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Modified Y molecular sieve and preparation method thereof

A molecular sieve and modification technology, applied in molecular sieve catalysts, chemical instruments and methods, hydrocarbon oil cracking, etc., can solve the problems of increased secondary cracking in the heating process, poor sensitivity of catalysts to heating, and increased hydrogen consumption, etc., to achieve wide application foreground effect

Active Publication Date: 2018-01-16
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] At present, modified Y molecular sieve is the most widely used in hydrocracking process. The conventional treatment method has uniform distribution of silicon and aluminum inside and outside the molecular sieve, and uniform distribution of acid centers. When the silicon aluminum ratio of Y molecular sieve is reduced, the acid center density of Y molecular sieve is increased, and the The temperature sensitivity is improved, but at the same time, the secondary cracking is also greatly increased, and the hydrogen consumption is greatly increased
However, when the Y molecular sieve is subjected to advanced treatment and the acid density is too low, the temperature-raising sensitivity of the catalyst is poor.
[0004] CN200710158784.0 discloses a hydrocracking catalyst containing Y molecular sieve and its preparation method. In this invention, Y-type molecular sieve is obtained after hydrothermal treatment with a mixed aqueous solution of aluminum salt and acid, and the temperature-raising sensitivity of the prepared catalyst is Higher, but at the same time, the secondary cracking during the heating process increases significantly, and the hydrogen consumption increases significantly, which is not conducive to the stable operation of the industrial hydrocracking unit during the heating process
[0005] CN200810012212.6 discloses a hydrocracking catalyst carrier and its preparation method. The hydrocracking catalyst prepared by the invention has poor temperature raising sensitivity

Method used

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  • Modified Y molecular sieve and preparation method thereof
  • Modified Y molecular sieve and preparation method thereof
  • Modified Y molecular sieve and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Molecular sieve modification process:

[0032] (1) Take 200g of NaY molecular sieve raw powder prepared in the laboratory, mix it with ammonium nitrate with a concentration of 0.5mol / L according to the liquid-solid ratio of 3:1, exchange at 70°C for 3 hours, repeat this process 3 times, and the exchanged Y molecular sieve Na content in Na 2 O is calculated as 2.5%;

[0033] (2) Hydrothermally treat the Y molecular sieve obtained in step (1) at 560°C and 0.1MPa for 2 hours;

[0034] (3) The molecular sieve obtained in step (2) was stirred and mixed with distilled water according to the liquid-solid ratio of 5:1, and then the temperature was raised to 80°C. During the stirring process, 400ml of 0.5mol / L aluminum sulfate solution was added, and the reaction was carried out at constant temperature for 2 hours.

[0035] (4) Dry the molecular sieve obtained in step (3) at 140°C for 8 minutes;

[0036] (5) Take the molecular sieve obtained in step (4) and place it in a clos...

Embodiment 2

[0040] Molecular sieve modification process:

[0041] (1) Take the NaY molecular sieve raw powder prepared in the laboratory, mix it with ammonium nitrate with a concentration of 0.8mol / L according to the liquid-solid ratio of 3:1, exchange at 70°C for 3 hours, repeat this process 3 times, and the Y molecular sieve after exchange Na content in Na 2 O is calculated as 2.0%.

[0042] (2) Hydrothermally treat the Y molecular sieve obtained in step (1) at 600°C and 0.1MPa for 3 hours;

[0043] (3) The molecular sieve obtained in step (2) is mixed with H at a liquid-solid ratio of 7:1 + A mixed solution of hydrochloric acid with a concentration of 1.0mol / L was mixed and treated at 95°C for 2 hours;

[0044] (4) The molecular sieve obtained in step (3) was dried at 250°C for 2 hours;

[0045] (5) Soak the molecular sieve obtained in step (4) in toluene solvent for 3 hours;

[0046] (6) The molecular sieve treated in step (5) was dried at 130°C for 25 minutes;

[0047] (7) The ...

Embodiment 3

[0050] Molecular sieve modification process:

[0051] (1) Take the NaY molecular sieve raw powder prepared in the laboratory, mix it with ammonium nitrate with a concentration of 0.8mol / L according to the liquid-solid ratio of 3:1, exchange at 70°C for 3 hours, repeat this process 3 times, and the Y molecular sieve after exchange Na content in Na 2 O is calculated as 2.0%.

[0052] (2) Hydrothermally treat the Y molecular sieve obtained in step (1) at 520°C and 0.1MPa for 3 hours;

[0053] (3) Step (2) sieve the citric acid solution (concentration in H + Meter) mixed, then heated to 50 ° C, constant temperature reaction for 2 hours;

[0054] (4) The molecular sieves treated in step (3) were dried at 130°C for 40 minutes;

[0055] (5) soak the molecular sieve obtained in step (4) in heptene for 4 hours, and then heat at 180°C for 30 hours in an air atmosphere;

[0056] (6) The molecular sieve obtained in step (5) is mixed with H at a liquid-solid ratio of 7:1 + A mixed so...

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Abstract

The invention discloses a modified Y molecular sieve and a preparation method thereof, which have the following properties: the silicon-aluminum ratio of the bulk phase is 10-70, wherein the silicon-aluminum ratio of the surface layer is 7-30, and the silicon-aluminum ratio of the surface layer is lower than the silicon-aluminum ratio of the bulk phase Ratio 5~40, wherein the surface layer refers to the thickness range from the outer surface of the molecular sieve to the inside of 5~400nm; the unit cell constant of the modified Y molecular sieve is 2.425~2.455nm; the specific surface area of ​​the modified Y molecular sieve is 600~900m2 / g, the pores Content 0.20~0.70ml / g; infrared acid content 0.3~1.5mmol / g. The preparation method of the modified Y molecular sieve of the present invention is as follows: the Y molecular sieve after ammonium exchange is subjected to primary dealumination treatment, rapid drying, carbon deposition reaction, high-temperature roasting treatment, and then secondary dealumination treatment, drying, and charcoal burning treatment, A modified Y molecular sieve is obtained. The silicon-aluminum ratio of the surface layer of the molecular sieve of the invention is lower than that of the bulk phase, and has broad application prospects in the hydrocracking reaction process.

Description

technical field [0001] The invention relates to a modified Y molecular sieve and a preparation method thereof. Background technique [0002] Hydrocracking technology has the characteristics of strong adaptability to raw materials, great flexibility in production operations and product plans, and good product quality. It can directly convert various heavy and low-quality feedstocks into high-quality jet fuel, diesel, and lubricating oil base materials that are urgently needed by the market. As well as chemical naphtha and tail oil steam cracking raw materials for ethylene production, it has become one of the most important heavy oil deep processing processes in modern oil refining and petrochemical industries, and has been increasingly widely used at home and abroad. The heart of the hydrocracking process is the hydrocracking catalyst. Hydrocracking catalyst is a typical dual-function catalyst, which has dual functions of hydrogenation and cracking. Among them, the hydrogen...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/16C10G47/20
Inventor 柳伟杜艳泽王凤来刘昶秦波张晓萍
Owner CHINA PETROLEUM & CHEM CORP
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