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Super-stable Y zeolite, preparation method and application thereof

A technology of zeolite and secondary pores, which is applied in the field of ultra-stable Y zeolite and its preparation and application, which can solve the problems of easily destroyed crystal structure, low acid center density, and decreased crystallinity, and achieve dry gas and coke selectivity Good, heavy oil conversion ability, high crystallinity effect

Active Publication Date: 2012-07-25
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

During the preparation process of the modified zeolite, the crystal structure of the zeolite is easily destroyed, the crystallinity decreases, and the unit cell constant is small, and the acid center density is low, so it is not suitable for heavy oil catalytic cracking

Method used

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  • Super-stable Y zeolite, preparation method and application thereof
  • Super-stable Y zeolite, preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] At room temperature, take 1000 grams (dry basis) of DZ1, add it to 10 liters of mixed acid aqueous solution with a concentration of 0.2N oxalic acid and a concentration of 0.1N hydrochloric acid, stir to make it evenly mixed, put it into a reaction kettle, seal it, and fill it with N 2 , keep the pressure of the system at 0.15MPa (gauge pressure), raise the temperature to 100°C at a rate of 10°C / min, keep at this temperature and pressure for 1 hour, filter, wash, and dry at 120°C for 5 hours to obtain the modification The ultra-stable Y-type zeolite sample, denoted as SZ1, table 1 has provided the composition of SZ1, unit cell constant, relative crystallinity, structure collapse temperature, specific surface area and larger pore diameter (pore diameter is ) of secondary pores accounted for the total secondary pores percentage.

Embodiment 2

[0037] At room temperature, take 2000 grams (dry basis) of DZ1, add it to 20 liters of mixed acid aqueous solution with a concentration of acetic acid of 0.1N and a concentration of hydrochloric acid of 0.15N, stir to make it evenly mixed, put it into a closed pressure reactor, and fill it with N 2 , control the pressure of the reactor to 0.3MPa (gauge pressure), raise the temperature to 115°C at a heating rate of 10°C / min, and keep it at this temperature and pressure for 30 minutes, then filter, wash, and dry the filter cake at 120°C for 5 hours , to get the modified ultrastable Y-type zeolite sample, denoted as SZ2, table 1 has provided the composition of SZ2, unit cell constant, relative crystallinity, structure collapse temperature, specific surface area and larger pore diameter (pore diameter is ) of secondary pores accounted for the total secondary pores percentage.

Embodiment 3

[0039] At room temperature, take 1500 grams (dry basis) of DZ1, add it to 20 liters of mixed acid aqueous solution with a citric acid concentration of 0.1N and a nitric acid concentration of 0.05N, stir to make it evenly mixed, put it into a closed pressure reactor, and fill it with He Gas, the control system pressure is 0.5MPa, the temperature is raised to 130°C at a rate of 10°C / min, and kept at this temperature and pressure for 10 minutes, then filtered, washed, and the filter cake is dried at 120°C for 5 hours, and the modified The ultra-stable Y-type zeolite sample is denoted as SZ3. Table 1 shows the composition of SZ3, unit cell constant, relative crystallinity, structure collapse temperature, specific surface area and larger pore size (pore size is ) of secondary pores accounted for the total secondary pores percentage.

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Abstract

The present invention provides a super-stable Y zeolite and the preparation method thereof. The ratio of silicate to aluminum in the super-stable Y zeolite is 6-11. The lattice constant of the zeolite is 2.446 to 2.458 nanometers. The percentage of non-skeleton aluminum in total aluminum in the zeolite is not higher than 30% by weight. The diameter of secondary pores with diameter of 2 to 100 nanometers in the zeolite shows a double probable distribution. The most probable diameter of the secondary pores with comparatively large diameter is 6-15 nanometers. The proportion of secondary pores with diameter between 8 to 100 nanometers in total secondary pores is 35% to 60%. The preparation method of the zeolite includes the step of making the super-stable Y zeolite come into contact with a solution containing organic acids and inorganic acids in the atmosphere of inert gases and / or nitrogen. The modified super-stable Y zeolite provided in the invention is applied to catalytic cracking; therefore the following effects can be realized: the cracking ability of heavy oil is strong, the selectivity of gasoline is high, and the selectivity of dry gas and carbon coke is good.

Description

technical field [0001] The invention relates to a Y zeolite and its preparation and application method. Furthermore, it is an ultra-stable Y-type zeolite and its preparation and application method. Background technique [0002] Zeolite Y has been the main active component of catalytic cracking (FCC) catalysts since it was first used in the 1960s. However, the pore diameter of Y-type zeolite is only 0.74nm, and the diffusion ability of macromolecular compounds in the oil product is low in its pores, and the accessibility to its active center is poor, so the heavy oil cracking ability of Y-type zeolite is not high. For this reason, in the prior art, the Y-type zeolite is usually super-stabilized to increase the secondary pores of the zeolite, improve the accessibility of the active center of the zeolite and the heavy oil cracking ability. [0003] The hydrothermal dealumination method (hydrothermal method) that C.V.Dvid et al. (Zeolite Chemistry and Catalysis, ACS Monograph ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C01B39/24B01J29/08C10G11/05
Inventor 周灵萍张蔚琳严加松李峥许明德朱玉霞田辉平达志坚
Owner CHINA PETROLEUM & CHEM CORP
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