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Preparation method of catalyst with modified binderless ZSM-11 molecular sieves and application

A ZSM-11, binder-free technology, applied to molecular sieve catalysts, including molecular sieve catalysts, catalysts, etc., can solve the problems of strength reduction, acid content reduction, etc., and achieve the effect of improving conversion rate

Active Publication Date: 2017-11-28
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

At present, silica and alumina are mostly used as binders, and the aluminum atoms in the alumina binder enter the molecular sieve skeleton to increase the acid content of the molecular sieve (C.D.Chang, S.D.Hellring, J.N.Miale, K.D.Schmitt, P. Brigandi, E.Wu, J.Chem.Soc.Faraday Trans, 81(1985) 2215~2224); while the silicon oxide binder reduces the acid content (X.Wu, A.Alkhawaldeh, R.Anthony, Stud.Surf.Sci.Catal , 143(2000) 217-225), strength decline

Method used

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  • Preparation method of catalyst with modified binderless ZSM-11 molecular sieves and application

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Experimental program
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Effect test

Embodiment 1

[0027] Binder-free product B in Comparative Example 1 was washed with distilled water, dried, calcined at 550°C for 4 hours, then exchanged with 0.8mol / L ammonium nitrate solution for 3 times at 80°C, washed twice with water, dried at 120°C, and calcined at 540°C 3h, get H-type molecular sieve, and then routinely impregnate and load rare earth and aluminum, use lanthanum nitrate and aluminum nitrate solution, dry at 85°C for 2h, and roast at 550°C for 4h, the loading capacity of the obtained catalyst La and Al is 2.5wt% and 4.0wt%, followed by steam treatment at 550°C for 2h, the obtained catalyst is designated as Cat-D.

Embodiment 2

[0029] Binder-free product B in Comparative Example 1 was washed with distilled water, dried, and roasted at 550°C for 4 hours, then exchanged with 0.6mol / L ammonium nitrate solution at 70°C for 3 times, washed twice with water, dried at 120°C, and dried at 500°C. Calcined at ℃ for 5 hours to obtain H-type molecular sieves, and then routinely impregnated and supported rare earth and aluminum, using lanthanum nitrate and aluminum nitrate solutions, dried at 90℃ for 1.5h, and calcined at 500℃ for 5h, the loading capacity of the obtained catalysts La and Al were 0.3 wt% and 1.2wt%, followed by steam treatment at 580°C for 3h, the obtained catalyst is designated as Cat-E.

Embodiment 3

[0031] Binder-free product B in Comparative Example 1 was washed with distilled water, dried, and roasted at 550°C for 4 hours, then exchanged three times with 0.7mol / L ammonium nitrate solution at 60°C, washed twice with water, dried at 120°C, and dried at 550°C. Calcined at ℃ for 4 hours to obtain H-type molecular sieves, and then routinely impregnated and supported rare earth and aluminum, using cerium nitrate and aluminum phosphate solutions, dried at 95℃ for 3 hours, and calcined at 580℃ for 5 hours, the loading capacity of the obtained catalysts Ce and Al were 5.3wt % and 9.2wt%, followed by steam treatment at 630°C for 7h, the resulting catalyst is designated as Cat-F.

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Abstract

The invention discloses a preparation method of a catalyst with modified binderless ZSM-11 molecular sieves and an application. The preparation method comprises the specific steps: exchanging the prepared binderless ZSM-11 molecular sieves with an ammonium nitrate solution, drying and roasting to prepare an H-molecular sieve catalyst; and adopting nitrates and aluminium salts of rare earth to load rare earth and aluminium on the H-molecular sieve catalyst by a conventional impregnation method, and carrying out steam treatment to prepare the needed catalyst. When the catalyst prepared by the invention is applied to alkylation reaction of dimethyl ether and benzene, the aromatics with high yield can be generated. The preparation method disclosed by the invention has the advantages that compared with the catalyst only containing the binderless ZSM-11 molecular sieves, the benzene conversion ratio can be obviously increased.

Description

technical field [0001] The invention relates to the production technology of petrochemical products, in particular to a preparation method and application of a modified binderless ZSM-11 molecular sieve catalyst. Background technique [0002] Aromatic hydrocarbons are important basic raw materials of petrochemical industry, among the total of about 8 million known organic compounds, aromatic hydrocarbons account for about 30%. The use of natural gas (mainly composed of methane) or petroleum refinery dry gas (mainly containing methane, ethane, ethylene) and petroleum liquefied gas or methanol (dimethyl ether) for the preparation of aromatics is currently an important field in academia and industry. popular research topic. [0003] Obtaining aromatics from methanol and dimethyl ether was first seen in the MTG (Methanol to Gasoline) technology developed by Mobil Corporation of the United States. In the 1970s, Mobil Corporation developed the ZSM-5 zeolite catalyst to convert me...

Claims

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Application Information

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IPC IPC(8): B01J29/40C07C2/86C07C15/06C07C15/08C07C15/02
CPCB01J29/405C07C2/865C07C2529/40C07C15/06C07C15/08C07C15/02Y02P20/52
Inventor 刘盛林张琬铄辛文杰张爽谢素娟徐龙伢刘惠
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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