and SnCl 4 The mixed solution was dried for 2 to 8 hours at 60 to 150°C for 3 to 24 hours, and then 20wt% Al was added 2 o 3 Binder and 1-15wt% scallop powder, while adding 1-10wt% dilute HNO 3 Aqueous solution, extrusion molding.

[0030] Then dry at 60-150°C for 2-24 hours, roast in ai...

Embodiment 3

[0034] Sn-SBA-15 containing Sn in the skeleton was prepared by hydrothermal synthesis method (the content of Sn was 1.2wt%). Dry at 60-150°C for 3-12h, roast at 500-650°C for 3-8h, then stir in 8wt% aluminum isopropoxide in n-hexane solution at room temperature for 6-12h, filter with suction, wash with n-hexane, 60- Drying at 150°C for 3-12 hours, calcining at 500-650°C for 3-8 hours, and cooling to obtain an AlSn-SBA-15 molecular sieve carrier (with an Al content of 4.5 wt%).

[0035] At 60-100°C, impregnate the AlSn-SBA-15 molecular sieve carrier into the mixed aqueous solution of NaCl and KCl for 2-8 hours, and after drying at 120°C for 3-5 hours, at 60-100°C, impregnate the above carrier into H 2 PtCl 6 and SnCl 4 The mixed solution was dried for 2 to 8 hours at 60 to 150°C for 3 to 24 hours, and then 20wt% Al was added 2 o 3 Binder and 1-15wt% scallop powder, while adding 1-10wt% dilute HNO 3 Aqueous solution, extrusion molding.

[0036] Then dry at 60-150°C for 2-2...

technical field

[0001] The invention relates to a catalyst for propane dehydrogenation to propylene, which is supported by AlSn-SBA-15 molecular sieves containing Sn and Al bimetals in the skeleton, and a preparation method thereof, which is suitable for gas-solid catalytic reactions and belongs to the technical field of industrial catalysis catalyst preparation technology. Background technique

[0002] As an important organic chemical raw material, propylene can be used in large quantities in the production of acrylonitrile, propylene oxide, butanol, octanol, isopropanol, cumene, acrylic acid, carbonyl alcohol and nonyl alcohol in addition to polypropylene. Chemical products such as phenol. Propylene mainly comes from by-products or co-productions such as naphtha cracking and refinery FCC processes, accounting for about 90% of propylene sources. Since the 1990s, with the gradual increase in the consumption of propylene, the traditional propylene production has been unable...

Examples

Embodiment 1

[0022] Sn-SBA-15 (the content of Sn is 1.0wt%) containing Sn in the skeleton was prepared by hydrothermal synthesis method. Dry at 60-150°C for 3-12h, roast at 500-650°C for 3-8h, then stir in 5wt% aluminum isopropoxide in n-hexane solution at room temperature for 6-12h, suction filter, wash with n-hexane, 60- Drying at 150°C for 3-12 hours, calcining at 500-650°C for 3-8 hours, and cooling to obtain an AlSn-SBA-15 molecular sieve carrier (with an Al content of 2.2 wt%).

[0023] At 60-100°C, impregnate the AlSn-SBA-15 molecular sieve carrier into NaCl aqueous solution for 2-8 hours, and after drying at 120°C for 3-5 hours, at 60-100°C, impregnate the above carrier into H 2 PtCl 6 Aqueous solution of 2~8h, after drying at 60~150℃ for 3~24h, add 20wt% Al 2 o 3 Binder and 1-15wt% scallop powder, while adding 1-10wt% dilute HNO 3 Aqueous solution, extrusion molding.

[0024] Then dry at 60-150°C for 2-24 hours, roast in air at 400-600°C for 3-10 hours, and reduce in hydrogen...

Embodiment 2

[0028]Sn-SBA-15 (the content of Sn is 0.3wt%) containing Sn in the skeleton was prepared by hydrothermal synthesis method. Dry at 60-150°C for 3-12h, roast at 500-650°C for 3-8h, then stir in 1wt% aluminum isopropoxide in n-hexane solution at room temperature for 6-12h, suction filter, wash with n-hexane, 60- Drying at 150°C for 3-12 hours, calcining at 500-650°C for 3-8 hours, and cooling to obtain an AlSn-SBA-15 molecular sieve carrier (with an Al content of 0.4 wt%).

[0029] At 60-100°C, impregnate the AlSn-SBA-15 molecular sieve carrier into MgCl 2 Aqueous solution for 2 to 8 hours, after drying at 120°C for 3 to 5 hours, at 60 to 100°C, impregnate the above carrier into H 2 PtCl 6 and SnCl 4 The mixed solution was dried for 2 to 8 hours at 60 to 150°C for 3 to 24 hours, and then 20wt% Al was added 2 o 3 Binder and 1-15wt% scallop powder, while adding 1-10wt% dilute HNO 3 Aqueous solution, extrusion molding.

[0030] Then dry at 60-150°C for 2-24 hours, roast in ai...

Embodiment 3

[0034] Sn-SBA-15 containing Sn in the skeleton was prepared by hydrothermal synthesis method (the content of Sn was 1.2wt%). Dry at 60-150°C for 3-12h, roast at 500-650°C for 3-8h, then stir in 8wt% aluminum isopropoxide in n-hexane solution at room temperature for 6-12h, filter with suction, wash with n-hexane, 60- Drying at 150°C for 3-12 hours, calcining at 500-650°C for 3-8 hours, and cooling to obtain an AlSn-SBA-15 molecular sieve carrier (with an Al content of 4.5 wt%).

[0035] At 60-100°C, impregnate the AlSn-SBA-15 molecular sieve carrier into the mixed aqueous solution of NaCl and KCl for 2-8 hours, and after drying at 120°C for 3-5 hours, at 60-100°C, impregnate the above carrier into H 2 PtCl 6 and SnCl 4 The mixed solution was dried for 2 to 8 hours at 60 to 150°C for 3 to 24 hours, and then 20wt% Al was added 2 o 3 Binder and 1-15wt% scallop powder, while adding 1-10wt% dilute HNO 3 Aqueous solution, extrusion molding.

[0036] Then dry at 60-150°C for 2-2...