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Selectively hydrogenating catalyst and preparation method thereof

A hydrogenation catalyst, catalyst technology, applied in the direction of selective hydrorefining, chemical instruments and methods, metal/metal oxide/metal hydroxide catalyst, etc., can solve the problem of impurity resistance to be improved, etc. Effects of diene hydrogenation performance and selectivity, suitable activity, impurity resistance and coking resistance improvement

Active Publication Date: 2009-05-20
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The anti-impurity performance of the palladium catalyst in the prior art needs to be improved

Method used

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  • Selectively hydrogenating catalyst and preparation method thereof
  • Selectively hydrogenating catalyst and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Preparation of vector

[0036] The well-known conventional extrusion molding method was used to prepare the carrier. Weighed 200 grams of alumina dry rubber powder produced by Lanzhou Petrochemical Xiangxin Company, added 8 grams of asparagus powder, dissolved 4 grams of citric acid and 5.5 grams of cerium nitrate and mixed with 3 mL of acetic acid and water to form a 160-180mL aqueous solution, poured into alumina powder, kneaded, extruded into a φ4.0 toothed spherical carrier, dried at 110°C, and then calcined at 1060°C for 4 hours to obtain the carrier of the present invention. The specific surface of the carrier is 70m 2 / g, the pore volume is 0.55mL / g, and the average pore radius is 12.0nm. Alumina is θ and α mixed crystal forms, and θ crystal form alumina accounts for more than 80%.

[0037] Catalyst preparation

[0038] Dissolve 5.0 g of palladium chloride to prepare 1000 mL of hydrochloric acid aqueous solution, and add 20 mL of 10% citric acid to prepare a p...

Embodiment 2

[0041] The carrier was prepared according to the method of Example 1, and lanthanum nitrate was added to replace cerium nitrate when the carrier was prepared, and the carrier was calcined at 1150°C for 4 hours. The specific surface area of ​​the carrier was 56m 2 / g, the pore volume is 0.51mL / g, and the average pore radius is 13.8nm. Alumina is θ and α mixed crystal forms, and θ crystal form alumina accounts for more than 80%.

[0042] Weigh 100g of the carrier, immerse it in 160mL of acidic aqueous solution containing magnesium nitrate and palladium chloride, take it out after about 40 minutes, dry it at 100-110°C for 5 hours, and bake it in a muffle furnace at 550°C for 3 hours. Catalyst B of the present invention was prepared. The weight percent content of the catalyst is 0.26% of Pd, 1.8% of La and 0.25% of Mg. Pd is distributed in the sub-outer layer of the catalyst as a shell layer, the thickness of the outermost carrier layer is 0.01 mm, and the thickness of the palla...

Embodiment 3

[0044] The carrier was prepared according to the method of Example 1, and magnesium nitrate was added during the preparation of the carrier, so that the final catalyst contained 0.50 (weight)% of Mg. The carrier is calcined at 1000°C for 4 hours, and the specific surface of the carrier is 79m 2 / g, the pore volume is 0.54mL / g, and the average pore radius is 11.8nm. Alumina is in θ and δ crystal forms, and θ crystal form alumina accounts for more than 80%.

[0045] Weigh 100g of the carrier, immerse it in 140mL of palladium chloride-containing acidic aqueous solution, take it out after about 30 minutes, dry it at 100-110°C for 5 hours, and bake it in a muffle furnace at 480°C for 3 hours. Catalyst C of the present invention was prepared. The weight percent content of the catalyst is 0.33% of Pd and 0.5% of Mg. Ce 1.0%. Pd is distributed in the sub-outer layer of the catalyst as a shell layer, the thickness of the outermost carrier layer is 0.05 mm, and the thickness of the ...

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Abstract

The invention provides an unsaturated hydrocarbon selective hydrogenation catalyst and a preparation method thereof. The catalyst uses alumina as a carrier and palladium as an active ingredient, and is characterized by comprising the following components by weight percentage: 0.1 to 1.0 percent of the palladium, 0.3 to 8.0 percent of a rare earth metal, 0.1 to 5.0 percent of alkaline-earth metal, and 0 to 3.0 percent of fluorine which can also be contained in the catalyst, based on the total weight of the catalyst. The catalyst carrier is theta or mix-crystal type Al2O3, and the priority is given to the theta crystal type. In the invention, the catalyst palladium is preferably distributed in a secondary outer layer of the catalyst. The catalyst has certain impurity resistance and coking resistance, is applicable to a section of selective hydrogenation process in full distillate cracked gasoline and unsaturated hydrocarbon selective hydrogenation process in other distillate oils.

Description

technical field [0001] The present invention is about a kind of selective hydrogenation catalyst and preparation method, more specifically about whole-run pyrolysis gasoline (C 5 ~C 9 Distillate) selective hydrogenation catalyst and preparation method. Background technique [0002] Full-run pyrolysis gasoline refers to the C by-product of ethylene cracking unit 5 ~C 9 Gasoline fraction, whose output accounts for about 50-80% of ethylene production. There are two processes for the one-stage hydrogenation of pyrolysis gasoline. One is to first cut the whole distillate gasoline into C 5 、C 9 distillate, for middle distillate C 6 ~C 8 carry out hydrogenation, and the other is directly to C without separation 5 ~C 9 Full-run pyrolysis gasoline is hydrogenated. At present, palladium catalysts are still used in most primary hydrogenation units of pyrolysis gasoline. [0003] The one-stage hydrogenation of pyrolysis gasoline generally adopts palladium catalyst with alumin...

Claims

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Application Information

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IPC IPC(8): B01J23/63B01J27/13C10G45/40
Inventor 吴美岩李赫龚光碧颉伟辛国萍韩伟张峰杨珊珊曹凤霞张翠兰
Owner PETROCHINA CO LTD
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