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Modification method of small grain nay type molecular sieve

A molecular sieve and small-grain technology, applied in crystalline aluminosilicate zeolite, octahedral crystalline aluminosilicate zeolite, etc., can solve the problem of poor hydrothermal stability of small-grain NaY molecular sieve and fine-grain Y-type molecular sieve. Poor performance, complex process steps and other problems, to achieve the effect of excellent selectivity of heavy naphtha, improved accessibility, and conducive to diffusion

Active Publication Date: 2016-08-17
CHINA PETROLEUM & CHEM CORP +1
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The method for preparing fine-grained Y-type molecular sieves proposed in CN1081425A is to precrystallize the NaY synthesis solution at 80°C to 180°C for 1 to 10 hours, then add the directing agent after cooling to room temperature, and then add the directing agent at 80°C to 100°C. Continue to crystallize for 5 to 25 hours, the process steps are more complicated and difficult to control, and the hydrothermal stability of the fine-grained Y-type molecular sieve obtained is poor
[0014] At present, due to the poor hydrothermal stability and unstable structure of small-grain NaY molecular sieves, small-grain Y-type molecular sieves with complete structure, high crystallinity and many secondary pores cannot be obtained after subsequent modification.

Method used

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  • Modification method of small grain nay type molecular sieve
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  • Modification method of small grain nay type molecular sieve

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Experimental program
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Effect test

Embodiment 1

[0045] This embodiment is to prepare raw material small grain NaY molecular sieve

[0046] Preparation of NY-1

[0047] (1) Preparation of guiding agent: Dissolve 8 g of sodium hydroxide solid in 80 g of water, add 2.5 g of sodium metaaluminate (Al 2 o 3 Content is 45wt%, Na 2 O content is 41wt%), then add 40g water glass (SiO 2 Content is 28wt%, Na 2 The O content is 8wt%), mixed evenly, and aged at 18° C. for 4 hours to prepare the directing agent.

[0048] (2) Preparation of amorphous silicon-aluminum precursor

[0049] Prepare solid sodium aluminate to a concentration of 0.3L for 100g A1 2 o 3 / L sodium aluminate working solution (a). Dilute the concentrated ammonia water with an appropriate amount of distilled water to obtain about 10wt% dilute ammonia water (b). SiO 2 28wt% sodium silicate solution, then diluted to 0.5L concentration is 140g SiO 2 / L sodium silicate working solution (c). Take a 5-liter steel reaction tank, add 0.5 liter of distilled water to ...

Embodiment 2

[0063] First, carry out alkali treatment on the raw material small-grain NaY molecular sieve, beat and mix 1000 grams of NY-1 with 5 L of NaOH solution with a concentration of 1 mol / L, and maintain the temperature of 80 ° C for 2 hours, filter and wash to the solution Close to neutrality; contact the filter cake with 10 liters of 0.5 mol / L ammonium nitrate aqueous solution, stir at 300 rpm, stir at 90°C for 1 hour, then filter molecular sieves, and leave a small sample for analysis of Na 2 O content; repeat the above operation until Na in the molecular sieve 2 The O content reached 2.5wt%, and the sample number after drying was NNY-1.

Embodiment 3

[0065] First, carry out alkali treatment on the raw material small-grain NaY molecular sieve, beat and mix 1000 grams of NY-2 with 5 L of KOH solution with a concentration of 0.8 mol / L, and keep stirring at 80°C for 2 hours, filter, and wash with water until the solution Close to neutral; contact the filter cake with 10 liters of 0.5 mol / L ammonium nitrate aqueous solution, stir at 300 rpm, stir at a constant temperature of 95 ° C for 1 hour, then filter molecular sieves, and leave a small sample for analysis of Na 2 O content; repeat the above operation until Na in the molecular sieve 2 The content of O reached 2.5wt%, and the number of the dried sample was NNY-2.

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Abstract

The invention discloses a modification method for a small-grain NaY molecular sieve. According to the method, an NaY molecular sieve with a high Si / Al ratio, high crystallinity and good stability is used as a raw material, caustic washing, ammonium exchange, hydrothermal treatment and treatment with a mixed solution of acid and ammonium salt are successively carried out, so the obtained small-grain NaY molecular sieve has a higher SiO2 / Al2O3 molar ratio and higher proportion of secondary pores, maintains the stability of the NaY molecular sieve, and has a great specific surface area and higher crystallinity. The small-grain NaY molecular sieve prepared in the invention is applicable as a cracking component of a light oil type hydrocracking catalyst and enables the catalyst to have good activity, heavy naphtha selectivity and excellent product nature.

Description

technical field [0001] The invention relates to a modification method of NaY molecular sieves, in particular to a modification method of small grain NaY molecular sieves. Background technique [0002] Y-type molecular sieve is currently the most common cracking active component in the field of heavy oil cracking. The crystal grain is generally about 1000nm. After the reaction, the product is also difficult to diffuse out, so its cracking activity and selectivity of the target product are restricted. Compared with conventional Y-type molecular sieves, small-grain Y-type molecular sieves have a larger outer surface area and more active centers on the outer surface, which is conducive to improving the cracking capacity of macromolecular hydrocarbons, and thus has superior catalytic performance. At the same time, reducing the grain size of the Y-type molecular sieve can also improve the utilization rate of active sites on the inner surface. In general, the diffusion of reactan...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C01B39/24
Inventor 樊宏飞孙晓艳王占宇
Owner CHINA PETROLEUM & CHEM CORP
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