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Porous zsm-5 zeolite with γ-al 2 o 3 Synthesis of Composite Materials and Preparation of Hydrodesulfurization Catalyst

A technology of MZSM-5-A and ZSM-5 is applied in the field of preparation of porous ZSM-5 zeolite and γ-Al2O3 composite carrier, which can solve the problems of low mechanical strength of porous zeolite, difficult application, and difficulty in molding, etc. High reproducibility, improved interaction, avoidance of agglomeration

Active Publication Date: 2019-10-11
CHANGZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the mechanical strength of porous zeolite is not high, it is difficult to form in the catalyst forming process, and it is difficult to apply to the actual industry

Method used

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  • Porous zsm-5 zeolite with γ-al <sub>2</sub> o <sub>3</sub> Synthesis of Composite Materials and Preparation of Hydrodesulfurization Catalyst
  • Porous zsm-5 zeolite with γ-al <sub>2</sub> o <sub>3</sub> Synthesis of Composite Materials and Preparation of Hydrodesulfurization Catalyst
  • Porous zsm-5 zeolite with γ-al <sub>2</sub> o <sub>3</sub> Synthesis of Composite Materials and Preparation of Hydrodesulfurization Catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Preparation of ZSM-5:γ-Al 2 o 3 The method of =9:1 composite material is realized by the following steps:

[0030] (1) Weigh 0.357g NaAlO 2 and 0.522g NaOH were dissolved in 19.6mL water, and a mixed solution of tetraethyl orthosilicate and TAPOH (10mL TEOS and 26mL 25wt.% TPAOH) was added, and after being completely dissolved, NaAlO 2 with Al 2 o 3 In terms of TEOS as SiO 2 Then add 2.5mL DEAB, the molar ratio of each material is Al 2 o 3 :Na 2 O:TPAOH:SiO 2 :DEAB:H 2 O=1:4:20:20:2:500. After the reaction is complete, add 0.72g of pseudo-boehmite and stir until completely dissolved. The reacted mixture was added to a 50 mL hydrothermal kettle, and then crystallized at 180° C. for 3 days. After natural cooling, wash and filter with water at room temperature, and then calcined at 550°C for 5 hours in an oven at 100°C. The texture properties of the obtained supports are shown in Table 1.

[0031] (2) Add 0.0699g (NH 4 ) 6 Mo 7 o 24 4H 2 O, 0.0576g Co(NO...

Embodiment 2

[0033] Preparation of ZSM-5:γ-Al 2 o 3 The method of =9:1 composite material is realized by the following steps:

[0034] (1) Weigh 0.357g NaAlO 2 Dissolve 0.522g NaOH in 19.6mL water, add the mixed solution of TEOS and TAPOH (10mL TEOS and 26mL 25wt.% TPAOH), after being completely dissolved, NaAlO 2 Take Al 2 o 3 In terms of TEOS as SiO 2 Then add 2.5mL DEAB, the molar ratio of each material is Al 2 o 3 :Na 2 O:TPAOH:SiO 2 :DEAB:H 2 O=1:4:20:20:2:500. After the reaction is complete, add 0.72g of pseudo-boehmite and stir until completely dissolved. The reacted mixture was added to a 50 mL hydrothermal kettle, and then crystallized at 180° C. for 3 days. Filter, wash and dry, and calcined at 550°C for 5h. The texture properties of the obtained supports are shown in Table 1.

[0035] (2) 0.2116g (NH 4 ) 6 Mo 7 o 24 4H 2 O, 0.1744g Co(NO 3 ) 2 ·6H 2 O and 0.1751g EDTA were dissolved in a certain amount of water, and after all dissolved, they were dropped in...

Embodiment 3

[0037] Preparation of ZSM-5:γ-Al 2 o 3 The method of =9:1 composite material is realized by the following steps:

[0038] (1) Weigh 0.357g NaAlO 2 Dissolve 0.522g NaOH in 19.6mL water, add the mixed solution of TEOS and TAPOH (10mL TEOS and 26mL 25wt.% TPAOH), after being completely dissolved, NaAlO 2 Take Al 2 o 3 In terms of TEOS as SiO 2 Then add 2.5mL DEAB, the molar ratio of each material is Al 2 o 3 :Na 2 O:TPAOH:SiO 2 :DEAB:H 2 O=1:4:40:20:2:500. After the reaction is complete, add 0.72g of pseudo-boehmite and stir until completely dissolved. The reacted mixture was added to a 50 mL hydrothermal kettle, and then crystallized at 180° C. for 3 days. Filter, wash and dry, and calcined at 550°C for 5h. The texture properties of the obtained supports are shown in Table 1.

[0039] (2) Add 0.1964g (NH 4 ) 6 Mo 7 o 24 4H 2 O, 0.1618g Co(NO 3 ) 2 ·6H 2 O and 0.1628g EDTA were dissolved in a certain amount of water, and after they were completely dissolved,...

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Abstract

The invention discloses synthesis of a porous ZSM-5 zeolite and gamma-Al2O3 composite material and preparation of a hydrodesulfurization catalyst and relates to the technical field of composite materials and the field of hydrodesulfurization catalysts. The composite material is roasted for 3-8 h at the temperature of 450-600 DEG C, and has the following properties that the content of porous ZSM-5 zeolite is 5-95 wt.%, the content of gamma-Al2O3 is 5-95 wt.%, the specific surface area is 400-600 m<2>.g1, the mesopore volume is 0.40-0.85 cm<3>.g1, and the micropore volume is 0.06-0.15 cm<3>. g1. The composite material has multiple stages of porous structures, good hydrothermal stability, high mechanical strength and weak interaction with loaded metal species, changes the existence state of the metal species and promotes reducing and vulcanizing of the metal species, multiple layers of high-activity molybdenum sulfide or tungsten sulfide active phases are easily formed on the composite material, and the hydrodesulfurization performance of the metal sulfide catalyst is improved.

Description

technical field [0001] The invention relates to the technical field of composite materials and the field of hydrodesulfurization catalysts, in particular to porous ZSM-5 zeolite and γ-Al 2 o 3 Preparation of composite support and its application of loaded metal sulfide in hydrodesulfurization reaction. Background technique [0002] In recent years, as the quality of crude oil has become heavier and worse worldwide, the content of difficult-to-remove dibenzothiophene compounds such as 4,6-dimethyldibenzothiophene in processed diesel fractions Increasingly, these sulfur-containing organic compounds inevitably generate sulfur oxides during the combustion process, resulting in the formation of acid rain and serious pollution of the atmospheric environment. Therefore, countries around the world have promulgated strict environmental protection regulations. For example, in September 2009, Europe implemented strict Euro VI standards, which clearly stipulated that the sulfur conten...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/40B01J29/48B01J35/10C10G45/12
CPCC10G45/12B01J29/40B01J29/48C10G2300/202C10G2300/70B01J35/60
Inventor 唐天地俞泉勇傅雯倩张磊
Owner CHANGZHOU UNIV
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