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Aromatized eutectic superfine zeolite grain catalyst and its preparation process and application

A technology of eutectic zeolite and ultrafine particles, which is applied in the field of ultrafine particle eutectic zeolite aromatization catalysts and its preparation and application, can solve the problems of unsatisfactory catalytic activity stability, unfavorable hydrocarbon molecular diffusion, and catalyst carbon deposition speed Faster and other problems, to save equipment investment, inhibit hydrogenation saturation, and reduce the loss of octane number

Active Publication Date: 2009-10-14
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The catalyst prepared by a single ultrafine particle zeolite has a single acidity, so it is not conducive to the aromatization of hydrocarbon molecules and other reactions; the catalyst made of mechanically mixed ultrafine particle zeolite has poor cross-linking and interconnection of pores of different sizes, which is not conducive to the reaction of hydrocarbon molecules. Therefore, it is easy to cause secondary reactions such as polymerization, the carbon deposition speed of the catalyst is fast, and the stability of the catalytic activity is not ideal.

Method used

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  • Aromatized eutectic superfine zeolite grain catalyst and its preparation process and application
  • Aromatized eutectic superfine zeolite grain catalyst and its preparation process and application
  • Aromatized eutectic superfine zeolite grain catalyst and its preparation process and application

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0048] This example prepares 4.0wt% NiO-1.5wt% ZnO-1.5wt% La 2 o 3 / HZSM-5 / HZSM-11 eutectic zeolite aromatization catalyst with a grain size of 20nm to 100nm.

[0049] Take by weighing 229.6g sodium type HZSM-5 / HZSM-11 eutectic zeolite (SiO 2 / Al 2 o 3 The molar ratio is 27, the grain size is 20nm-100nm, the weight ratio of HZSM-5 and HZSM-11 is 80:20), 140.0g Al 2 o 3 , and grind and mix them evenly, add 150ml of dilute nitric acid solution with a concentration of 5.6g / 100ml, and grind them into a uniform powder cake. Extrude into rods with a diameter of 2.0 mm on a rod extruder. After drying at room temperature, dry at 100°C for 12 hours, and bake at 500°C for 10 hours to make ultrafine particle HZSM-5 / HZSM-11 aromatization catalyst carrier intermediate.

[0050] 100ml of the above-mentioned catalyst carrier intermediates were loaded into a vertical activation furnace, heated up to 510°C in an atmosphere of water vapor at 150ml / hour, and subjected to constant temperat...

example 2

[0054] This example prepares 6.0wt% MoO 3 -2.0wt%CoO-3.0wt%La 2 o 3 / The crystal size is 70nm~150nm HZSM-5 / HBeta eutectic zeolite aromatization catalyst.

[0055] Weigh 239.6g HZSM-5 / HBeta(SiO 2 / Al 2 o 3 The molar ratio is 33, the grain size is 70nm~150nm, the weight ratio of HZSM-5 and HBeta is 60:40), 140.0g Al 2 o 3 , and grind and mix them evenly, add 180ml of dilute nitric acid solution with a concentration of 3.6g / 100ml, and grind them into a uniform powder cake. Extrude into rods with a diameter of 2.0 mm on a rod extruder. After drying at room temperature, drying at 120° C. for 10 hours, and calcining at 510° C. for 8 hours to prepare an ultrafine particle HZSM-5 / HBeta eutectic zeolite aromatization catalyst carrier intermediate.

[0056] 100ml of the above-mentioned catalyst carrier intermediate was loaded into a vertical activation furnace, and the temperature was raised to 520° C. under an atmosphere of water vapor of 300ml / hour, and a constant temperature ...

example 3

[0060] This example prepares WO 3 7.0wt%-2.0wt%NiO-1.0wt%La 2 o 3 / HZSM-5 / HZSM-11 aromatization catalyst with a grain size of 20nm-100nm rare earth-containing ultrafine particle eutectic zeolite.

[0061] Weigh 229.6g containing rare earth HZSM-5 / HZSM-11 eutectic zeolite (La 2 o 3 Content is 1.0wt%, SiO 2 / Al 2 o 3 The molar ratio is 26, the grain size is 20nm-100nm, the weight ratio of HZSM-5 and HZSM-11 is 70:30), 140.0g Al 2 o 3 , and grind and mix them evenly, add 150ml of dilute nitric acid solution with a concentration of 5.6g / 100ml, and grind them into a uniform powder cake. Extrude into rods with a diameter of 2.0 mm on a rod extruder. After air drying at room temperature, drying at 100°C for 12 hours and calcining at 500°C for 10 hours to prepare rare earth-containing ultrafine particle eutectic zeolite HZSM-5 / HZSM-11 aromatization catalyst carrier intermediate.

[0062] 100ml of the above-mentioned catalyst carrier intermediate is charged into a vertical ac...

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Abstract

The invention discloses an ultrafine-particle eutectic zeolite aromatization catalyst, a preparation method thereof and an application in the process of hydrogenation, desulfurization and olefin reduction of whole fraction catalytic cracking gasoline. The composition of the catalyst is as follows: the transition metal oxide content is 0.5wt% to 10.0wt%, the lanthanide rare earth metal oxide content is 0.5wt% to 5.0wt%, and the ultrafine particle eutectic zeolite content is 50.0wt% to 90.0wt% %, the rest is an inorganic oxide binder, and the grain size of the ultrafine particle eutectic zeolite is 20nm to 500nm. The ultrafine particle eutectic zeolite catalyst prepared by the method of the present invention is applied in the FCC gasoline hydrodesulfurization / aromatization combined process, which can greatly reduce the FCC gasoline sulfur and olefin content, and the gasoline product antiknock index ((R+M) / 2) The loss is small. Especially compared with the mechanically mixed ultrafine particle zeolite aromatization catalyst, the carbon deposition of the ultrafine particle eutectic zeolite aromatization catalyst is reduced by more than 23%.

Description

1. Technical field [0001] The invention relates to an ultrafine particle eutectic zeolite aromatization catalyst, a preparation method thereof, and an application in a combined process of hydrogenation desulfurization and aromatization of full fraction catalytic cracking gasoline. 2. Background technology [0002] Reducing the olefin and sulfur content in gasoline can effectively reduce the emission of harmful substances in automobile exhaust. For this reason, countries around the world have formulated their own new standards for clean gasoline marked by low sulfur and low olefin. The European Class IV vehicle exhaust emission standard (EU2005 standard) stipulates that the sulfur content of gasoline after 2005 is ≯50μg / g, and the olefin content is 14v%~18v%. 80μg / g, olefin content≯14v%. The new clean gasoline standard Q / SHR010-2005 formulated by China requires that after July 1, 2005, the sulfur content of gasoline is ≯500μg / g, and the olefin content is ≯35.0v%. On July 1,...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/80B01J29/076B01J29/072B01J23/10C10G45/68C10G45/08C10G45/12
Inventor 赵乐平方向晨尤百玲庞宏刘继华王继锋关明华胡永康
Owner CHINA PETROLEUM & CHEM CORP