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A kind of zsm-5 catalyst and its preparation and application

The technology of ZSM-5 and catalyst is applied in the field of ZSM-5 molecular sieve catalyst and its preparation and application, which can solve the problems of low ethylbenzene selectivity, short catalyst life, low pure benzene conversion rate, etc. The effect of long activity period and high ethylbenzene yield

Active Publication Date: 2012-02-15
BAOWU CHARCOAL MATERIAL TECH CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0010] At present, the alkylation of benzene and ethanol to produce ethylbenzene mainly focuses on the basic research of the reaction mechanism. The main disadvantage is that the conversion rate of pure benzene is low, and the selectivity of ethylbenzene is not high, there are many by-products, and the catalyst life is short.

Method used

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  • A kind of zsm-5 catalyst and its preparation and application
  • A kind of zsm-5 catalyst and its preparation and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] The hydrogen-type ZSM-5 molecular sieve with a silicon-aluminum ratio of 60 was treated at 500° C. for 6 hours. Weigh 26 grams of the roasted hydrogen ZSM-5 molecular sieve powder, add it to 200 ml of 0.1mol / L titanium sulfate solution, stir at room temperature for 30 hours, then stir and evaporate to dryness at 80°C, and dry at 110°C After 12 hours, roast at 500° C. for 7 hours to obtain a molecular sieve with a titanium content of 3%, then add 14 grams of pseudo-boehmite, grind and mix evenly. Add 3wt% dilute nitric acid and knead evenly, extrude, dry at 120°C for 10 hours, and bake at 540°C for 6 hours to obtain the catalyst. The prepared catalyst was heated at a temperature of 380°C, a molar ratio of benzyl to alcohol of 4:1, and a weight hourly space velocity of 4h -1 Reaction evaluation under the conditions. The evaluation results show that the selectivity of ethylbenzene is 92.78%, and the conversion rate of benzene is 24.76%.

Embodiment 2

[0048] The hydrogen type ZSM-5 molecular sieve with a silicon-aluminum ratio of 90 was calcined at 600°C for 3 hours in advance. Measure 200 mL of titanium sulfate solution with a molar concentration of 0.02 mol / L, add 18 g of roasted hydrogen-type ZSM-5 molecular sieve powder, stir at room temperature for 10 hours, then stir and evaporate to dryness at 65°C, and bake at 100°C Dry for 24 hours and bake at 600°C for 10 hours. To obtain a molecular sieve with a titanium content of 1%, weigh 15 grams of the modified molecular sieve, add 5 grams of pseudoboehmite, add 5 wt% of dilute nitric acid, mix evenly, extrude, dry at 100°C for 20 hours, and roast at 600°C 4 hours to obtain the desired catalyst. At a temperature of 400°C, the molar ratio of benzene to ethanol is 5:1, and the weight hourly space velocity is 4h -1 Under the conditions of evaluation, the selectivity of ethylbenzene was evaluated to be 93.75%, and the conversion rate of benzene was 18.65%.

Embodiment 3

[0050] Treat the hydrogen-type ZSM-5 molecular sieve with a silicon-aluminum ratio of 96 at 500°C for 8 hours in advance, weigh 20 grams of the roasted hydrogen-type ZSM-5 molecular sieve powder, and add it to 250 ml of 0.2mol / L titanium sulfate solution , exchanged at 90°C for 3 hours, washed with 2500 ml of deionized water, dried at 110°C for 12 hours, and roasted at 500°C for 7 hours to obtain titanium ion-exchange modified molecular sieves, weighed 14 grams of modified molecular sieves and added 6 g γ-Al 2 o 3 , adding 5wt% dilute nitric acid, kneading evenly, extruding, drying at 110°C for 9 hours, and roasting at 540°C for 10 hours. Crush into 20-40 mesh at a temperature of 380°C, the molar ratio of benzene to ethanol is 2:1, and the weight hourly space velocity is 3h -1 Under the conditions of evaluation, the selectivity of ethylbenzene was evaluated to be 88.54%, and the conversion rate of benzene was 46.29%.

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Abstract

The invention provides a ZSM-5 molecular sieve catalyst and a preparation method thereof and the use thereof in reaction of preparing ethylbenzene by benzene and ethanol. The preparation method comprises: sulfate or nitrate solution of iron or titanium for the ZSM-5 catalyst with certain silica alumina ratio is adopted and modified by an immersion method or an ion exchange method, and the modified solution contains 1 to 10 percent of modified metals in percentage by weight; and then the modified metals are grinded and mixed evenly with binder pseudo-boehmite or gamma-Al2O3 molecular sieve according to the mass ratio of the molecular sieve to the binder of 85-65: 15-35, dilute nitric acid is added into the mixture, and the mixture is mixed, molded, dried and roasted and the modified ZSM-5 molecular sieve catalyst is obtained. The catalyst is applied to the reaction of synthesizing the ethylbenzene by the benzene and the ethanol, and the selectivity and conversion rate of the ethylbenzene are increased when the mol ratio of the benzene to the ethanol is 1 to 10.

Description

technical field [0001] The invention relates to a catalyst, in particular to a ZSM-5 molecular sieve catalyst and its preparation and application. Background technique [0002] Ethylbenzene is an important chemical raw material, mainly used in the production of styrene. Styrene is a basic organic chemical raw material, mainly used in the field of polymer materials to produce polystyrene and its copolymers, such as ABS, AS, styrene-butadiene rubber and its unsaturated polyester. Due to the strong growth in the consumption of styrene downstream products such as polystyrene and ABS resin, the demand for ethylbenzene, the raw material for styrene production, has grown rapidly in recent years. [0003] Most of the ethylbenzene currently on the market is produced by the alkylation of benzene and ethylene. The main process technology is AlCl 3 Liquid phase alkylation method, molecular sieve alkylation method and catalytic distillation process. [0004] AlCl 3 The liquid-phase ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/46B01J29/40C07C2/86C07C15/073
CPCY02P20/52
Inventor 陶军李文怀胡津仙伊汀孙剑高俊华
Owner BAOWU CHARCOAL MATERIAL TECH CO LTD
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