A method for refining aromatics using a microporous mesoporous core-shell structure composite molecular sieve

A composite molecular sieve and core-shell structure technology, applied in the field of aromatics refining, can solve the problems of catalyst pore blockage, catalyst deactivation, etc., and achieve the effects of catalytic performance recovery, good regeneration performance, and high reaction selectivity

Active Publication Date: 2022-05-24
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The research of patent CN 105413758 A shows that in the deene refining process with alumina and Y-type molecular sieve as the main component catalyst, metals such as Fe and Ni in the raw oil will gradually deposit on the catalyst, and the coke generated will also deposit on the catalyst. , leading to blockage of the catalyst pores and gradual deactivation of the catalyst

Method used

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  • A method for refining aromatics using a microporous mesoporous core-shell structure composite molecular sieve
  • A method for refining aromatics using a microporous mesoporous core-shell structure composite molecular sieve
  • A method for refining aromatics using a microporous mesoporous core-shell structure composite molecular sieve

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] Example 1: Preparation of ZrPO / HZSM-5 core-shell structure composite molecular sieve catalyst

[0041] (1) Synthesis of ZrPO / HZSM-5 core-shell composite molecular sieve powder with HZSM-5 microporous molecular sieve as the core and ZrPO mesoporous molecular sieve as the shell

[0042] According to the solid-liquid mass ratio of 1:10, 2.0 g of HZSM-5 microporous molecular sieve powder with inner core and 1.0% mass concentration of triblock copolymer FI27 (EO 106 PO 70 EO 106 ) ethanol solution was stirred and mixed, and was continuously stirred at 30° C. for 10 h to obtain mixture A. According to the molar ratio of P to Zr n P / n Zr =0.8, the molar ratio of F127 to P+Zr n F127 / (n P +n Zr )=0.014 ratio, dissolve 57.6g (4.57mmol) F127 in 600mL absolute ethanol, stir at 40°C for 30min to obtain F127 ethanol solution; dissolve 58.0g (180.0mmol) zirconium oxychloride in 300mL absolute ethanol , and stirred at 40°C for 30min to obtain zirconium oxychloride ethanol sol...

Embodiment 2

[0045] Example 2: Al 0.25 Zr 0.75Preparation of PO / Hβ Core-Shell Composite Molecular Sieve Catalyst

[0046] (1) Al 0.25 Zr 0.75 Synthesis of PO / Hβ Core-Shell Composite Molecular Sieve

[0047] According to the solid-liquid mass ratio of 1:30, 5.0 g of the inner core microporous Hβ molecular sieve powder was stirred and mixed with the FI27 ethanol solution with a mass concentration of 3.0%. According to the molar ratio of P to total metal n P / (n Zr +n Al )=0.75, the mole ratio n of F127 and P+Zr+Al F127 / (n P +n Zr +n Al )=0.016 ratio, dissolve 63.0g (5.0mmol) F127 in 600mL absolute ethanol, stir at 30°C for 60min to obtain F127 ethanol solution; dissolve 43.5g (135.0mmol) zirconium oxychloride in 300mL absolute ethanol , and stirred at 30°C for 60min to obtain zirconium oxychloride ethanol solution; 6.0g (45.0mmol) of anhydrous aluminum chloride was dissolved in 150mL of absolute ethanol, and stirred at 30°C for 60min to obtain aluminum chloride ethanol solution ...

Embodiment 3

[0050] Example 3: Ca 0.05 Zr 0.95 Preparation of PO / HY Core-Shell Structure Composite Molecular Sieve Catalyst

[0051] (1)Ca 0.05 Zr 0.95 Synthesis of PO / HY Core-Shell Composite Molecular Sieve

[0052] According to the solid-liquid mass ratio of 1:50, 10.0 g of the inner core microporous HY molecular sieve powder was stirred and mixed with the FI27 ethanol solution with a mass concentration of 5.0%. According to the molar ratio of P to metal n P / (n Zr +n Ca )=0.95, the molar ratio n of F127 to P+Zr+Ca F127 / (n P +n Zr +n Ca )=0.036 ratio, dissolve 126.0g (10.0mmol) F127 in 800mL absolute ethanol, stir at 40°C for 30min to obtain F127 ethanol solution; dissolve 43.5g (135.0mmol) zirconium oxychloride in 300mL absolute ethanol , stirred at 40°C for 30min to obtain an ethanolic solution of zirconium oxychloride; dissolve 0.79g (7.1mmol) of anhydrous calcium chloride with 100mL of anhydrous ethanol, and stirred at 30°C for 60min to obtain a calcium chloride ethanol s...

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Abstract

The invention discloses a method for refining aromatics by using a composite molecular sieve with a microporous mesoporous core-shell structure. ‑1 Under certain conditions, the liquid-phase aromatics are contacted with a solid acid catalyst, so that the trace olefins in the aromatics undergo alkylation and superimposition reactions, and the trace olefins in the aromatics are removed, thereby refining the aromatics and obtaining aromatics from which olefins have been removed The solid acid catalyst is a core-shell structure composite molecular sieve catalyst or a modified core-shell structure composite molecular sieve catalyst loaded with tungsten trioxide; the solid acid catalyst prepared by the present invention has high activity, and the removal rate is above 98%; the catalyst activity is stable Good stability, activity stability time over 3000h; high selectivity of aromatics deolefination reaction, the mass fraction of toluene produced from C8 aromatics refining is less than 0.1%, which can avoid frequent switching operation of reactor reaction and regeneration.

Description

(1) Technical field [0001] The invention relates to an aromatic hydrocarbon refining method for removing trace olefins in aromatic hydrocarbons, in particular to an aromatic hydrocarbon refining method utilizing a microporous mesoporous core-shell structure composite molecular sieve. (2) Background technology [0002] The increased demand for paraxylene has driven the new construction and capacity expansion of catalytic reforming units in petrochemical enterprises. In the process of producing aromatic hydrocarbons in the reformer, the bifunctional reforming catalyst will lead to the formation of a small amount of by-product olefins, and with the promotion of low-pressure reforming technology, the content of olefin impurities in aromatics increases significantly. The active properties of these olefins not only easily form gums and affect product quality, but also lead to the failure of adsorbents for adsorption and separation, and the deactivation of catalysts such as toluene...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/84C07C7/148C07C15/04C07C15/06C07C15/08C07C15/02C10G55/06
CPCB01J29/005B01J35/0073C07C7/14833C10G55/06B01J29/84B01J29/40B01J29/7007B01J29/084B01J2229/186B01J29/7876B01J29/166C07C2529/84C10G2400/30C07C15/04C07C15/06C07C15/08C07C15/02Y02P20/584Y02P20/52
Inventor 任杰刘冰邓优金辉
Owner ZHEJIANG UNIV OF TECH
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