Nitrogen-resisting hydrocracking catalyst and preparation method thereof

A hydrocracking and catalyst technology, applied in the direction of physical/chemical process catalysts, catalyst carriers, molecular sieve catalysts, etc., can solve the problems of low cracking activity, poor nitrogen tolerance, poor catalyst activity, etc., to improve liquid yield, increase The number of secondary holes, the effect of facilitating contact reaction and

Active Publication Date: 2016-06-01
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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  • Nitrogen-resisting hydrocracking catalyst and preparation method thereof
  • Nitrogen-resisting hydrocracking catalyst and preparation method thereof
  • Nitrogen-resisting 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 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%;

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

[0042] (3) Molecular sieve obtained in step (2) according to liquid-solid ratio of 5:1 and 0.3mol / L citric acid solution (concentration in H + Total) 300ml mixed, then heated up to 40°C, and reacted at constant temperature 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 a closed container filled with butene atmosphere, control the pressure of 0.3MPa and fully contact it f...

Embodiment 2

[0054] Molecular sieve modification process:

[0055] (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%.

[0056] (2) Hydrothermally treat 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 in H + Total) 400ml mixed, then heated up to 50°C, and reacted at constant temperature 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 at 200°C for 22 hours in an air atmosphere;

[0060] (6) The molecular sieve treated in step (5) is directly put into a muffle furnace heated to 500°...

Embodiment 3

[0069] Molecular sieve modification process:

[0070] (1) Take the original NaY molecular sieve powder 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, exchange at 90°C for 1.5 hours, repeat this process twice, and the Y molecular sieve after exchange The Na content is 1.8% as Na2O.

[0071] (2) Hydrothermally treat 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 in H + Total) 400ml mixed, then heated up to 60°C, and reacted at constant temperature for 2 hours;

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

[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 put into a muffle furnace heated to 500°C in adv...

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Abstract

The invention discloses a nitrogen-resisting hydrocracking catalyst and a preparation method thereof. The nitrogen-resisting hydrocracking catalyst comprises the following components according to the total weight of the catalyst: 55-85% of a silicon-aluminum carrier containing a modified Y type molecular sieve, and 15-45% of an active metal in the form of a metal oxide, wherein the mass percentage of the modified Y type molecular sieve in the silicon-aluminum carrier is 15-90%, and the balance is amorphous silicon-aluminum and / or aluminum oxide; the crystal cell constant of the modified Y type molecular sieve is 2.425-2.455nm; the bulk phase silicon-aluminum ratio is 8-30, wherein 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 the modified Y type molecular sieve is 600-800m<2> / g; the pore volume is 0.40-0.70ml / g; the infrared acid content is 0.3-1.5mmol / g; and the relative crystallinity is 70-110%. The hydrocracking catalyst disclosed by 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 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 d...

Claims

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Application Information

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Patent Type & Authority Applications(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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