A kind of modification method of small grain nay type molecular sieve

A molecular sieve and small-grain technology, applied in molecular sieve catalysts, chemical instruments and methods, crystalline aluminosilicate zeolites, etc., can solve the problem of poor hydrothermal stability of small-grain NaY molecular sieves and fine-grain Y-type molecular sieves. 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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  • A kind of modification method of small grain nay type molecular sieve
  • A kind of modification method of small grain nay type molecular sieve
  • A kind of modification method of small grain nay type molecular sieve

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Embodiment 1

[0047] This embodiment is to prepare raw material small grain NaY molecular sieve

[0048] Preparation of NY-1

[0049] (1) Preparation of guiding agent: Dissolve 10 g of sodium hydroxide solid in 80 g of water, add 2 g of sodium metaaluminate (Al 2 o 3 Content is 45wt%, Na 2 O content is 41wt%), then add 36g water glass (SiO 2 Content is 28wt%, Na 2 The O content is 8wt%), mixed evenly, and aged at 15° C. for 4 hours to prepare the directing agent.

[0050] (2) Preparation of amorphous silicon-aluminum precursor

[0051] Prepare solid sodium aluminate to a concentration of 40gAl 2 o 3 / L sodium aluminate working solution, take SiO 2 28wt% sodium silicate solution, then diluted to a concentration of 100g SiO 2 / L sodium silicate working solution. Take 1L of sodium aluminate working solution and place it in a gel-forming tank, then add 0.2L of sodium silicate working solution, control the reaction temperature at 20°C, and feed CO with a concentration of 50v%. 2 gas, ...

Embodiment 2

[0065] 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

[0067] 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 of a small-grain NaY-type molecular sieve. According to the invention, the NaY-type molecular sieve raw material with relatively high silica-to-alumina ratio, high crystallinity and good stability is adopted. Through sequential steps of alkali wash, ammonium exchange, hydrothermal treatment, and acid and ammonium salt mixed solution treatment, the obtained small-grain Y-type molecular sieve has relatively high SiO2 / A12O3 molar ratio as well as relatively high secondary pore proportion. Also, the stability of the Y-type molecular sieve is maintained. The molecular sieve has relatively high specific surface area and relatively high crystallinity. The Y-type molecular sieve provided by the invention is suitable to be used as a cracking component of a light oil hydrocracking catalyst. With the Y-type molecular sieve, the catalyst has the advantages of good activity, good heavy naphtha selectivity and excellent product quality.

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): C01B39/24B01J29/08
CPCB01J29/084C01B39/24C01P2002/72C01P2004/03C01P2004/62C01P2006/12C01P2006/14
Inventor 王占宇孙晓艳樊宏飞
Owner CHINA PETROLEUM & CHEM CORP
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