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Modified zeolite catalyst

A technology for modifying zeolite and catalyst, applied in catalysts, molecular sieve catalysts, carbon compound catalysts, etc., can solve problems such as deactivation and blocking, and achieve the effect of improving selectivity

Inactive Publication Date: 2012-05-23
BP OIL INT LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, their needle-like crystallite morphology combined with a one-dimensional microporous structure makes them particularly susceptible to deactivation due to coking mechanisms that block the access to the internal microporous structure.

Method used

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  • Modified zeolite catalyst
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  • Modified zeolite catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] 3 g of zeolite θ1 in the hydrogen form (H-θ-1, Si / Al=50) was suspended in 100 ml of 0.2 M aqueous sodium hydroxide solution and vigorously stirred at 80° C. for 30 minutes. The reaction was then quenched by cooling in an ice bath. The remaining solid was isolated by filtration, washed with distilled water and dried overnight at 100°C. Then use 0.1M NH4NO 3 Three consecutive exchanges of the solution at 83 °C for 2 h and using a solution-to-solid weight ratio of 20 converted base-treated θ-1 to its acidic form. Finally the samples were calcined at 450 °C for 5 hours. When studied using transmission electron microscopy and nitrogen absorption (77°K) and the BJH method (V 中孔 =0.107cm 3 g -1 ) measured, the product of this method shows distinct mesopores compared to untreated zeolites.

Embodiment 2

[0042] 3 g of zeolite θ-1 in the hydrogen form (H-θ-1, Si / Al=50) was suspended in 100 ml of 0.2 M aqueous sodium hydroxide solution and vigorously stirred at 85° C. for 30 minutes. The reaction was then quenched by cooling in an ice bath. The remaining solid was isolated by filtration, washed with distilled water and dried overnight at 100°C. The base-treated θ-1 was then suspended in 2.0M aqueous oxalic acid solution (solution / solid ratio 10 wt / wt) and stirred at 70°C for 2 hours. The solid was isolated by filtration, washed with distilled water and dried overnight at 100°C. Finally the samples were calcined at 375°C for 3 hours. When studied using transmission electron microscopy and nitrogen absorption (77°K) and the BJH method (V 中孔 =0.117cm 3 g -1 ) measured, the product of this method shows distinct mesopores compared to untreated zeolites.

Embodiment 3

[0043] Embodiment 3 (comparative example)

[0044] 3 g of the theta-1 zeolite in the hydrogen form (H-θ-1, Si / Al=25) used in Example 8 was suspended in 100 ml of 0.2 M aqueous sodium hydroxide solution and vigorously stirred at 85° C. for 30 minutes . The reaction was then quenched by cooling in an ice bath. The remaining solid was isolated by filtration, washed with distilled water and dried overnight at 100°C. Then use 0.1M NH4NO 3 Three consecutive exchanges of the solution at 80 °C for 2 h and using a solution-to-solid weight ratio of 20 converted base-treated θ-1 to its acidic form. Finally the samples were calcined at 450 °C for 5 hours. When studied using transmission electron microscopy and nitrogen absorption (77°K) and the BJH method (V 中孔 =0.067cm 3 g -1 ) measured, the product of this method showed fewer mesopores compared to untreated zeolites. Although not in accordance with the present invention, this example demonstrates that mesopores can be introduced...

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PUM

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Abstract

A modified zeolite catalyst derived from a zeolite of a structural type which consists of a one-dimensional micropore structure of channels made from rings containing between 8 and 12 silicon / aluminium atoms is disclosed. It consists substantially of a plurality of crystallites having additional mesoporosity whose volume is in the range 0.09 to 0.25 ml3g-1 as measured by nitrogen absorption at 77 K and calculated by the BJH method. The mesoporosity may be introduced into the crystallites by e.g. treatment with aqueous sodium hydroxide at a pH at 25 C in excess of 8 for an extended period at elevated temperature. The catalyst shows improved resistance to catalyst deactivation and greater selectivity to higher hydrocarbons when used to e.g. oligomerize light alkenes e.g. propene or the butenes.

Description

technical field [0001] The present invention relates to a modified zeolite catalyst having a one-dimensional microporous structure consisting of channels formed by rings containing 8 to 12 silicon / aluminum atoms, especially those of the 10-ring TON structure type, which are especially suitable as lower Catalysts for the oligomerization of hydrocarbons and alcohols to produce higher hydrocarbon fractions suitable for use as gasoline or diesel fuel. Background technique [0002] Oligomerization of light olefins such as propylene and butene represents an important industrial route to produce environmentally friendly synthetic liquid fuels free of sulfur and aromatics. These methods allow the production of hydrocarbon mixtures in the gasoline or diesel boiling range, depending on the exact nature of the catalyst and its operating conditions. For example, high temperature (>300°C) and low pressure (≤30 bar) are known to increase gasoline yield, while low temperature and high ...

Claims

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Application Information

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IPC IPC(8): B01J29/70B01J37/06
CPCC07C2529/70C10G2300/70B01J29/7284B01J2229/16C07C2521/12B01J2229/22B01J2229/37C07C2521/08C01B39/026B01J29/7092B01J37/06B01J29/7884B01J2229/32C10G50/00B01J35/1038B01J2229/38C07C1/20C07C2521/04B01J29/7042B01J35/1061B01J35/633B01J35/647C07C2529/76B01J29/44C07C2529/78B01J35/69
Inventor 阿韦利诺·科玛克里斯蒂娜·马蒂内兹埃里克·J·多斯科奇尔乔治·亚路里斯
Owner BP OIL INT LTD
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