A kind of anti-nitrogen hydrocracking catalyst and preparation method thereof

A hydrocracking and catalyst technology, applied in physical/chemical process catalysts, catalyst carriers, molecular sieve catalysts, etc., can solve the problems of poor catalyst activity, poor nitrogen resistance, low cracking activity, etc. The number of secondary holes, the effect of improving the liquid yield

Active Publication Date: 2017-10-03
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In this way, there is an unsolvable contradiction between improving the nitrogen resistance of the catalyst and maintaining the hydrocracking activity. It is difficult to take care of these two problems at the same time in the conventional molecular sieve modification process.
[0003] 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 obtained catalyst has high activity. But nitrogen tolerance is poor
[0004] CN200810012212.6 discloses a hydrocracking catalyst carrier and its preparation method. The hydrocracking catalyst prepared by the invention has high nitrogen tolerance but low cracking activity
[0005] CN98114489.6 discloses a nitrogen-resistant hydrocracking catalyst for high-yielding middle oil, which is used for one-stage serial hydrocracking of heavy distillate oil to produce a large amount of middle distillate oil. The nitrogen content of the feed in the cracking section can reach 100 μg / g, but the Catalyst activity is poor

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  • A kind of anti-nitrogen hydrocracking catalyst and preparation method thereof
  • A kind of anti-nitrogen hydrocracking catalyst and preparation method thereof
  • A kind of anti-nitrogen hydrocracking catalyst and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Molecular sieve modification process:

[0040] (1) Take 200g of the original NaY molecular sieve powder prepared in the laboratory, mix 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, the Y molecular sieve after exchange Na content in Na 2 O counts as 2.5%;

[0041] (2) hydrothermally heat the Y molecular sieve obtained in step (1) at 540°C and 0.1Mpa for 2 hours;

[0042] (3) The molecular sieve obtained in step (2) is citric acid solution with a liquid-solid ratio of 5:1 and 0.3mol / L (concentration is H + meter) 300ml mixed, and then heated to 40 ℃, constant temperature reaction for 2 hours;

[0043] (4) The molecular sieve obtained in step (3) was dried at 150°C for 8 hours;

[0044] (5) Take the molecular sieve obtained in step (4) and place it in an airtight container filled with butene atmosphere, control the pressure to 0.3MPa and fully contact for 2...

Embodiment 2

[0054] Molecular sieve modification process:

[0055] (1) Take the original powder of NaY molecular sieve 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, and exchange it at 70 °C for 3 hours. Repeat this process 3 times. Na content in Na 2 O counts as 2.0%.

[0056] (2) Hydrothermal treatment of the Y molecular sieve obtained in step (1) at 560°C and 0.1Mpa for 2 hours;

[0057] (3) Step (2) Sieve the citric acid solution (concentration is H + meter) 400ml mixed, then heated to 50 ℃, constant temperature reaction for 2 hours;

[0058] (4) The molecular sieve obtained in step (3) was dried at 200°C for 4 hours;

[0059] (5) soak the molecular sieve obtained in step (4) in heptene for 4 hours, and then heat it in an air atmosphere at 200°C for 22 hours;

[0060] (6) The molecular sieve treated in step (5) is directly placed in a muffle furnace preheated to 500°C, and calcined for 12 minute...

Embodiment 3

[0069] Molecular sieve modification process:

[0070] (1) Take the original powder of NaY molecular sieve prepared in the laboratory, mix it with ammonium nitrate with a concentration of 0.5mol / L according to the liquid-solid ratio of 5:1, and exchange it at 90 °C for 1.5 hours. Repeat this process twice. The Na content was 1.8% as Na2O.

[0071] (2) Hydrothermal treatment of the Y molecular sieve obtained in step (1) at 550°C and 0.1Mpa for 2 hours;

[0072] (3) Step (2) Sieve the citric acid solution (concentration is H + meter) 400ml mixed, and then heated to 60 ℃, constant temperature reaction for 2 hours;

[0073] (4) The molecular sieve obtained in step (3) was dried at 250°C for 2h;

[0074] (5) soak the molecular sieve obtained in step (4) in heptene for 4 hours, and then heat at 200°C for 10 hours in an air atmosphere;

[0075] (6) The molecular sieve treated in step (5) is directly placed in a muffle furnace preheated to 500°C, and calcined for 30 minutes;

[00...

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Abstract

The invention discloses a nitrogen-resistant hydrocracking catalyst and a preparation method thereof. Based on the total weight of the catalyst, the catalyst comprises the following components: 55% to 85% of a silicon-aluminum carrier containing modified Y molecular sieve, and the active metal is calculated as a metal oxide. is 15%~45%; the mass percentage of the modified Y molecular sieve in the silica-alumina carrier is 15%~90%, and the balance is amorphous silica-alumina and / or alumina; the unit cell constant of the modified Y molecular sieve is 2.425~2.455nm; the bulk silicon-aluminum ratio is 8~30, of which the surface layer silicon-aluminum ratio is 20-80, and the surface layer silicon-aluminum ratio is higher than the bulk phase silicon-aluminum ratio; the specific surface area of ​​modified Y molecular sieve is 600~800m2 / g ; Pore volume 0.40~0.70ml / g; Infrared acid content 0.3~1.5mmol / g; Relative crystallinity 70~110%. The hydrocracking catalyst of the invention has good reactivity and nitrogen resistance.

Description

technical field [0001] The invention relates to a hydrocracking catalyst and a preparation method thereof, in particular to a hydrocracking catalyst with strong nitrogen resistance and a preparation method thereof. Background technique [0002] Hydrocracking technology has the characteristics of strong adaptability of raw materials, great flexibility in production operation and product scheme, and good product quality. As well as chemical naphtha and tail oil steam cracking to produce ethylene raw materials, it has become one of the most important heavy oil deep processing technologies in modern oil refining and petrochemical industries, and has been widely used at home and abroad. At the heart of the hydrocracking process is the hydrocracking catalyst. Hydrocracking catalysts are typical bifunctional catalysts with dual functions of hydrogenation and cracking. Among them, the hydrogenation function is usually provided by the sulfided form of active metals such as W, Mo, a...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/16B01J35/10B01J32/00C10G47/20
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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