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Method for preparing selective hydrogenation ring-opening catalyst for aromatic hydrocarbons with double rings or more

A hydrogenation ring-opening and selective technology, which is applied in the direction of molecular sieve catalysts, chemical instruments and methods, physical/chemical process catalysts, etc. Isomerization activity and other issues to achieve the effect of preventing secondary cracking, improving selectivity, and increasing hydrogenation saturation

Active Publication Date: 2015-05-27
CNOOC TIANJIN CHEM RES & DESIGN INST +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Disadvantages: first, a single type of molecular sieve cannot match the cracking activity and isomerization activity of the catalyst, which makes the selective ring-opening ability of the catalyst worse; High requirements, it is difficult to directly apply as a hydrogenation catalyst for low-quality distillate oil

Method used

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  • Method for preparing selective hydrogenation ring-opening catalyst for aromatic hydrocarbons with double rings or more
  • Method for preparing selective hydrogenation ring-opening catalyst for aromatic hydrocarbons with double rings or more
  • Method for preparing selective hydrogenation ring-opening catalyst for aromatic hydrocarbons with double rings or more

Examples

Experimental program
Comparison scheme
Effect test

Embodiment -1

[0033] The synthesis of SAPO-5 / ZSM-5 composite molecular sieve: add 136.0g phosphoric acid (AR, mass concentration 85%) to 432.0g deionized water and mix uniformly, add 93.0g pseudo-boehmite (Shandong Aluminum Co., Ltd., Al 2 o 3 Mass content is 72.0wt%), after uniform mixing reaction certain hour, add 74.0g templating agent triethylamine (abbreviation TEA, Tianjin, purity 99%) and 25.0g acidic silica sol (Qingdao, SiO 2 Content 30wt%), after mixing uniformly to form a sol, 125.0g of 10wt.% hexadecyltrimethoxyorganosilicon ammonium chloride (TPHAC, Shanghai, chemically pure) ethanol solution is added in the above-mentioned sol system, and the sol is transferred to Put the sol into a polytetrafluoroethylene autoclave, and age at 100°C for 4 hours to obtain SAPO-5 seed crystals, then add 80.0g of ZSM-5 zeolite, and crystallize at 180°C After 24 hours. The crystallized product was separated, the obtained solid product was washed with deionized water to pH = 7-8, and dried at 12...

Embodiment -2

[0035] With 47.0g modified Beta molecular sieve (dry basis content 85%), 45.0g SAPO-5 / ZSM-5 composite molecular sieve (dry basis content 90%), 160.0g modified macroporous alumina (dry basis content 75%), Mix 6.0g of scallop powder and 6.0g of methyl cellulose and put it into a kneader for 10 minutes, then add 225.0g of acidic solution prepared by water, nitric acid and citric acid into the dry powder one by one, and knead until it can be extruded. Extruded once each through an empty plate and a cylindrical orifice plate with a diameter of 8 mm, and finally formed into a butterfly-shaped bar with a diameter of 1.6 mm; the obtained wet bar was first cured in an oven at 30°C for 24 hours, and then dried in an oven at 120°C for 8 hours. Finally, it was placed in a muffle furnace and the temperature was programmed to rise to 550° C. for 4 h to obtain the carrier ZT-1.

Embodiment -3

[0037] With 94.0g modified Beta molecular sieve (dry basis content 85%), 45.0g SAPO-5 / ZSM-5 composite molecular sieve (dry basis content 90%), 107.0g modified macroporous alumina (dry basis content 75%), Mix 6.0g of scallop powder and 6.0g of methyl cellulose and put it into a kneader for 10 minutes, then add 225.0g of acidic solution prepared by water, nitric acid and citric acid into the dry powder one by one, and knead until it can be extruded. Extruded once each through an empty plate and a cylindrical orifice plate with a diameter of 8 mm, and finally formed into a butterfly-shaped bar with a diameter of 1.6 mm; the obtained wet bar was first cured in an oven at 30°C for 24 hours, and then dried in an oven at 120°C for 8 hours. Finally, it was placed in a muffle furnace and the temperature was programmed to rise to 550° C. for 4 h to obtain the carrier ZT-2.

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Abstract

The invention discloses a method for preparing a selective hydrogenation ring-opening catalyst for aromatic hydrocarbons with double rings or more. The method is characterized in that the selective hydrogenation ring-opening catalyst for aromatic hydrocarbons with double rings or more is prepared from a carrier, active ingredients and aids, wherein the carrier is prepared from alumina, amorphous silica-alumina, a modified small grain Beta-type molecular sieve and an SPAO-5 / ZSM-5 composite molecular sieve; the active ingredients at least include an oxide of Mo or W and at least include an oxide of Co or Ni; and the aids refer to one or two out of F and P. The invention also relates to a preparation method of the catalyst and a method for synthesizing the SPAO-5 / ZSM-5 composite molecular sieve. The catalyst is effectively matched with a hydrogenation active center, an isomerization active center and a cracking active center, so that the catalyst has excellent aromatic hydrocarbon hydrogenation ring-opening selectivity in the hydrogenation process of low-quality distillate oil enriched in aromatic hydrocarbons with double rings or more.

Description

technical field [0001] The invention relates to the technical field of catalysts, and relates to a preparation method of a selective hydrogenation and ring-opening catalyst for aromatic hydrocarbons with more than two rings, in particular to the preparation and application of a hydrogenation ring-opening catalyst containing multi-element modified alumina and composite molecular sieves. technical background [0002] Aromatics enriched in low-quality diesel fractions, especially double-ring aromatics, are the key factors leading to high diesel density and low cetane number. High aromatics content has become a bottleneck restricting refining and chemical enterprises to produce high-quality clean diesel. The contradiction between increasingly stringent diesel quality standards for aromatics content and the increasing aromatics content in secondary processed diesel has prompted petrochemical researchers to urgently solve how to efficiently convert and economically utilize double-r...

Claims

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Application Information

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IPC IPC(8): B01J29/85C10G49/08
Inventor 于海斌肖寒张玉婷朱金剑臧甲忠张景成南军张国辉耿珊彭雪峰张尚强宋国梁王梦迪
Owner CNOOC TIANJIN CHEM RES & DESIGN INST
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