Aromatic hydrocarbon olefin removal catalyst as well as preparation method and application thereof

A catalyst and de-olefin technology, which is applied in molecular sieve catalysts, chemical instruments and methods, and hydrogenation and refining of aromatics, can solve the problems of weak carbon capacity and short one-way life, and achieve long service life and surface acidity distribution Appropriate and strong charcoal capacity

Active Publication Date: 2022-05-03
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0009] The present invention aims at the problem that the previous Y molecular sieve de-olefin catalyst has low carbon capacity and short one-way life, and provides an aromatic hydrocarbon de-olefin catalyst, which has the characteristics of strong carbon capacity and long one-way life.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0051] Disperse 5 g of NaY molecular sieve with a molecular silicon-aluminum ratio of 3.6 in 180 mL of 1M HCl solution, stir at room temperature for 2 h, then put it into a crystallization tank at 100 ° C for 10 h to form a gel. Use NaOH to adjust the pH to about 13, slowly drop 13g of 16wt% octadecyltrimethylammonium chloride solution into the gel, stir at 50°C for 40min, adjust the pH to about 10 with acetic acid, stir evenly, and put it into the crystallization The kettle was crystallized at 140°C for 2d, filtered, washed, dried, and calcined at 550°C for 8h to obtain Na-Y / MCM-41. Wherein MCM-41 content is 25%,

[0052] After treating Na-Y / MCM-41 under the condition of 500°C water vapor for 2h, extruded with alumina, dried, and calcined at 600°C for 2h; the calcined catalyst was treated in 3% citric acid solution for 2h, and dried to obtain Deolefination catalyst, wherein the ratio of acid amount of L acid to acid amount of B acid is 1.6:1.

[0053] Take 5g of the above c...

Embodiment 2

[0055] The synthesis procedure of the Y / MCM-41 symbiotic molecular sieve is the same as in Example 1, except that the crystallization condition is changed to 110° C. for 3 hours to obtain 18% MCM-41 in Na-Y / MCM-41.

[0056] Treat Na-Y / MCM-41 under 680°C water vapor condition for 1h, extrude with alumina, dry, and calcinate at 500°C for 3h; treat the calcined catalyst in 1% hydrochloric acid solution for 4h, dry to obtain Olefin catalyst, wherein the ratio of acid amount of L acid to acid amount of B acid is 0.62:1.

[0057] Take 5g of the above catalyst in a fixed-bed reactor to carry out reformate non-hydrodeolefin test. The raw material is mixed xylene at the bottom of the reforming deheptanizer, and the bromine index is 1000 mg Br / 100 g oil. Reaction pressure: 2.0MPa, temperature: 200°C, space velocity: 10.0 hours -1 , with the export bromine index of 200 mg Br / 100 g oil as the standard, the catalyst will be deactivated after 220 hours of reaction.

Embodiment 3

[0059] The preparation process of Na-Y / MCM-41 is the same as embodiment 1.

[0060] After treating Na-Y / MCM-41 under the condition of 500°C water vapor for 2h, extruded with alumina, dried, and calcined at 600°C for 2h; the calcined catalyst was treated in 3% sulfuric acid solution for 2h, dried to obtain Olefin catalyst, wherein the ratio of acid amount of L acid to acid amount of B acid is 2.8:1.

[0061] Take 5g of the above catalyst in a fixed-bed reactor to carry out reformate non-hydrodeolefin test. The raw material is mixed xylene at the bottom of the reforming deheptanizer, and the bromine index is 1000 mg Br / 100 g oil. Reaction pressure: 2.0MPa, temperature: 180°C, space velocity: 10.0 hours -1 , with the export bromine index of 200 mg Br / 100 g oil as the standard, the catalyst will be deactivated after 345 hours of reaction.

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Abstract

The invention provides an olefin removal catalyst as well as a preparation method and application thereof, the olefin removal catalyst mainly comprises a Y/MCM-41 symbiotic molecular sieve, and the ratio of the acid amount of L acid to the acid amount of B acid of the catalyst is (0.2-3): 1 according to a pyridine infrared 200 DEG C desorption result. In terms of XRD crystallinity, the crystallinity of the fresh catalyst is 100%, and the crystallinity of the regenerated catalyst is greater than 70%. The mass ratio of the Y molecular sieve to the MCM-41 molecular sieve is (1-10): 1 based on the XRD diffraction peak area. The preparation method comprises the following steps: carrying out molding roasting, acid treatment and drying on the Y/MCM-41 symbiotic molecular sieve to obtain the aromatic hydrocarbon olefin removal catalyst. The catalyst has the advantages of proper pore structure and surface acidity distribution, high reaction stability and the like.

Description

technical field [0001] The invention relates to the technical field of catalytic deolefinization, in particular to a catalyst for deolefinization of aromatic hydrocarbons, a preparation method and application thereof. Background technique [0002] Aromatics are the basic raw materials of the petrochemical industry, which mainly come from aromatics complexes. The aromatic products after catalytic reforming reaction all contain a certain amount of olefin impurities. Olefins are active, not only easy to polymerize to form colloids, but also may react with other components to form non-ideal components, which will have a great impact on the quality of aromatic products. [0003] On the other hand, certain petrochemical processes such as xylene adsorption separation are particularly sensitive to olefins, even if the content of olefin impurities is only a few parts per million, it will have a very adverse effect on the process. In order to obtain qualified chemical raw materials ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/80B01J29/08C10G45/54C07C15/08C07C7/163C07C7/13C07C7/00
CPCB01J29/80B01J29/084C10G45/54C07C7/163C07C7/13C07C7/00B01J29/03B01J29/04B01J2229/37C07C15/08Y02P20/52
Inventor 周亚新王月梅李为孔德金
Owner CHINA PETROLEUM & CHEM CORP
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