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Industrial sulfur tolerant catalyst for vapor ethylation of coking benzene to prepare ethyl benzene

A catalyst and ethylation technology, applied in physical/chemical process catalysts, molecular sieve catalysts, catalyst activation/preparation, etc., can solve problems such as difficult to meet long-term stable operation

Active Publication Date: 2012-07-25
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Due to the high content of thiophene and other sulfides in coked benzene, the existing benzene alkylation catalysts are difficult to meet the requirements of long-term stable operation

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0015] Nano NaZSM-5 (silicon aluminum molar ratio SiO 2 / Al 2 o 3 is 30) and α-Al 2 o 3 ·H 2 O is mixed at a ratio of 70:30, adding 2 to 3% of the dry basis of scallop powder and 10wt% of concentrated nitric acid aqueous solution, kneaded, extruded into strips, dried at 110°C, and roasted at 540°C for 3 hours to make sodium ZSM- 5 zeolite molecular sieves; use 0.4mol / L NH 4 NO 3 Exchange three times, wash with deionized water between each two times, dry at 110°C, bake at 540°C for six hours; finally soak in 0.6 mol / L nitric acid aqueous solution for 24 hours, wash with deionized water to pH ≈ 7, and dry at 110°C , Calcined at 540° C. for 3 hours to obtain a nano-hydrogen ZSM-5 catalyst with a diameter of 1.5 mm.

[0016] The above catalyst is treated with water steam for 2 hours at 500°C, and the weight space velocity is 0.5h -1 , and then impregnated with 0.06 mol / L lanthanum nitrate aqueous solution at room temperature for 4 hours, the weight ratio of lanthanum nitra...

Embodiment 2

[0025] The difference with Example 1 is that it is treated with high-temperature ammonia water vapor, and its treatment condition is 500 ° C, with 0.5 mol / liter of ammonia water vapor for 2 hours, and the weight space velocity is 0.5h -1 , all the other are identical with embodiment 1.

[0026] The conversion rate of coked benzene decreased from 57.2% to 24.0% after the catalyst was operated for 11 hours, the total selectivity of ethylbenzene increased from 85.6% to 96.0%, and the deactivation rate of the catalyst was 3.0% / hour.

Embodiment 3

[0028] The difference from Example 1 is that the water vapor treatment temperature is different, the specific process: under the condition of 400 ° C, water vapor treatment for 2 hours, the weight space velocity is 0.5h -1 , all the other are identical with embodiment 1.

[0029] The conversion rate of coked benzene dropped from 53.6% to 31.7% after the catalyst was operated for 25 hours, the total selectivity of ethylbenzene rose from 81.5% to 94.1%, and the deactivation rate of the catalyst was 0.88 percentage points / hour.

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Abstract

The present invention relates to industrial sulfur tolerant catalyst for vapor ethylation of coking benzene to prepare ethyl benzene and its preparation process. The catalyst consists of nanometer HZSM-5 zeolite molecular sieve, alpha-Al2O3, and metal or non-metal oxide as modifier. Its preparation process includes high temperature water vapor or ammonia water vapor treatment of 20-200 nm crystal grain size HZSM-5 zeolite molecular sieve catalyst; and soaking the molecular sieve catalyst to support oxide of IIB element zinc, oxide of IIIB element La, oxide of VIB element Microwave oven and / oroxide one non-metal element P for modification. It may be used in the vapor ethylation of coking benzene with sulfur content of 200-800 preparation directly without needing desulfurizing and with the catalyst regenerating period as long as 60 days and other advantages.

Description

technical field [0001] The invention relates to a nanometer HZSM-5 molecular sieve catalyst with excellent sulfur resistance performance and a preparation method thereof, which is used for gas-phase alkylation of coking benzene and ethylene, ethanol or dilute ethanol to produce ethylbenzene. Background technique [0002] Ethylbenzene is an important petrochemical raw material, about 90% is used for the production of macromolecular monomer - styrene, and the rest is used for paint solvent and pharmaceutical industry. In the field of petrochemical industry, the alkylation of benzene and ethylene is widely used to produce ethylbenzene. Phenylethylation to Ethylbenzene The traditional Friedel-Craftes alkylation process uses aluminum trichloride catalyst, but it is gradually eliminated due to the high corrosiveness of the reaction medium and the safety and waste disposal problems brought about by it. Mobil Corporation successfully developed ZSM-5, a mesoporous molecular sieve wi...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/40B01J29/48B01J29/46B01J37/02C07C2/66C07C15/073
CPCY02P20/52Y02P20/584
Inventor 郭新闻孙林平王祥生
Owner DALIAN UNIV OF TECH
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