High silicon Y-type zeolite containing rare-earth and its preparing method

A zeolite and rare earth technology, which is applied in the directions of crystalline aluminosilicate zeolite and octahedral crystalline aluminum silicate zeolite, etc. problems, to achieve the effects of high structural stability and hydrothermal stability, easy large-scale industrial application, and uniform contact reaction

Active Publication Date: 2006-10-25
CHINA PETROLEUM & CHEM CORP +1
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  • Abstract
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  • Claims
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AI Technical Summary

Problems solved by technology

The formation of a large number of dense lumps makes the contact between silicon tetrachloride gas and zeolite solid extremely uneven. Less contact, or even contact with silicon tetrachloride gas, also makes the hydrothermal stability of the rare earth-containing high-silicon Y-type zeolite product not good, and the initial unit cell is not easy to shrink, and the equilibrium unit cell constant is low Shortcomings
The formation of a large number of dense lumps also causes the formed lumps to stick to the walls of the reactor causing product loss and the need to clean the walls
[0008] Moreover, the method for preparing high-silicon Y-type zeolite by adopting the existing gas-phase extraction of aluminum and supplementing silicon, the zeolite solid particles in the zeolite solid particle bed layer are static and cannot move, and the mass transfer and heat transfer properties of the zeolite solid particles are relatively poor, while The process of gas-phase extraction of aluminum and silicon supplementation is an exothermic reaction, the heat is not easy to spread rapidly, and it is easy to produce local overheating, resulting in a large reaction temperature gradient in the fixed bed, making the reaction between zeolite solid particles and silicon tetrachloride gas uneven , which also makes the hydrothermal stability of the obtained rare earth-containing high-silicon Y-type zeolite product not good
[0009] In addition, the high silicon Y-type zeolite is prepared by using the existing method of gas-phase extraction of aluminum to supplement silicon. Since the zeolite solid particles are a static fixed bed, fillers must be filled at both ends, which causes the inconvenience of disassembling the zeolite solid particles. , it is also necessary to separate the zeolite solid particles from the filler, which is not only labor-intensive, but also the transportation of zeolite solid particles and unloading from the reaction equipment is not easy to automate
And because zeolite is an ultrafine powder, when the zeolite solid is transported and unloaded from the reaction equipment, it is easy to pollute the environment and damage the health of the operators.
[0010] It is also because the zeolite solid particles in the existing gas-phase extraction method for aluminum supplementation is a static fixed bed, and the gas that reacts with the zeolite solid particles must be a flowing gas that carries silicon tetrachloride. Another disadvantage of the silicon method is that the amount of silicon tetrachloride and the gas carrying silicon tetrachloride and the waste gas generated by the reaction is very large.

Method used

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preparation example Construction

[0024]According to the preparation method of the zeolite provided by the present invention, the silicon-aluminum ratio of the rare earth-containing Y-type zeolite is 3-8, preferably 4-6; and the unit cell constant is 2.45-2.48 nanometers. In terms of rare earth oxides, the rare earth content in the rare earth-containing Y-type zeolite is greater than zero to 20% by weight, preferably 6-18% by weight. The rare earth-containing Y-type zeolite can be obtained commercially, or can be prepared from NaY zeolite with a unit cell constant of 2.45-2.48 nanometers by means of rare earth ion exchange. If using the NaY zeolite and rare earth chloride aqueous solution according to NaY:RECl 3 :H 2 The weight ratio of O=1:0.1-0.25:5-15, under the conditions of pH>3.5 and temperature 80-95°C, perform rare earth ion exchange at least once, each exchange for 30-60 minutes, wash and dry after exchange to obtain . The method of preparing rare earth-containing Y-type zeolite from NaY zeolite th...

Embodiment approach 1

[0029] The first specific embodiment of the present invention is as follows figure 1 shown. Described reaction equipment comprises a reactor 1, a feed port 2 and a gas outlet 3, also has a stirrer 4 inside the reactor 1, and wherein, a gas-solid separator 5 is installed on the gas outlet 3, gas The hole diameter and porosity of the holes contained in the solid separator 5 ensure that the gas can pass through but the solid particles cannot pass through. The stirring rod of the stirrer 4 stretches out of the reaction kettle 1, and the place where the stirring rod contacts the reaction kettle 1 is airtight, so that the reaction kettle 1 is not connected to the outside world.

[0030] When preparing the zeolite provided by the present invention, the rare earth-containing Y-type zeolite solid particles are loaded from the feed port 2, the agitator 4 is started, and silicon tetrachloride liquid is added, and the feed port 2 and the gas outlet 3 are sealed. Heat the reaction kettl...

Embodiment approach 2

[0032] The second specific embodiment of the present invention is as figure 2 shown. The reaction device includes all components of the first embodiment, and also includes an air inlet 6 . The air inlet 6 can be located at any position of the reactor 1 , preferably, the feed inlet 2 and the gas outlet 3 are located at the upper part of the reactor 1 , and the air inlet 6 is located at the lower part of the reactor 1 . Air inlet 6 is used to add silicon tetrachloride liquid. With the gas inlet 6, the silicon tetrachloride liquid is fed from the gas inlet 6, and the feed inlet 2 is specially used for feeding the rare earth-containing Y-type zeolite solid particles, and the operation is more convenient.

[0033] When preparing the zeolite provided by the present invention, the rare earth-containing Y-type zeolite solid particles are loaded from the feed port 2, the agitator 4 is started, and the feed port 2 and the gas outlet 3 are sealed. Add silicon tetrachloride liquid fro...

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Abstract

A rare-earth-containing high-silicon Y-type zeolite, the zeolite contains rare earths, is characterized in that the silicon-aluminum ratio of the zeolite is 5-30, the initial unit cell constant is 2.430-2.465 nanometers, and the balance unit cell constant and the initial unit cell constant The ratio is at least 0.985. The zeolite has the characteristics of small initial unit cell constant and large equilibrium unit cell constant. It has high structural stability and hydrothermal stability. The cracking catalyst containing this zeolite is not easy to deactivate. The choice of gasoline, diesel oil, dry gas and coke Good sex.

Description

technical field [0001] The present invention relates to a Y-type zeolite and a preparation method thereof, and more particularly relates to a rare earth-containing high-silicon Y-type zeolite and a preparation method thereof. Background technique [0002] Since US3293192 proposed the hydrothermal dealumination method to prepare high-silicon Y-type zeolite, the preparation of high-silicon Y-type zeolite by hydrothermal method has been widely used. US3,442,715 discloses dealuminated Y zeolite (DAY), US3,449,070 discloses ultrastable Y zeolite (USY), US4,51,694 and US4,401,556 disclose ultrastable hydrophobic Y zeolite and so on. [0003] Introducing rare earths into high-silicon Y-type zeolite to prepare rare-earth-containing high-silicon Y-type zeolite is a way to improve the activity and hydrothermal stability of high-silicon Y-type zeolite. [0004] Rare earth-containing high-silicon Y-type zeolite can be prepared by subjecting NaY zeolite to s...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C01B39/22
Inventor 杜军李峥周灵萍田辉何鸣元龙军
Owner CHINA PETROLEUM & CHEM CORP
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