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Catalyst suitable for aromatization of low carbon hydrocarbons in Fischer-Tropsch synthetic oil and its preparation and application

A Fischer-Tropsch synthetic oil and catalyst technology, which is applied in the direction of carbon compound catalysts, physical/chemical process catalysts, catalysts, etc., can solve the problems of increasing the difficulty of industrial scale-up preparation, complex ion solution process, and low selectivity of aromatic hydrocarbons, etc., to achieve optimal Reaction stability, inhibition of carbon deposition rate, low yield of aromatics

Active Publication Date: 2022-06-07
YANKUANG ENERGY R&D CO LTD
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] The aromatization catalysts disclosed in Chinese patents CN1069906A and CN1069999A are micron-sized ZSM-5 supported noble metals (Pt), VII transition metals and a small amount of non-metallic elements. They are mainly used for C8~C9 aromatization, and the conversion rate of alkane reaches 88%, selectivity for aromatics was 45.6%, lower selectivity for aromatics
But since [Zn(NH 3 ) 4 ] 2+ The complex ion solution introduces Zn into the impregnating solution, and prepares [Zn(NH 3 ) 4 ] 2+ The complex ion solution process is more complicated, which increases the difficulty of industrial scale-up preparation
[0008] Disclosed in Chinese patent CN 1070847 for C 5 -C 8 A catalyst for the aromatization of low-carbon chain hydrocarbons as a raw material and a preparation method thereof. The catalyst uses HZSM-5 zeolite as a carrier, and the conventional impregnation method is used to introduce Ga, Zn, and Pt as active components. Through steam treatment, the catalyst has a good activity, but the total aromatics yield of the catalyst is up to 54%, and there is still room for improvement in the yield; and the raw material is normal C5-C8 alkanes, which are somewhat different from the low-carbon olefin raw materials produced in Fischer-Tropsch synthetic oil; The catalyst contains noble metal Pt, and the cost of the catalyst is high

Method used

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  • Catalyst suitable for aromatization of low carbon hydrocarbons in Fischer-Tropsch synthetic oil and its preparation and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Take HZSM-5 molecular sieve with a silicon-to-alumina ratio of 25, and roast it in a muffle furnace at 500 °C for 6 hours for pretreatment; 40g of pretreated HZSM-5 molecular sieve and 10g of SB powder are fully mixed, and then use 10g of dilute nitric acid and an appropriate amount to remove Kneading with ionized water, molding on an extruder to obtain a 2-5mm bar-shaped solid, drying at 80°C for 3 hours, calcining at 550°C for 6 hours, crushing and sieving to obtain a precursor of 20-40 meshes; 500°C, airspeed 5.0 hours -1 The catalyst carrier was obtained by steam treatment for 2 hours; 15g of the catalyst carrier was impregnated into 0.1mol / LZn(NO) 3 )2, 0.1mol / L Ga(NO 3 )3 and 0.1mol / L Ni(NO 3 ) 2 The mixed aqueous solution was stirred at room temperature for 1 hour, stood for 24 hours, dried at 120 °C for 12 hours, and then calcined at 500 °C for 6 hours to obtain a catalyst with a loading content of 1%Zn-1%Ga-1%Ni / ZSM-5 .

Embodiment 2

[0035] Take HZSM-5 molecular sieve with a silicon-alumina ratio of 38, and calcinate it in a muffle furnace at 520 ° C for 4 hours for pretreatment; 20g of pretreated HZSM-5 molecular sieve and 10g of SB powder are fully mixed, and then 8.5g of dilute nitric acid and an appropriate amount are added. Deionized water, shape on an extruder to obtain a 2-5mm bar-shaped solid, dry at 100°C for 4 hours, calcinate at 520°C for 3 hours, and crush the sieved 20-40 mesh precursor; 550°C, airspeed 5.0 hours -1 The catalyst carrier was obtained by steam treatment for 2 hours; 15 g of the precursor was impregnated into 0.15 mol / L Zn(NO 3 ) 2 , 0.05mol / L Ga(NO 3 ) 3 and 0.10mol / L Ni(NO 3 ) 2 In aqueous solution, stirred at room temperature for 1 hour, stood for 18 hours, dried at 120°C for 24 hours, and then calcined at 550°C for 2 hours to obtain 1.5%Zn-0.5%Ga-1%Ni / ZSM-5 catalyst.

Embodiment 3

[0037] Take HZSM-5 molecular sieve with a silicon-to-alumina ratio of 80, and roast it in a muffle furnace at 600 °C for 2 hours for pretreatment; 50g of pretreated HZSM-5 molecular sieve is fully mixed with 40g of SB powder, and then 28g of dilute nitric acid and an appropriate amount are added. Deionized water, shape on an extruder to obtain a 2-5mm bar-shaped solid, dry at 110°C for 6 hours, calcinate at 550°C for 3 hours, and crush the sieved 20-40 mesh precursor; 600°C, airspeed 8.0 hours -1 The catalyst carrier was obtained by steam treatment for 1 hour; 15g of the precursor was impregnated into 0.35mol / LZn(NO3)2, 0.1mol / L Ga(NO3)2 3 ) 3 and 0.05mol / L Ni(NO 3 ) 2 In the aqueous solution, stirred at room temperature for 1 hour, stood for 18 hours, dried at 120°C for 24 hours, and then calcined at 480°C for 6 hours to obtain 3.5%Zn-1%Ga-0.5%Ni / ZSM-5 catalyst.

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Abstract

The invention relates to a low-carbon hydrocarbon aromatization catalyst suitable for Fischer-Tropsch synthetic oil, which is composed of HZSM‑5 molecular sieve loaded with active components Zn, Ga and Ni, and includes components with the following weight content: the Zn content is 0.05-4 %, the Ga content is 0.05-2.0%, the Ni content is 0.05-1.5%, and the rest is the carrier HSM-5 molecular sieve. The present invention introduces Zn, Ga and Ni as active components by conventional impregnation method, and removes HZSM by steam treatment Part of the aluminum in the ‑5 skeleton appropriately improves the acid distribution on the surface of the molecular sieve, ensures the activity of the catalyst for aromatization of low-carbon hydrocarbons, and at the same time inhibits the carbon deposition rate on the catalyst. Compared with the prior art, the invention can be directly used in the aromatization reaction of low-carbon hydrocarbons in Fischer-Tropsch synthetic oil, and has the advantages of high activity, good selectivity, low carbon deposition, good stability and the like.

Description

technical field [0001] The invention relates to a catalyst for aromatization of low-carbon hydrocarbons and a preparation method thereof, in particular to a catalyst suitable for aromatization of low-carbon hydrocarbons in Fischer-Tropsch synthetic oil, and a preparation method and application thereof. Background technique [0002] In recent years, with the rapid development of the three major synthetic material industries of synthetic rubber, fibers and resins and the rising domestic demand for fine chemicals, aromatic hydrocarbons have very broad market prospects as a blending component of high-octane clean gasoline. [0003] Light hydrocarbon aromatization is a new process for producing aromatic hydrocarbons developed in recent years, which is used to produce aromatic hydrocarbons or blending components of high-octane gasoline. Dehydrogenation, oligomerization, cyclization, isomerization, and hydrogen transfer are a series of complex reactions to convert aromatic hydrocar...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/46C07C2/76C07C15/04C07C15/06C07C15/08
CPCC07C2/76B01J29/46C07C2529/46B01J2229/36B01J2229/18C07C15/04C07C15/06C07C15/08Y02P20/52
Inventor 孙启文孙燕张宗森曹志红
Owner YANKUANG ENERGY R&D CO LTD
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