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Preparation method of isomerization catalyst with MTW type structural molecular sieve serving as carrier

A molecular sieve and isomerization technology, which is applied in the field of isomerization catalyst preparation, can solve the problems of increasing strong acid sites, affecting catalyst performance, and reducing the number of micropores, achieving high micropore volume, high isomerization selectivity and isomerization The effect of reducing the volume yield and reducing the demoulding temperature of roasting

Active Publication Date: 2019-03-15
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Similar to the aforementioned molecular sieve release methods, the preparation of catalysts based on MTW molecular sieves often uses high-temperature (not lower than 450°C) roasting to remove the template agent in the molecular sieve. This conventional high-temperature (not lower than 450°C) roasting release The method affects the distribution of acid sites, the amount of acid and the number of micropores on the MTW molecular sieve, so that the number of micropores decreases, the number of medium-strength acid sites decreases, and the strong acid sites increase, which in turn affects the performance of the catalyst

Method used

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  • Preparation method of isomerization catalyst with MTW type structural molecular sieve serving as carrier
  • Preparation method of isomerization catalyst with MTW type structural molecular sieve serving as carrier

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] Get 120g ZSM-12 molecular sieve former powder (same as comparative example) that contains tetraethylammonium hydroxide template agent (content is 10wt.% of molecular sieve weight), roasting 12h under 210 ℃ of nitrogen atmospheres, after roasting, molecular sieve load volume carbon and The content of organic matter is 7.2wt.%; and then roasted at 250°C for 6 hours in an air atmosphere to obtain about 105g of ZSM-12 molecular sieve carrier from which the template agent is partially removed. Capacity is 0.013cm 3 / g. With 5mL of H containing Pt0.05g / mL 2 PtCl 6 The solution was impregnated with 50 g of the above carrier, dried naturally at 120° C. for 4 h, and reduced with hydrogen at 400° C. for 4 h to prepare a 0.5 wt.% Pt / ZSM-12 catalyst. The content of carbon deposits and organic matter in the catalyst is 0, the amount of medium-strong acid is 0.81mmol / g, the amount of strong acid is 0.17mmol / g, and the volume of micropores is 0.056cm 3 / g. See Table 1 for the cha...

Embodiment 2

[0048] Get 120g of TPZ-12 molecular sieve former powder containing tetraethylammonium hydroxide template (content is 12wt.% of the molecular sieve weight), and roast it under nitrogen atmosphere at 220°C for 6h. %; then roasted at 350°C for 12h in an air atmosphere to obtain about 105g of TPZ-12 molecular sieve carrier from which the template was partially removed. 3 / g. With 5mL of H containing Pt 0.05g / mL 2 PtCl 6 The solution was impregnated with 50 g of the above-mentioned carrier, dried naturally at 120° C. for 4 h, and reduced with hydrogen at 400° C. for 2 h to prepare a 0.5 wt.% Pt / TPZ-12 catalyst. The content of carbon deposits and organic matter in the catalyst is 0, the amount of medium-strong acid is 0.85mmol / g, the amount of strong acid is 0.15mmol / g, and the volume of micropores is 0.055cm 3 / g. See Table 1 for the characterization results of carbon deposits, organic matter content, and micropore volume of the molecular sieve catalyst, the medium-strong acid ...

Embodiment 3

[0050] Get 120g of NU-13 molecular sieve powder containing tetraethylammonium bromide template (content is 20wt.% of the molecular sieve weight), and roast it under nitrogen atmosphere at 250°C for 2h. %; then roasted at 200°C for 12 hours in an ozone atmosphere to obtain about 105 g of NU-13 molecular sieve carriers from which the template was partially removed. 3 / g. With 5mL of H containing Pt 0.05g / mL 2 PtCl 6 The solution was impregnated with 50 g of the above carrier, dried naturally at 120° C. for 4 h, and reduced with hydrogen at 200° C. for 8 h to prepare a 0.5 wt.% Pt / NU-13 catalyst. The content of carbon deposits and organic matter in the catalyst is 0, the amount of medium-strong acid is 0.87mmol / g, the amount of strong acid is 0.14mmol / g, and the volume of micropores is 0.057cm 3 / g. See Table 1 for the characterization results of carbon deposits, organic matter content, and micropore volume of the molecular sieve catalyst, the medium-strong acid content, stro...

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Abstract

The invention discloses a preparation method of an isomerization catalyst with an MTW type structural molecular sieve serving as a carrier. The preparation method comprises the following specific steps: firstly, performing partial templating agent removal treatment on templating agent-containing molecular sieve raw powder with an MTW structure in an inert atmosphere at 50 to 300 DEG C; then performing further templating agent removal treatment on the molecular sieve having the MTW structure and subjected to the partial templating agent removal in an oxygen atmosphere at 50 to 400 DEG C; carrying metal active ingredients on an obtained molecular sieve carrier, and performing drying and reduction to obtain the target catalyst. Effective regulation of the acid properties and pore properties of the catalyst is realized by controlling a removal mode of a templating agent in the molecular sieve carrrier. Compared with a catalyst prepared in the prior art, the catalyst prepared with the method disclosed by the invention is higher in isomerization selectivity and isomer yield in the normal paraffin isomerization reaction.

Description

technical field [0001] The invention belongs to the fields of petrochemical industry, fine chemical industry and molecular sieve catalyst, and specifically relates to a preparation method and application of an isomerization catalyst with MTW structure molecular sieve as a carrier. Background technique [0002] The bifunctional solid catalyst is widely used in the process of alkane hydroisomerization, which is composed of hydrogenation-dehydrogenation component and acid carrier. Among them, the hydrogenation-dehydrogenation components are mainly Group VIII metals such as Pt, Pd, Rh, Ir and Ni, etc.; the acidic supports can be divided into the following three categories: 1. Amorphous single metal oxide or composite oxide, as halide-treated Al 2 o 3 , SiO 2 / Al 2 o 3 , superacid ZrO 2 / SO 4 2- 、WO 3 / ZrO 2 2. Aluminosilicate molecular sieve series, such as Y, Beta, ZSM-5, etc.; 3. Aluminum phosphate molecular sieve series, such as SAPO-5, SAPO-11, SAPO-31 and SAPO-41....

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/74C10G45/64
CPCC10G45/64B01J29/7469B01J35/633
Inventor 王从新田志坚吕广王冬娥潘振栋马怀军曲炜李鹏
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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