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Selective hydrogenation catalyst and preparation method thereof

A hydrogenation catalyst and selective technology, applied in chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, etc., can solve the problems of poor catalyst stability, increased operating costs, and specific surface area and low pore volume, to achieve large specific surface area and pore volume, high hydrogenation selectivity, and increase the specific surface area

Active Publication Date: 2014-01-01
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

CN85100761A discloses a fiber-supported catalyst for selective hydrogenation of diolefins in pyrolysis gasoline fractions, with a specific surface area of ​​20-200m 2 / g, η-Al with a pore volume of 0.1-0.3ml / g 2 o 3 Porous fibrous carrier, the initial activity of the catalyst is high, but the pore volume is too small. When the colloid in the raw material of the pyrolysis gasoline hydrogenation unit exceeds the standard, the upper pores of the catalyst are easy to coke and block, which affects the hydrogenation stability of the catalyst
This catalyst is more suitable for the whole fraction of pyrolysis gasoline, but for the heavier fraction, due to the relatively low specific surface area and pore volume, it affects the activity and selectivity of the catalyst, and the catalyst deactivates quickly, the stability of the catalyst is poor, and the cycle is short, which increases the Operating costs

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Prepare solid sodium aluminate to a concentration of 200gAl 2 o 3 / l concentrated sodium aluminate solution, then diluted to a concentration of 25gAl 2 o 3 / L and 35gAl 2 o 3 / L sodium aluminate working solution, take a 30L steel to make a plastic tank, first add 5L containing 25gAl 2 o 3 / L sodium aluminate working solution, while ventilating and feeding CO with a concentration of 45v% 2 gas, the reaction temperature is 25°C, the reaction time is 1 hour, when the pH value reaches 11.5, quickly adjust the CO 2 flow rate, add 8.3L containing 35gAl 2 o 3 / L sodium aluminate working solution, add 17g polyethylene glycol with a molecular weight of 20,000 at the same time, keep the pH of the system at about 10.0, the reaction temperature is 25°C, and the reaction time is 1 hour. After the reaction is completed, stop feeding CO 2 , and then ventilate and stabilize for 60 minutes, the slurry was filtered and washed with 60°C deionized water until neutral, and then dr...

Embodiment 2

[0041] Prepare solid sodium aluminate to a concentration of 200gAl 2 o 3 / l concentrated sodium aluminate solution, then diluted to a concentration of 25gAl 2 o 3 / L sodium aluminate working solution, take a 30L steel to make a plastic tank, first add 5L containing 25gAl 2 o 3 / L sodium aluminate working solution, while ventilating and feeding CO with a concentration of 40v% 2 gas, the reaction temperature is 25°C, the reaction time is 1.2 hours, when the pH value reaches 12.0, quickly adjust the CO 2 The flow rate, add 11L containing 25gAl 2 o 3 / L sodium aluminate working solution, add 21g polyethylene glycol with a molecular weight of 20,000 at the same time, keep the pH of the system at about 10.0, the reaction temperature is 25°C, and the reaction time is 0.8 hours. After the reaction is completed, stop feeding CO 2 , and then the ventilation was stable for 60 minutes, and the slurry was filtered and washed with deionized water at 60°C until neutral. Dry at 120°C...

Embodiment 3

[0043] Carrier A, catalyst intermediate TA and catalyst catA involved in the present invention. Take 85g of large-pore aluminum hydroxide Y-1, 66g of small-pore SB alumina and 4g of dilute nitric acid, mix and knead, and roll to make a paste that can be extruded, extruded, dried at 110°C for 2 hours, and roasted at 1000°C for 4 hours , to obtain carrier A.

[0044] Weigh 0.5g of palladium chloride powder with a palladium content of not less than 59wt%, add water, then add hydrochloric acid, dissolve and dilute to 80ml, and adjust the pH to 3.5; weigh 100g of carrier A, and prepare the prepared palladium chloride solution Spray and impregnate on the carrier A, dry in the air at 120°C, and bake at 500°C for 4 hours to obtain the catalyst intermediate TA.

[0045] Weigh 3.7 g of ammonium heptamolybdate, configure it into 80 ml of aqueous solution, spray and dip it onto the above-mentioned catalyst intermediate TA, dry it in the air at 120° C., and bake it at 500° C. for 4 hours....

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Abstract

The present invention discloses a selective hydrogenation catalyst and a preparation method thereof. According to the catalyst, macroporous alumina is adopted as a carrier, an active metal component is palladium, an additive component is Mo and / or Co, and the active metal component and the additive component are distributed on the carrier surface in an eggshell form. The macroporous alumina is prepared by a sodium aluminate and carbon dioxide precipitation method, wherein the single flow coprecipitation is performed under the conditions that the pH value of one part of the sodium aluminate is changed and the pH value of the other part of the sodium aluminate is maintained to the constant value, and a polymer surfactant is added. The resulting macroporous alumina by the method has large specific surface area and large pore volume, and the pore size distribution is centralized in the range of 10-20 nm so as to contribute to improvement of the hydrogenation activity and the selectivity of the catalyst. In addition, the interaction can be generated between the additive component and the active component palladium so as to contribute to the uniform distribution of the palladium particles, and enhance the interaction between the palladium and the carrier, such that the palladium loss is reduced, the palladium utilization rate is improved, and the service life of the catalyst is prolonged.

Description

technical field [0001] The invention relates to a selective hydrogenation catalyst and a preparation method thereof. The catalyst is suitable for selective hydrogenation of middle and low distillate oils, especially for pyrolysis gasoline C 9 Distillate stage selective hydrogenation process. Background technique [0002] Using light hydrocarbons, naphtha, diesel oil or heavy oil as raw materials, in the process of producing ethylene by high temperature cracking in the presence of water vapor, liquid by-products containing more than five hydrocarbons are produced, and the liquid with a dry point of 205°C is obtained by fractional distillation. For pyrolysis gasoline. Ethylene cracking C 9 Distillate, which is separated from pyrolysis gasoline by extraction and C 5 Fraction, C 6 ~C 8 The remaining fraction after fractionation accounts for about 10% to 20% of the total ethylene production. [0003] With the rapid development of the petrochemical industry, especially the s...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/652B01J23/89B01J35/04C10G45/08C10G45/10
Inventor 樊宏飞孙晓艳王占宇
Owner CHINA PETROLEUM & CHEM CORP