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Superfine granular zeolite aromatizing catalyst and its preparation and use

A technology of ultra-fine particles and catalysts, which is applied in the petroleum industry, hydrotreating process, and hydrocarbon oil treatment, etc. It can solve the problems of catalyst coking, weakening catalyst catalytic activity, and shortening the start-up period of the device.

Inactive Publication Date: 2004-12-08
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At high temperature, diolefins are easy to polymerize on the strong acid sites on the surface of the acidic molecular sieve catalyst, causing coking of the catalyst, weakening the catalytic activity of the catalyst, and reducing the stability of the catalyst
In severe cases, a large pressure difference (referred to as pressure drop) will be generated between the inlet and outlet of the reactor, shortening the start-up period of the device

Method used

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Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0027] The specific preparation method of the ultrafine particle zeolite aromatization catalyst provided by the present invention comprises the following steps:

[0028] a. Mix and grind ultra-fine particle zeolite and inorganic oxide binder evenly, add nitric acid aqueous solution with a concentration of 3.0-8.0g / 100ml, roll it into a micellar wet cake and then extrude it into strips. Drying at 8°C for 8-15 hours, and roasting at 400°C-600°C for 3-10 hours to prepare an ultrafine particle zeolite aromatization catalyst carrier intermediate;

[0029] b. Put the above-mentioned catalyst carrier intermediate into the activation furnace, raise the temperature to 500-600° C. under the atmosphere of water vapor with a water / solid volume ratio of 1:1-10:1, and conduct a constant temperature hydrothermal treatment at this temperature for 3-600° C. After 15 hours, stop the water vapor intake, change into nitrogen-oxygen mixed gas with nitrogen content of 85wt% to 95wt%, replace the mo...

Embodiment 1

[0032] This example prepares 2.0wt% NiO-0.50wt% ZnO-1.50wt% La 2 o 3 / The grain size is 90nm~500nmHZSM-5 aromatization catalyst.

[0033] Weigh 229.6gHZSM-5 (SiO 2 / Al 2 o 3 The molar ratio is 27), 140.0gAl 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 aromatization catalyst carrier intermediate.

[0034] 100ml of the above-mentioned catalyst carrier intermediate was loaded into a vertical activation furnace, and the temperature was raised to 510° C. under a water vapor atmosphere with a water flow rate of 150ml / h, and a constant temperature hydrothermal treatment was carried out at this temperature for 12 hours. Then, stop feeding water vapor, change into a nitrogen-oxyge...

Embodiment 2

[0038] This example prepares 4.0wt% MoO 3 -1.0wt%ZnO-3.0wt%La 2 o 3 / HBeta aromatization catalyst with a grain size of 70nm to 150nm.

[0039] Weigh 239.6gHBeta (SiO 2 / Al 2 o 3 The molar ratio is 33), 140.0gAl 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 HBeta zeolite aromatization catalyst carrier intermediate.

[0040] Put 100ml of the above-mentioned catalyst carrier intermediate into a vertical activation furnace, raise the temperature to 520°C in an atmosphere with a water flow rate of 300ml / h steam, and perform a constant temperature hydrothermal treatment at this temperature for 10 hours. Then, stop the water vapor, and replace it with nitrogen-oxygen m...

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Abstract

Preparation of micro-size particle zeolite catalyst for aromatization and its application in complete fractional FCC gasoline hydrogenation-aromatization composite process are disclosed. The catalyst consists of: transition metal oxide and lanthanide metal oxide is 1.0wt% - 10.0wt%, micro-size particle zeolite of 20nm-800nm 50.0wt% - 90.0wt%, and balanced inorganic oxide binder. Its advantages include low total and L acidity, unblocked pore canal, good stability and strong anticoking ability, low antiknock index ((R+M) / 2) loss of gasoline product with reduced S and olefin contents of FCC gasoline.

Description

1. Technical field [0001] The invention relates to an ultra-fine particle 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] With the rapid improvement of people's awareness of environmental protection, the air pollution caused by automobile exhaust has attracted more and more attention. Reducing olefin and sulfur content in gasoline can reduce volatile organic compounds (VOCs), nitrogen oxides (NO X ), sulfur dioxide and other harmful substances. To this end, countries around the world have formulated their own new standards for clean gasoline marked by low sulfur and low olefination. The EU EU2005 standard stipulates that after 2005, the sulfur content of clean gasoline in Europe shall not exceed 50 μg / g, and the olefin content shall be 14v%~18v%. Not more than 14v%; my country's new clean ga...

Claims

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Application Information

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IPC IPC(8): C10G65/04
Inventor 赵乐平胡永康韩崇仁周勇刘继华王祥生
Owner CHINA PETROLEUM & CHEM CORP
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