Method for preparing hierarchically porous ZSM-5 molecular sieve for methanol to propylene

A ZSM-5, methanol-to-propylene technology, applied in molecular sieve catalysts, chemical instruments and methods, hydrocarbon production from oxygen-containing organic compounds, etc. Effects of methanol conversion activity, shortened diffusion path, and good carbon deposition resistance

Active Publication Date: 2018-05-18
CHNA ENERGY INVESTMENT CORP LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The purpose of the present invention is to provide a method for preparing a multi-stage porous ZSM-5 molecular sieve for methanol to propylene, so as to solve the problems of low propylene selectivity and poor carbon deposition resistance of the catalyst in the prior art

Method used

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  • Method for preparing hierarchically porous ZSM-5 molecular sieve for methanol to propylene
  • Method for preparing hierarchically porous ZSM-5 molecular sieve for methanol to propylene
  • Method for preparing hierarchically porous ZSM-5 molecular sieve for methanol to propylene

Examples

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Embodiment 1

[0031] Embodiment 1: with 40% silica sol as silicon source, sodium metaaluminate (NaAlO2) is aluminum source, sodium hydroxide (NaOH) is alkali source, according to 1Al2O3: 200SiO2: 25NaOH: 1500H2O ratio prepares gel, crystal The amount of addition is 5% (mass fraction). Place in a crystallization kettle, first crystallize at 120°C for 6h, cool rapidly, add 5wt% octadecyltrimethylammonium bromide (STPA) of the pre-crystallized product, reflux at 90°C for 6h, then move into In a hydrothermal synthesis reaction kettle, crystallize at 180°C for 24 hours, centrifuge and wash with deionized water several times, and dry at 120°C for 12 hours to obtain ZSM-5 molecular sieve powder I. Exchange with 0.1mol / L hydrochloric acid at a liquid-solid mass ratio of 20:1 and a temperature of 90°C to obtain H-type molecular sieve precursor II after washing, drying, and roasting; use 3mol / L ammonium sulfate at 90 Under the condition of ℃, it was exchanged twice for 2 hours each time, and then wa...

Embodiment 2

[0032] Example 2: Using the molecular sieve raw powder I prepared in Example 1, exchange it with 3mol / L hydrochloric acid at a liquid-solid mass ratio of 5:1, and at a temperature of 90°C, and obtain after washing, drying, and roasting H-type molecular sieve precursor II; use 1mol / L ammonium chloride at a liquid-solid ratio of 10:1, exchange twice at 90°C for 3h each time, wash, dry, and roast at 350°C for 12h to obtain Desired catalyst (sample 3). Under the same evaluation conditions as in Comparative Example 1, the distribution of main products is shown in Table 1, and the BET characterization results of the catalyst are shown in Table 2.

Embodiment 3

[0033] Example 3: Using the molecular sieve powder I prepared in Example 1, exchange it with 3 mol / L hydrochloric acid at a liquid-solid mass ratio of 15:1, and at a temperature of 90°C, and obtain after washing, drying, and roasting H-type molecular sieve precursor II; use 2mol / L ammonium sulfate at a liquid-to-solid ratio of 10:1, exchange twice at 90°C for 4h each time, wash, dry, and roast at 450°C for 12h to obtain Desired catalyst (sample 4). Under the same evaluation conditions as in Comparative Example 1, the distribution of main products is shown in Table 1, and the BET characterization results of the catalyst are shown in Table 2.

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Abstract

The invention discloses a method for preparing a hierarchically pore porous ZSM-5 molecular sieve for methanol to propylene. The method comprises the steps as follows: a, mixing an aluminum source, asilicon source, an alkali source and a ZSM-5 molecular sieve seed crystal with water to form a gel; b, pre-crystallizing the gel in a reactor at 80-140 DEG C for 6-48 h; c, quenching a pre-crystallized product obtained in step b, adding an organic template, heating the pre-crystallized product containing the template to 100-180 DEG C for crystallization reaction, performing solid-liquid separation, washing and drying on a crystallized product after the reaction to obtain molecular sieve original powder; d, placing the molecular sieve original powder obtained in step c in an ammonium salt solution for ion exchange to obtain an ammonia-type ZSM-5 molecular sieve, and then performing calcination to obtain the HZSM-5 molecular sieve. The prepared molecular sieve catalyst has good propylene selectivity and good carbon deposition resistance.

Description

technical field [0001] The invention belongs to the technical field of molecular sieve preparation, and relates to a method for preparing a multi-stage porous ZSM-5 molecular sieve for methanol to propylene. Background technique [0002] Propylene is one of the most important chemical raw materials, and currently it mainly comes from petroleum routes such as FCC and naphtha cracking. In recent years, domestic demand for propylene has grown rapidly, but my country's oil production is far from meeting market demand, and the import rate has exceeded 50%. Under such circumstances, the diversification of raw materials for propylene production has become a major issue related to the adjustment of the country's energy structure . The gas-phase methanol conversion technology from natural gas and coal synthesis has been mature, which has laid a good foundation for the development of the methanol-to-olefins process. The methanol-to-propylene process will become another important stabl...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01B39/40B01J29/40C07C1/20C07C11/06
CPCB01J29/40C01B39/40C01P2006/12C01P2006/14C07C1/20C07C11/06Y02P20/52
Inventor 关翀齐静王林李云张伟雍晓静罗春桃
Owner CHNA ENERGY INVESTMENT CORP LTD
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