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Alumina-zirconia-titania composite carrier and its preparation method

A composite carrier, zirconia technology, applied in catalyst carriers, chemical instruments and methods, hydrocarbons, etc., can solve the problem of low dispersion of catalyst active component Pd, high catalyst surface acidity, specific surface and pore size distribution unsuitable for catalysts requirements, etc., to achieve the effect of improving the ability to resist heavy metal poisoning, low surface acidity, and avoiding the reduction of activity

Active Publication Date: 2014-12-24
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-titania composite carrier and its preparation method
  • Alumina-zirconia-titania composite carrier and its preparation method
  • Alumina-zirconia-titania composite carrier and its preparation method

Examples

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Effect test

Embodiment 1

[0036] Under stirring, containing 1286g NaAlO 2 solution and containing 378g of ZrCl 4 , 475g of TiCl 4 The solution was mixed at 50°C, then neutralized with NaOH solution, aluminum zirconium titanium hydroxide co-precipitated, stirred for 10 hours to make the aluminum zirconium titanium hydroxide form uniform fine particles, filtered and washed with distilled water to remove Na + and Cl - ions, adding 7.65% citric acid as a pore-expanding agent, kneading and extruding to make a Φ4mm strip, drying at 120°C for 4 hours and then roasting at 1200°C for 5 hours to obtain an alumina-zirconia-titania composite carrier, where α -Al 2 o 3 and TiO 2 , ZrO 2 The weight ratio is 8:1:1, the bulk density is 0.88g / ml, the pore volume is 0.497ml / g, and the specific surface area is 17.1m 2 / g, the carrier has a bimodal distribution at 60nm and 220nm, and the average pore size is 90nm. The carrier pore size distribution is as follows: less than 10nm is 0%; 10-100nm is 74.30%; greater t...

Embodiment 2

[0039] 700g of alumina, 150g of zirconia, 150g of titanium oxide, 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 1250°C After 4 hours, the alumina-zirconia-zirconia-titania mixed carrier was obtained, with a pore volume of 0.421ml / g, a bulk density of 0.92g / ml, and a specific surface area of ​​12.4m 2 / g (mercury intrusion method); the carrier has a bimodal distribution at 95nm and 310nm, and the average pore size is 150nm; the carrier pore size distribution is as follows: 1% for less than 10nm; 71.16% for 10-100nm; 27.66% for greater than 100nm and less than or equal to 1000nm ; greater than 1000nm is 0.18%.

[0040] Take 10ml palladium ions containing palladium nitrate solution with a concentration of 0.04g / ml and 990ml water, mix well, impregnate 1000g carrier, dry at 150°C for 4 hours, and roast at 450°C for 5 hours to obtain an impregnated catalyst. Take 10m...

Embodiment 3

[0047] Under stirring, containing 402g NaAlO 2 solution and containing 473g of ZrCl 4 , 594g of TiCl 4 The solution was mixed at 50°C, then neutralized with KOH solution, aluminum-zirconium-titanium hydroxide co-precipitated, stirred for 10 hours to make the aluminum-zirconium-titanium 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 the ball after kneading, drying at 130°C for 2 hours, and then calcining at 1350°C for 6 hours to obtain an alumina-zirconia-titania composite carrier, in which α-Al 2 o 3 and TiO 2 , ZrO 2 The weight ratio is 2:1:1, the bulk density is 1.04g / ml, the pore volume is 0.337ml / g, and the specific surface area is 6.8m 2 / g, the carrier has a bimodal distribution at 105nm and 355nm, and the average pore size is 190nm. The carrier pore size distribution is as follows: less than 10nm is 0%; 10-10...

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Abstract

The invention discloses an alumina-zirconia-titania composite carrier and its preparation method. 100% by mass of the alumina-zirconia-titania composite carrier comprises 1-95% by mass of alumina, 5-60% by mass of zirconia and 5-60% by mass of titania, the physical properties of the alumina-zirconia-titania composite carrier comprise a bulk density of 0.7-1.1g / ml, a pore volume of 0.2-0.6ml / g, a specific surface area of 3-60m<2> / g and an average aperture of 50-300nm, and two peaks of the alumina-zirconia-titania composite carrier appear at 40-120nm and 200-400nm respectively. The invention also discloses the preparation method of the alumina-zirconia-titania composite carrier, and a hydrogenation catalyst containing the alumina-zirconia-titania composite carrier.

Description

technical field [0001] The invention relates to a carrier and a preparation method thereof, in particular to an alumina-zirconia-titania 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 m...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J32/00B01J21/06B01J35/10B01J23/50B01J23/89C07C11/04C07C11/06C07C7/167C07C7/163
CPCY02P20/52
Inventor 车春霞谭都平张峰梁玉龙梁琨王书峰高源韩伟李赫景喜林常晓昕颉伟黄德华林宏
Owner PETROCHINA CO LTD
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