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Epoxidation catalyst

a technology of epoxidation catalyst and catalyst, which is applied in the direction of catalyst activation/preparation, physical/chemical process catalyst, organic chemistry, etc., can solve the problems of prone to produce by-products and silver catalysts that have not proved useful in commercial epoxidation of higher olefins, and achieve the effect of higher selectivity to the desired epoxid

Inactive Publication Date: 2006-06-22
LYONDELL CHEM TECH LP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

The process achieves higher selectivity and reduced formation of by-products, improving the efficiency of epoxide production from olefins and hydrogen peroxide.

Problems solved by technology

Unfortunately, the silver catalyst has not proved useful in commercial epoxidation of higher olefins.
One disadvantage of the described direct epoxidation catalysts is that they are prone to produce by-products such as glycols or glycol ethers formed by the ring-opening of the epoxide product or alkane by-product formed by the hydrogenation of olefin.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

example 1

Edta Treatment of TS-1 Catalyst

[0036] TS-1 can be made according to any known literature procedure. See, for example, U.S. Pat. No. 4,410,501, DiRenzo, et. al., Microporous Materials (1997), Vol. 10, 283, or Edler, et. al., J. Chem. Soc., Chem. Comm. (1995), 155.

[0037] Catalyst 1A: Spray dried TS-1 (15 g, 80% TS-1, silica binder, 2.0 wt. % Ti, calcined at 550° C. in air) is suspended in a saturated aqueous ethylenediaminetetraacetic acid (EDTA) solution (150 mL of 0.5 wt. % EDTA) solution and stirred at 60° C. for 18 hours. After filtration and washing (3 times with 100 mL water), the obtained solid is air-dried at 110° C., and calcined in air at 550° C. for 4 hours. Catalyst 1A contains 1.8 wt. % Ti.

[0038] Catalyst 1B: Spray dried TS-1 (20 g, 80% TS-1, silica binder, 2.0 wt. % Ti, calcined at 550° C. in air) is suspended in an aqueous dipotassium ethylenediaminetetraacetic acid dihydrate (K2EDTA) solution (300 g of 3 wt. % K2EDTA solution) and stirred at 60° C. for 18 hours. Aft...

example 2

Epoxidation of Propylene with Hydrogen Peroxide

[0039] Spray dried TS-1 (as a comparative example), Catalysts 1A and 1B are used in batch epoxidation of propylene with hydrogen peroxide according to the following procedure:

[0040] A solution of methanol, water and hydrogen peroxide (40 g of solution, 84% MeOH, 11% H2O, and 5% H2O2) is added to a 125-mL PARR reactor equipped with a stirring bar. The catalyst (0.15 g) is suspended in the reaction solution, and the reactor is charged with propylene (20 g). The closed system is then heated at 50° C. for 30 minutes. The concentration of unreacted hydrogen peroxide is determined by titration (sodium thiosulfate method) and the products are analyzed with GC.

[0041] The results are shown in Table 1.

example 3

Preparation of Pd / TS-1 Catalysts

[0042] Comparative Catalyst 3A: Spray dried TS-1 (16 g, 80% TS-1, silica binder, 2.0 wt. % Ti, calcined at 550° C. in air) is slurried in water (14 g). An aqueous solution of tetra ammine palladium dinitrate (0.299 g aqueous solution containing 5.37 wt. % Pd) is then added, and the slurry is stirred at 30° C. for 10 minutes. The pH is adjusted to 7.0 with 30 wt. % ammonium hydroxide and the slurry is stirred at 30° C. for an additional 35 minutes before adjusting the pH to 7.6. The slurry is filtered and the filter cake is washed with water (100 mL, three times). The solids are vacuum dried at 55° C. for 6 hours, then calcined in air at 300° C. for 4 hours. The calcined solids are then transferred to a quartz tube, heated to 100° C. and treated with 5 vol. % hydrogen in nitrogen (100 cc / min) for 1 hour. The dried solid contains 0.1 wt. % Pd and 2.0 wt. % Ti.

[0043] Catalyst 3B: Catalyst 3B is made according to the procedure of Comparative Catalyst 3A...

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Abstract

Titanium or vanadium zeolites are pretreated by contacting with an amino polyacid compound, such as ethylenediaminetetraacetic acid or a salt thereof, prior to use in olefin epoxidation with hydrogen peroxide.

Description

FIELD OF THE INVENTION [0001] This invention relates to an epoxidation process to produce epoxides from olefins and hydrogen peroxide using a titanium or vanadium zeolite catalyst that has been pre-treated by contacting with an amino polyacid compound, such as ethylenediaminetetraacetic acid or a salt thereof. BACKGROUND OF THE INVENTION [0002] Many different methods for the preparation of epoxides have been developed. Generally, epoxides are formed by the reaction of an olefin with an oxidizing agent in the presence of a catalyst. The production of propylene oxide from propylene and an organic hydroperoxide oxidizing agent, such as ethylbenzene hydroperoxide or tert-butyl hydroperoxide, is commercially practiced technology. This process is performed in the presence of a solubilized molybdenum catalyst, see U.S. Pat. No. 3,351,635, or a heterogeneous titania on silica catalyst, see U.S. Pat. No. 4,367,342. Another commercially practiced technology is the direct epoxidation of ethyle...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C07D301/12
CPCB01J29/04B01J29/89B01J37/0045B01J37/0203B01J2229/20B01J2229/37C07D301/12C07D303/04C07D301/06B01J29/076B01J29/00
Inventor QIN, KUNGREY, ROGER A.WHITMAN, PETER J.
Owner LYONDELL CHEM TECH LP