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Catalytic cracking catalyst and preparation method thereof

A catalytic cracking and catalyst technology, applied in catalytic cracking, physical/chemical process catalysts, molecular sieve catalysts, etc., can solve the problems of rare earth loss and rare earth utilization rate reduction, and achieve high crystallization retention, high rare earth utilization rate, and precise control Effect

Active Publication Date: 2015-11-25
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0011] In the prior art, regardless of the rare earth Y molecular sieve obtained by the double-cross-two-baking process or the one-cross-one-baking process, the rare earth content in the product is always lower than the total rare earth amount input, such as CN1053808A, CN1069553C, several disclosed in CN1026225C All kinds of rare earth Y molecular sieves have this feature. Even if more rare earth ions are located in the small cages, it is inevitable that some rare earth ions still exist in the supercages, and the rare earth ions in the supercages will be washed in the subsequent washing process. It is backwashed down, resulting in the loss of rare earths, resulting in a decrease in the utilization rate of rare earths

Method used

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Embodiment 5、6 and 8

[0029] The second Y-type molecular sieve is a gas-phase ultra-stable Y-type molecular sieve containing rare earths, and its preparation method includes: contacting the Y-type molecular sieves containing rare earths with silicon tetrachloride under stirring, and the contact temperature is 100-500 ° C, The contact time is 0.1-10 hours, and the weight ratio of the rare earth-containing Y-type molecular sieve to silicon tetrachloride is 1:0.05-0.5. The specific preparation method of the second gas-phase ultra-stable Y-type molecular sieve can refer to the patent application CN1683244A, especially the examples 5, 6 and 8;

[0030] In the present invention, the third Y-type molecular sieve is a rare earth-containing DASY molecular sieve, and the rare earth-containing DASY molecular sieve is a rare earth-containing hydrothermal ultrastable molecular sieve, wherein RE 2 o 3 The rare earth content in terms of (rare earth oxide) is preferably 1.5 to 3.0% by weight. The rare earth-cont...

Embodiment 1

[0054](1) Preparation of rare earth Y-type molecular sieve

[0055] Take 2.6 kg of NaY molecular sieve (Qilu Catalyst Factory, ignited 22.5% by weight, silicon-aluminum ratio 2.7, crystallinity 88%, the same below) and 15 kg of deionized water to mix and beat, add 1.0 liter concentration of 160gRE 2 o 3 / L of rare earth chloride solution and 0.24 kg of ammonium chloride solid, stir well, raise the temperature to 70°C and adjust the pH of the slurry to 4.0 with dilute hydrochloric acid, continue to exchange for 1.5 hours, filter, wash with water, and dry, under the condition of 100% water vapor Calcined at 550°C for 2 hours to obtain cross-calcined rare earth sodium Y molecular sieve Y-A1. The chemical composition of Y-A1 is 5.1% by weight of sodium oxide and 7.8% by weight of rare earth oxide. Then by molecular sieve: NH 4 Cl:H 2 The ratio of O=1:0.2:10 is beaten and exchanged at 70°C for 1 hour. After filtering and washing, re-beating and adding 0.27 liters of concentratio...

Embodiment 2

[0060] The pseudo-boehmite of 20 weight parts on a dry basis is mixed with deionized water for beating, and adding concentration to the obtained slurry is 36% by weight hydrochloric acid peptization, the acid-aluminum ratio (the 36% by weight hydrochloric acid and The weight ratio of pseudo-boehmite on a dry basis) is 0.20, the temperature is raised to 65°C for acidification for 1 hour, and 39 parts by weight of kaolin slurry on a dry basis and 9 parts by weight of aluminum sol on a dry basis are added , stirred for 20 minutes, then added 15 parts by weight of rare earth Y-type molecular sieve Y-A in dry basis and the second Y-type molecular sieve of 15 parts by weight in dry basis and DASY2.0 in 2 parts by weight in dry basis The slurry was mixed with molecular sieves, stirred for 30 minutes to obtain a slurry with a solid content of 30% by weight, and spray-dried to make a microsphere catalyst. The microsphere catalyst was calcined at 500°C for 1 hour, and then heated at 60°...

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Abstract

The invention relates to a catalytic cracking catalyst and a preparation method. The catalytic cracking catalyst contains a cracking activity component, clay and an adhesive, wherein the cracking activity component a first Y-type molecular sieve, a second Y-type molecular sieve and a third Y-type molecular sieve; the first Y-type molecular sieve is a rare-earth Y-type molecular sieve, the rare-earth content in the first Y-type molecular sieve is 10-25 wt% on the basis of rare-earth oxides, the cell constant is 2.440-2.472nm, the crystallinity is 35-65%, the silicon / aluminum atomic ratio in the framework is 2.5-5.0, and the product of the ratio (I1 / I2) of 2theta=11.8+ / -0.1 degree peak intensity I1 to 2theta=12.3+ / -0.1 degree peak intensity I2 in an X-ray diffraction pattern and the rare-earth weight percent in the molecular sieve on the basis of rare-earth oxides is greater than 50; the second Y-type molecular sieve is a rare-earth-containing gas-phase overstable Y-type molecular sieve; and the third Y-type molecular sieve is a rare-earth-containing DASY molecular sieve. The preparation method comprises the following steps: preparing a slurry containing the cracking activity component, adhesive and clay, and carrying out spray drying. The catalyst has higher conversion rate and gasoline yield, and can reduce the consumption of the molecular sieves, thereby lowering the cost.

Description

Background technique [0001] Catalytic cracking (FCC) is an important secondary processing process of crude oil and occupies a pivotal position in the oil refining industry. In the catalytic cracking process, heavy fractions such as vacuum distillate oil or residues of heavier components react in the presence of catalysts and are converted into high value-added products such as liquefied gas, gasoline, and diesel oil. In this process, it is usually necessary to use Catalytic material with high cracking activity. Microporous zeolite catalytic materials are widely used in petroleum refining and processing industries due to their excellent shape-selective catalytic performance and high cracking reactivity. Among them, Y-type molecular sieve has been the main active component of catalytic cracking catalyst since it was first used in the 1960s. Especially the Y-type molecular sieve modified by rare earth has a significant effect on improving the acidity and structural stability of...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/80C10G11/05
Inventor 任飞杨雪朱玉霞罗一斌邓景辉郑金玉
Owner CHINA PETROLEUM & CHEM CORP
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