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Zn/ZSM-11 molecular sieve catalyst modification method

A technology of ZSM-11 and molecular sieve, which is applied in molecular sieve catalysts, physical/chemical process catalysts, chemical instruments and methods, etc., can solve the problems of catalyst skeleton dealumination, overheating, high energy consumption, etc., and achieve the effect of increasing the yield of aromatics

Active Publication Date: 2015-05-20
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0009] However, the aromatization of light hydrocarbons has the disadvantages of many cracking products and high energy consumption (the aromatization of alkane raw materials is a strong endothermic process), while the aromatization of methanol is a strong exothermic reaction, which is easy to cause pyrolysis during the reaction. temperature; in addition, the catalytic conversion of methanol will generate a large amount of water, which will dealuminate the catalyst framework and lead to irreversible deactivation

Method used

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  • Zn/ZSM-11 molecular sieve catalyst modification method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Put 20g of Na-type ZSM-11 molecular sieve in 100ml of sodium hydroxide with a concentration of 0.3mol / L and a mixed solution of CTAB with a concentration of 0.1mol / L, heat treatment in a water bath at 75°C for 3 hours, filter and wash to medium Drying at 110°C for 3 hours, calcination at 540°C for 3 hours. The prepared molecular sieve was exchanged with 0.8mol / L ammonium nitrate solution three times (1 hour / time), washed with water three times (1 hour / time), dried at 110°C for 10 hours, roasted at 540°C for 4 hours, and then used with an equal volume of Catalyst Cat-C was prepared by impregnation method with zinc metal loaded at 4.0wt%, dried at 110°C for 10 hours, and calcined at 540°C for 4 hours. Wherein ammonium nitrate exchange and water washing temperature is 85 ℃. Gained catalyst detects through XRF, and the Na in this catalyst 2 O is less than 0.05 wt%.

Embodiment 2

[0028] Put 20g of Na-type ZSM-11 molecular sieve in 100ml of sodium hydroxide with a concentration of 0.4mol / L and a mixed solution of PDADMAC with a concentration of 0.1mol / L, heat it in a water bath at 80°C for 2 hours, filter and wash to medium Properties, drying at 100°C for 6 hours, calcination at 580°C for 3 hours. The prepared molecular sieve was exchanged with 0.6mol / L ammonium nitrate solution three times (1 hour / time), washed with water three times (1 hour / time), dried at 110°C for 5 hours, and then roasted at 540°C for 3 hours with an equal volume of Catalyst Cat-D was prepared by impregnation method with zinc metal loaded at 6.0wt%, dried at 95°C for 8 hours, and calcined at 480°C for 7 hours. Wherein ammonium nitrate exchange and washing temperature is 75 ℃. Gained catalyst detects through XRF, and the Na in this catalyst 2 O is less than 0.05 wt%.

Embodiment 3

[0030] Put 20g of Na-type ZSM-11 molecular sieve in 100ml of a mixed solution of sodium hydroxide with a concentration of 0.6mol / L and TBAOH with a concentration of 0.4mol / L, heat it in a water bath at 70°C for 2 hours, filter and wash to medium Drying at 110°C for 4 hours, calcination at 550°C for 6 hours. The prepared molecular sieves were exchanged with 0.9mol / L ammonium nitrate solution three times (1 hour / time), washed with water three times (1 hour / time), dried at 120°C for 3 hours, roasted at 500°C for 6 hours, and then used an equal volume Catalyst Cat-E was prepared by impregnation method with zinc metal loaded at 7.0wt%, dried at 95°C for 11 hours, and calcined at 550°C for 7 hours. Wherein ammonium nitrate exchange and washing temperature is 80 ℃. Gained catalyst detects through XRF, and the Na in this catalyst 2 O is less than 0.05 wt%.

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Abstract

The present invention provides a Zn / ZSM-11 molecular sieve catalyst modification method, which concretely comprises: carrying out heating stirring on a Na-type ZSM-11 molecular sieve for 1-5 h at a temperature of 65-85 DEG C by using an alkali and organic surfactant mixing solution; washing to achieve a neutral state; carrying out drying baking; carrying out exchange at a temperature of 70-90 DEG C by using a 0.5-1.0 mol / L ammonium nitrate solution; drying, and then baking to prepare an H- type molecular sieve; loading zinc on the obtained molecular sieve by using an equal volume impregnation method, wherein the zinc loading amount is 0.5-10.0 wt%; and drying, and then baking to prepare the catalyst. According to the present invention, the aromatic hydrocarbon yield of the Zn / ZSM-11 molecular sieve catalyst treated by the surfactant and the alkali can be further increased compared with the aromatic hydrocarbon yield of the Zn / ZSM-11 molecular sieve catalyst being subjected to the conventional alkali treatment or with no alkali treatment.

Description

technical field [0001] The invention belongs to the field of molecular sieve catalysts, in particular to a method for modifying a Zn / ZSM-11 molecular sieve catalyst for co-feeding aromatization of methanol and n-butane. Background technique [0002] Aromatics are one of the most important basic raw materials for the production of petrochemical products. They are mainly used in the production of synthetic materials such as nylon, polyurethane, polyester, and alkyd resins, and as plasticizing raw materials for phthalic anhydride. At present, they mainly come from catalytic reforming oil and cracking Gasoline by-products. As we all know, petroleum is a non-renewable resource, and it is estimated that it can only be exploited for several decades according to the current consumption rate [G.A.Olah, Angew.Chem.Int.Ed.Engl.44(2005)2636]. With the depletion of petroleum resources, the source of aromatics is increasingly challenged. [0003] One of the ways to solve this problem is...

Claims

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Application Information

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IPC IPC(8): B01J29/40C07C15/02C07C2/86
Inventor 徐龙伢宋超李秀杰谢素娟刘盛林刘惠
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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