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
4 Cites 46 Cited by

AI-Extracted Technical Summary

Problems solved by technology

The anti-impurity performance of the palladium...
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Method used

As can be seen from table 2, table 3 test result, add rare earth oxide and alkaline earth metal oxide and fluoride etc. in catalyst ...
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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.

Application Domain

Metal/metal-oxides/metal-hydroxide catalystsRefining by selective hydrogenation

Technology Topic

Image

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

Examples

  • Experimental program(8)
  • Comparison scheme(5)

Example Embodiment

[0034] Example 1:
[0035] Carrier preparation
[0036] The carrier was prepared by the well-known conventional extrusion molding method, weighed 200 grams of alumina dry rubber powder produced by Lanzhou Petrochemical Xiangxin Company, added 8 grams of sesame powder, 4 grams of citric acid, 5.5 grams of cerium nitrate were dissolved and mixed with 3 mL of acetic acid , Water is mixed into 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 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 a mixed crystalline form of θ and α, and θ crystal type alumina accounts for more than 80%.
[0037] Catalyst preparation
[0038] Dissolve 5.0 grams of palladium chloride to prepare 1000 mL of hydrochloric acid aqueous solution, and add 20 mL of 10% citric acid to prepare palladium chloride impregnation solution.
[0039] Weigh 100 g of the aforementioned carrier, immerse it in 160 mL of an aqueous solution containing magnesium nitrate, immerse for 30 minutes, dry at 100-110°C for 3 hours, and fire in a muffle furnace at 500°C for 3 hours. The Mg-containing carrier is immersed in a palladium chloride solution containing 0.3 g of Pd, shaken and heated uniformly, drained after about 15 minutes, dried at 100-110°C for 5 hours, and calcined in a muffle furnace at 500°C for 3 hours. The catalyst A of the present invention was prepared. The weight percentage of the catalyst is 0.30% Pd, 1.2% Ce, and 0.35% Mg. Pd is distributed on the secondary outer layer of the catalyst as a shell layer, the outermost carrier layer has a thickness of 0.03 mm, and the palladium layer has a thickness of 0.23 mm.

Example Embodiment

[0040] Example 2
[0041] The carrier was prepared according to the method of Example 1, and lanthanum nitrate was added to replace the cerium nitrate when the carrier was prepared. The carrier was calcined at 1150°C for 4 hours, and the carrier had a specific surface area of ​​56 m 2 /g, the pore volume is 0.51mL/g, and the average pore radius is 13.8nm. Alumina is a mixed crystalline form of θ and α, and θ crystal type alumina accounts for more than 80%.
[0042] Weigh 100 g of the carrier, immerse it in 160 mL of an 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 roast it in a muffle furnace at 550°C for 3 hours. The catalyst B of the present invention was prepared. The catalyst weight percentage content is 0.26% of Pd, 1.8% of La, and 0.25% of Mg. Pd is distributed on the secondary outer layer of the catalyst as a shell layer, the outermost carrier layer has a thickness of 0.01 mm, and the palladium layer has a thickness of 0.30 mm.

Example Embodiment

[0043] Example 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, the specific surface area of ​​the carrier is 79m 2 /g, the pore volume is 0.54mL/g, and the average pore radius is 11.8nm. Alumina is theta and delta crystal type, and theta crystal type alumina accounts for more than 80%.
[0045] Weigh 100 g of the carrier, immerse it in 140 mL of an acidic aqueous solution containing palladium chloride, take it out after about 30 minutes, dry it at 100-110°C for 5 hours, and roast it in a muffle furnace at 480°C for 3 hours. The catalyst C of the present invention was prepared. The weight percentage of the catalyst is 0.33% Pd and 0.5% Mg. Ce 1.0%. Pd is distributed on the secondary outer layer of the catalyst as a shell layer, the outermost carrier layer has a thickness of 0.05 mm, and the palladium layer has a thickness of 0.23 mm.
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PUM

PropertyMeasurementUnit
Specific surface70.0m
Average hole radius12.0nm
Pore volume0.51ml/g
tensileMPa
Particle sizePa
strength10

Description & Claims & Application Information

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