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Alumina-zirconia composite carrier and preparation method thereof

A technology of composite carrier and zirconia, which is applied in the direction of catalyst carrier, chemical instrument and method, metal/metal oxide/metal hydroxide catalyst, etc., can solve the problem of low dispersion of active component Pd, specific surface and pore size distribution It does not meet the requirements of the catalyst, and the surface acidity of the catalyst is high, so as to improve the ability of anti-heavy metal poisoning, the surface acidity is low, and the effect of avoiding the reduction of activity is achieved.

Active Publication Date: 2011-11-23
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0009] In the prior art, the carrier with bimodal pore size distribution is used to prepare carbon dioxide pre-hydrogenation catalysts, and there are defects that the specific surface and pore size distribution do not meet the requirements of the catalyst, resulting in a low dispersion of the active component Pd of the catalyst, or a high acidity on the surface of the catalyst Shortcomings

Method used

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  • Alumina-zirconia composite carrier and preparation method thereof
  • Alumina-zirconia composite carrier and preparation method thereof
  • Alumina-zirconia composite carrier and preparation method thereof

Examples

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Effect test

Embodiment 1

[0035] Under stirring, containing 1286g NaAlO 2 solution and containing 378g of ZrCl 4 The solution was mixed at 50°C, then neutralized with NaOH solution, aluminum-zirconium hydroxide co-precipitated, stirred for 10 hours to make the aluminum-zirconium hydroxide form uniform fine particles, filtered and washed with distilled water to remove Na + and Cl - ions, adding 6.56% citric acid as a pore-expanding agent, kneading and extruding to form a Φ4mm strip, drying at 120°C for 4 hours and then roasting at 1250°C for 5 hours to obtain a composite carrier of alumina and zirconia, in which α-Al 2 o 3 and ZrO 2 The weight ratio is 8:2, the bulk density is 0.9g / ml, the pore volume is 0.608ml / g, and the specific surface area is 16.6m 2 / g, the carrier has a bimodal distribution at 105nm and 375nm, with an average pore size of 210nm. The carrier pore size distribution is as follows: 0% for 1-10nm; 67.60% for 10-100nm; 32.27% for 100-1000nm; 0.13% for 1000-10000nm.

[0036] Take ...

Embodiment 2

[0038] 700g of alumina, 150g of zirconia, 20g of citric acid and 30g of carbon black were stirred in a mechanical stirrer, extruded into strips of Φ4.2mm, dried at 110°C for 5 hours, and then calcined at 1300°C for 4 hours to obtain Alumina and zirconia mixed carrier, pore volume 0.46ml / g, bulk density 0.88g / ml, specific surface area 9.8m 2 / g (mercury intrusion method); the carrier has a bimodal distribution at 118nm and 472nm, and the average pore size is 314nm; the carrier pore size distribution is as follows: 1~10nm is 0%; 10~100nm is 42.32%; 100~1000nm is 57.50%; 1000 ~10000nm is 0.18%.

[0039] Take 10ml of palladium nitrate solution with a palladium ion concentration of 0.035g / ml and 990ml of water, mix thoroughly, impregnate 1000g of carrier, dry at 150°C for 4 hours, and roast at 450°C for 5 hours to obtain an impregnated catalyst. Take 10ml of silver nitrate solution containing 0.07g / ml of silver ions, add 990ml of water, mix thoroughly, impregnate and impregnate th...

Embodiment 3

[0046] Under stirring, containing 402g NaAlO 2 solution and containing 946g of ZrCl 4 The solution was mixed at 50°C, then neutralized with KOH solution, aluminum-zirconium hydroxide co-precipitated, stirred for 10 hours to make the aluminum-zirconium hydroxide form uniform fine particles, and the product was filtered and washed with deionized distilled water to remove Na + and Cl - ions, adding 15% polyvinyl alcohol as a pore-expanding agent, rolling balls after kneading, drying at 130°C for 2 hours and then calcining at 1350°C for 6 hours to obtain a composite carrier of alumina and zirconia, in which α-Al 2 o 3 and ZrO 2 The weight ratio is 5:5, the bulk density is 0.87g / ml, the pore volume is 0.508ml / g, and the specific surface area is 8.6m 2 / g, the carrier has a bimodal distribution at 135nm and 385nm, with an average pore size of 240nm. The carrier pore size distribution is as follows: 0% for 1-10nm; 27.50% for 10-100nm; 72.25% for 100-1000nm; 0.25% for 1000-10000n...

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Abstract

The invention relates to an alumina-zirconia composite carrier and a preparation method thereof. The carrier comprises the following components in percentage by mass: 1 to 95 percent of alumina and 5 to 99 percent of zirconia; the carrier has the following physical properties that: the bulk density is 0.8 to 1.1g / ml, the pore volume is 0.3 to 0.6ml / g, the specific surface area is 5 to 60m<2> / g, and the average pore size is 80 to 350nm, 100 to 250nm preferably; and the carrier has two peaks when the pore size is 90 to 140nm and 250 to 500nm. The invention also discloses the preparation method of the carrier, and a carrier-containing hydrogenation catalyst.

Description

technical field [0001] The invention relates to a carrier and a preparation method thereof, in particular to an alumina-zirconia composite carrier and a preparation method thereof. Background technique [0002] The pyrolysis gas produced in the steam cracking process of petroleum hydrocarbons often contains a small amount of impurities such as acetylene, propyne and propadiene, and their existence will affect the high-efficiency polyethylene and polyethylene used in the homogeneous polymerization and copolymerization processes in the subsequent sections to varying degrees. Propylene catalyst. According to the requirements of polyethylene, ethylene propylene rubber, polypropylene and other post-processing procedures, the mole fraction of acetylene in polymer grade ethylene must be lower than 5ppm, and the mole fraction of acetylene in ethylene must be lower than 1ppm in the production of ethylene glycol. Catalytic selective hydrogenation is the most widely used and most effe...

Claims

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Application Information

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IPC IPC(8): B01J32/00B01J35/10B01J23/50C07C11/04C07C11/06C07C7/167
CPCY02P20/52
Inventor 车春霞谭都平黄德华梁琨梁玉龙颉伟常晓昕景喜林高源李晓银林宏赵育榕
Owner PETROCHINA CO LTD
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