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A kind of method of organophosphide modified ZSM-5 molecular sieve

A technology of ZSM-5 and molecular sieves, which is applied in organic chemistry, molecular sieve catalysts, chemical instruments and methods, etc., can solve the problems of reduced catalytic performance, poor hydrothermal stability, easy deactivation, etc., achieve high conversion rate, slow down skeleton desorption Aluminum, excellent selective effect

Active Publication Date: 2019-05-21
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although HZSM-5 molecular sieve has good shape-selective performance and isomerization performance, its disadvantage is poor hydrothermal stability, and it is easy to deactivate under harsh high-temperature hydrothermal conditions, which reduces the catalytic performance.

Method used

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  • A kind of method of organophosphide modified ZSM-5 molecular sieve
  • A kind of method of organophosphide modified ZSM-5 molecular sieve
  • A kind of method of organophosphide modified ZSM-5 molecular sieve

Examples

Experimental program
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Effect test

Embodiment 1

[0034] This example illustrates the process of modifying the HZSM-5 molecular sieve with the organophosphorus compound of the present invention.

[0035] Weigh tetrabutylphosphorus hydroxide (Sinopharm Chemical Reagent Co., Ltd., analytically pure, TBPOH content 40%, the same below) and add deionized water, then add 54.0g of HZSM-5 molecular sieve, dip and stir to form P 2 o 5 The mixture is 3.5wt%, and the mixture is dried and calcined, and the product is recovered to obtain the modified HZSM-5 molecular sieve of the present invention, denoted as P-Z-2.

[0036] The crystallinity of P-Z-2 was 83.5.

[0037] The acidity data are shown in Table 1, and Table 1 shows that P-Z-2 is hydrothermally treated at 100% water vapor and 800°C for 17 hours, and the amount of acid centers is measured by pyridine infrared spectroscopy.

[0038] The pore structure data are shown in Table 2. Table 2 illustrates the pore structure data of P-Z-2 after hydrothermal treatment at 100% water vapor...

Embodiment 2

[0051] This example illustrates the process of modifying the HZSM-5 molecular sieve with the organophosphorus compound of the present invention.

[0052] Weigh tetrabutylphosphorus hydroxide (Sinopharm Chemical Reagent Co., Ltd., analytically pure, TBPOH content 40%, the same below) and add deionized water, then add 54.0g of HZSM-5 molecular sieve, dip and stir to form P 2 o 5 The mixture is 5.5 wt%, and the mixture is dried and calcined, and the product is recovered to obtain the modified HZSM-5 molecular sieve of the present invention, which is marked as P-Z-4.

[0053] The crystallinity of P-Z-4 was 85.3.

[0054] The acidity data are shown in Table 3, and Table 3 shows that P-Z-4 is hydrothermally treated at 100% water vapor and 800°C for 17 hours, and the amount of acid centers is measured by pyridine infrared spectroscopy.

[0055] The pore structure data are shown in Table 4. Table 4 illustrates the pore structure data of P-Z-4 after hydrothermal treatment at 100% wa...

Embodiment 3

[0068] This example illustrates the process of modifying the HZSM-5 molecular sieve with the organophosphorus compound of the present invention.

[0069] Weigh tetrabutylphosphorus hydroxide and add deionized water, then add 54.0g of HZSM-5 molecular sieve, impregnate and stir to form P 2 o 5 The mixture was 7.0 wt%, and the mixture was dried and calcined, and the product was recovered to obtain the modified HZSM-5 molecular sieve of the present invention, which was designated as P-Z-6.

[0070] The crystallinity of P-Z-6 was 86.0.

[0071] The acidity data are shown in Table 5, and Table 5 shows that P-Z-6 is hydrothermally treated at 100% water vapor and 800°C for 17 hours, and the amount of acid centers is measured by pyridine infrared spectroscopy.

[0072] The pore structure data are shown in Table 6. Table 6 illustrates the pore structure data of P-Z-6 after hydrothermal treatment at 100% water vapor and 800 °C for 17 h.

[0073] table 5

[0074]

[0075] Table 6...

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Abstract

The invention provides a method for modifying a ZSM-5 molecular sieve through an organophosphorous compound. The method comprises mixing an HZSM-5 molecular sieve and one or more organophosphorous compounds such as tetrabutylphosphonium hydroxide, tetrabutylphosphonium bromide, di-n-butyl phosphate, 1-butylphosphoric acid, tri-n-butylphosphonium oxide, tributylphosphine, fosetyl-aluminum, tetraphenylphosphonium bromide, triphenylethylphosphonium bromide, triphenylbutylphosphonium bromide and triphenylbenzylphosphonium bromide, and drying and calcining the mixture. The organophosphorous compound-modified ZSM-5 molecular sieve has a high pore volume and a high specific surface area and contains more B acid centers.

Description

technical field [0001] The present invention relates to the method for modifying ZSM-5 molecular sieve, the obtained molecular sieve product and application, more specifically, the present invention relates to the method for phosphorus modified ZSM-5 molecular sieve, the obtained phosphorus-containing molecular sieve product and the Converting apps. Background technique [0002] ZSM-5 molecular sieve is a medium-pore molecular sieve (USP3702886) with a high-silicon three-dimensional straight channel with an MFI structure. Stability, high specific surface area, wide variation range of silicon-aluminum ratio, unique surface acidity and low carbon formation. ZSM-5 molecular sieves are widely used as catalysts and catalyst supports, and have been successfully used in production processes such as alkylation, isomerization, disproportionation, catalytic cracking, methanol-to-gasoline, and methanol-to-olefins. [0003] Propylene is an important petrochemical basic raw material se...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/40C07C11/06C07C4/06C10G11/05
CPCY02P20/52
Inventor 张欣罗一斌欧阳颖徐广通高秀枝付颖舒兴田
Owner CHINA PETROLEUM & CHEM CORP
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