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Hydrofining catalyst as well as preparation method and application thereof

A hydrofining and catalyst technology, applied in the direction of chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, heterogeneous catalyst chemical elements, etc., can solve the problem of low demetallization rate and achieve specific surface area Large, large pore volume, good activity and stability

Active Publication Date: 2019-02-05
NINGBO INST OF MATERIALS TECH & ENG CHINESE ACADEMY OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The patent with the publication number CN104368332A proposes to use halogen-containing bimodal porous alumina as the carrier, and the pore size of the catalyst is 5-20nm. The deasphaltene rate of the catalyst is 88%, but the demetallization rate is low, only 81%.

Method used

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  • Hydrofining catalyst as well as preparation method and application thereof
  • Hydrofining catalyst as well as preparation method and application thereof

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preparation example Construction

[0024] Preferably, the preparation method of the carrier includes: mixing alumina and modified graphene, adding an extrusion aid, extruding into a strip, and then drying and calcining.

[0025] Further, the temperature of the drying treatment is 80-160°C.

[0026] Further, the temperature of the calcination treatment is 400-700° C., and the calcination time is 1-15 hours.

[0027] Preferably, the amount of the modified graphene is 0.05-0.5 wt%, especially preferably 0.1-0.3 wt%, of the total mass of the carrier.

[0028] Preferably, the modified graphene is formed by modifying graphene by water vapor spraying.

[0029] In the catalyst of the present invention, before the graphene in the carrier is mixed with alumina, it is modified by water vapor spraying, and the temperature of the water vapor used in the water vapor spraying modification is 100-180° C., and the pressure is It is 0.10~0.25MPa, and the spraying time is 1~5min.

[0030] Further, the graphene adopts single-la...

Embodiment 1

[0060] (1) Preparation of catalyst carrier:

[0061] a1. Thickness 2.0nm, particle size 2.5μm, specific surface area 750m 2 / g of graphene powder 0.20g, spray modification with water vapor at 0.10MPa and 150°C for 5min to obtain bulky modified graphene;

[0062] b1. Mix macroporous alumina (commercially available common macroporous alumina powder with a pore volume of 0.8 to 1.2ml / g) and small pore alumina (commercially available with a pore volume of 0.3 to 0.6ml / g) Ordinary small-pore alumina powder) is mixed and stirred according to the mass ratio of 2:1 as alumina raw material;

[0063] c1. Take 99g of the alumina raw material mixed in step b1, then add the modified graphene in step a1, stir and mix thoroughly, then add extrusion aids, such as citric acid, in an amount that meets the requirements of carrier molding, then knead and roll Pressing and forming into strips;

[0064] d1. Dry the strip-shaped carrier extruded in step c1 at room temperature, then put it in an o...

Embodiment 2

[0072] (1) Preparation of catalyst carrier:

[0073] a1. The thickness is 2.5nm, the particle size is 1.8μm, and the specific surface area is 600m 2 0.25g of graphene powder per gram was sprayed and modified with water vapor at 0.18MPa and 100°C for 1min to obtain fluffy and flocculent modified graphene;

[0074] b1~d1 are the same as embodiment 1;

[0075] e1. Finally, place the dried strip in step d1 in a muffle furnace and calcinate at 400° C. for 15 hours to obtain a carrier.

[0076] (2) Preparation of catalyst:

[0077] a2, the preparation of metal active component and auxiliary agent impregnating solution is as above-mentioned, takes tungsten-cobalt-barium solution (WO 3 content of 22.0g / 100ml, CoO content of 14.0g / 100ml, BaO content of 9g / 100ml) 50ml, add lauryl alcohol polyether in an amount of 2% to 10% of the total mass of the carrier, and make an aqueous solution;

[0078] b2. Take 54g of the carrier prepared in step (1), add it to the prepared aqueous solution...

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Abstract

The invention discloses a hydrofining catalyst. The hydrofining catalyst comprises a metal active component, a carrier loaded with the metal active component and auxiliaries, wherein the carrier is mainly formed by mixing, extrusion-moulding, drying and roasting modified graphene and aluminium oxide; the metal active ingredient comprises metal oxides which comprise oxides of VIB-family and / or VIII-family metal elements; the auxiliaries comprise oxides of magnesium and / or barium; the average pore size of the catalyst is 30-80 nm, the specific surface area is 100-300 m<2> / g, and crushing strength is 300 N.cm<-1> or more. The invention further provides a preparation method for the catalyst and application thereof. Compared with a conventional hydrofining catalyst, the catalyst provided by theinvention has the advantages of high strength, intensive pore distribution, great pore volume and great specific surface area, is good in activity and stability, and is suitable for treating bad oilwith high asphalt content.

Description

technical field [0001] The invention relates to the field of preparation of hydrorefining catalysts, in particular to a hydrorefining catalyst for pretreatment of low-quality oil stocks and its preparation method and application. Background technique [0002] In recent years, my country's air quality has become worse and worse, and there is an urgent need for cleaner vehicle motors to transport fuel oil; Catalytic external oil slurry, catalytic heavy cycle oil, etc. These raw materials contain high content of residual carbon and asphaltenes. In addition, more coal-based oil fixed-bed hydrogenation units have been built in recent years, and there is an urgent need to process heavier and lower-quality feedstock oils. All of the above current situations require hydrotreating catalysts that can handle lower-quality raw materials. Converted into clean and environmentally friendly light fuel oil. Current fixed bed hydrotreating catalysts can only treat feedstocks with an asphalte...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/882B01J23/888B01J35/10C10G45/08
CPCC10G45/08B01J23/002B01J23/8872B01J23/888B01J2523/00C10G2300/70B01J35/651B01J35/647B01J35/615B01J2523/25B01J2523/69B01J2523/847B01J2523/845B01J2523/22B01J2523/68
Inventor 尹宏峰许杰
Owner NINGBO INST OF MATERIALS TECH & ENG CHINESE ACADEMY OF SCI
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