Method for preparing low-carbon olefin by using phosphorus-containing hierarchical pore ZSM-5/Y composite molecular sieve

一种复合分子筛、ZSM-5的技术，应用在分子筛催化剂、烃裂化制烃、化学仪器和方法等方向，能够解决低碳烯烃收率低、催化剂裂化活性低等问题，达到高选择性、好工业应用前景和经济价值、改善产品组成的效果

Active Publication Date: 2021-04-16
SHANDONG DUOYOU TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0008] The purpose of the present invention is to provide a preparation method of phosphorus-containing hierarchically porous ZSM-5 / Y composite molecular sieve, which is simple to operate, low in raw material cost, and effectively solves the problem of low catalyst cracking activity and low carbon in existing FCC units. To solve the technical problem of low olefin yield, effectively obtain high-selectivity propylene, and improve the product composition of the catalytic cracking process unit

Method used

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  • Method for preparing low-carbon olefin by using phosphorus-containing hierarchical pore ZSM-5/Y composite molecular sieve
  • Method for preparing low-carbon olefin by using phosphorus-containing hierarchical pore ZSM-5/Y composite molecular sieve

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Embodiment 1

[0051] The embodiment of the present invention provides a preparation method of a phosphorus-containing hierarchical porous ZSM-5 / Y composite molecular sieve, comprising the following steps:

[0052] (1) 236.6g H 2 O, 9.1g NaOH, 138.7g TPAOH are mixed to form a solution, add 5.0g NaY molecular sieve (silicon-aluminum ratio is 5.3) and mix well, then add 372.3g silica sol and 1.24g boric acid to the above solution gradually in batches under full stirring And shake vigorously at room temperature for 1 hour, the molar ratio in the mixed slurry is:

[0053] Na 2 O:SiO 2 :Al 2 o 3 :B 2 o 3 :OSDA:H 2 O=0.075:1:0.0048:0.0198:0.1:20

[0054] Then put the material in a PTFE-lined stainless steel reaction kettle, crystallize at 180°C for 24 hours, filter and wash the product until the pH value is 7-8, dry at 120°C for 12 hours, and roast at 550°C for 2 hours to obtain NaZSM-5 / Y compound molecular sieve.

[0055] (2) use the NaZSM-5 / Y molecular sieve that 10g step (1) obtains ...

Embodiment 2-8

[0058]Embodiments 2-8 of the present invention respectively provide a preparation method of phosphorus-containing hierarchically porous ZSM-5 / Y composite molecular sieves. The types of silicon source, boron source, organic template agent, phosphorus source and ammonium salt selected are as follows: As shown in Table 1, conventional industrial NaY molecular sieves (silicon-aluminum ratio of 5.3) are used to provide aluminum source and additional silicon source, and the same process method as in Example 1 is used for preparation. The composition of the compound molecular sieve crystallization precursor mixture obtained is shown in Table 1 shown. The finally prepared samples are designated as PZ5Y-2 to PZ5Y-8.

[0059] Table 1

[0060]

[0061] The physical and chemical characterization parameters of the sample PZ5Y-1-8 prepared in Example 1-8 and the sample VS-1-3 prepared in Comparative Example 1-3 are shown in Table 2.

[0062] Table 2

[0063]

Embodiment 9-19

[0065] Examples 9-16 of the present invention respectively provide a method for using samples PZ5Y-1-PZ5Y-8 prepared in Examples 1-8 as catalysts to catalytically crack naphtha to produce ethylene and propylene. Examples 17-19 of the present invention A method of using the samples VS-1~VS-3 prepared in Comparative Examples 1-3 as a catalyst to catalytically crack naphtha to produce ethylene and propylene is provided, and the catalyst samples PZ5Y-1~PZ5Y-8 are tested by this method Evaluation was performed with VS-1 to VS-3.

[0066] The catalyst was evaluated in a continuous flow fixed-bed reactor. The composition of the naphtha raw material is shown in Table 3, and the evaluation conditions and reaction results can be seen in Table 4. The material of the reactor is stainless steel, the inner diameter is 19 mm, and a thermocouple sleeve with an outer diameter of 6 mm is built in. The loading amount of the catalyst is 10g, and the particle size is 20-40 mesh. Naphtha and wate...

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Abstract

The invention discloses a method for preparing low-carbon olefin by using a phosphorus-containing hierarchical pore ZSM-5 / Y composite molecular sieve, which comprises the following steps: under the conditions that the reaction temperature is 600-720 DEG C, the reaction pressure is 0.1-2.0 MPa, the weight ratio of water to petroleum hydrocarbon is 0.1-6.0 and the weight space velocity is 0.1-6.0h-1, contacting a raw material with a phosphorus-containing hierarchical pore ZSM-5 / Y composite molecular sieve catalyst, and reacting to generate a material flow containing ethylene and propylene. The composite molecular sieve has the beneficial effects that the composite molecular sieve can be used as a catalyst to solve the technical problems of low cracking activity of the catalyst and low yield of low-carbon olefins in the existing catalytic cracking (FCC) unit, high-selectivity propylene is effectively obtained, and the product composition of the catalytic cracking process unit is improved.

Description

[0001] This case is a divisional application. The invention name of the original application is: a method for preparing a phosphorus-containing hierarchical porous ZSM-5 / Y composite molecular sieve. The filing date of the original application is: 2018-06-11, and the application number of the original application For: 201810592367.5. technical field [0002] The invention relates to the field of molecular sieve materials and their preparation, in particular to a method for preparing a phosphorus-containing hierarchically porous ZSM-5 / Y composite molecular sieve and the preparation of low-carbon olefins using the phosphorus-containing hierarchically porous ZSM-5 / Y composite molecular sieve Methods. Background technique [0003] At present, the production of light olefins from petroleum as raw materials is mainly produced through hydrocarbon steam cracking and catalytic cracking processes. Traditional steam cracking is carried out by free radical reaction, with high temperatur...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/80C07C4/06C07C11/06C07C11/04B01J35/10
CPCC10G70/00C01B39/24C01B39/40B01J29/084B01J29/40B01J29/80B01J2229/186B01J2229/62C10G2400/20Y02P20/52
Inventor 于心玉王志光石文记魏胜华
Owner SHANDONG DUOYOU TECH
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