Graded composition of heavy oil hydrogenation catalysts

A gradation combination, heavy oil hydrogenation technology, applied in refining to remove heteroatoms, etc., can solve the problem of low catalyst efficiency, and achieve the effect of high denitrification activity and stability, long service life, and slowing down the deactivation speed.

Active Publication Date: 2010-12-29
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In general, the main disadvantage of the existing technology is the low efficiency of the different types of catalysts in the graded system

Method used

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  • Graded composition of heavy oil hydrogenation catalysts
  • Graded composition of heavy oil hydrogenation catalysts
  • Graded composition of heavy oil hydrogenation catalysts

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] This example shows the preparation process of a graded combination of catalysts.

[0025] The preparation method of demetallization catalyst is as follows:

[0026] Take Al 2 o 3 As a carrier, a catalyst whose active metal components are Mo, Co, and Ni is prepared according to the step-by-step, multiple-impregnation method provided by European Patent No. 0204314. Take 500g Al 2 o 3 The carrier is immersed in 750mL Co-Ni hydrochloric acid solution with Co and Ni contents of 4.0m% and 3.0m% respectively at room temperature for 4 hours, and then soaked in deionized water for 30 minutes after taking it out. Then dry at 120°C for 3h, and then bake in air at 500°C for 2h after drying. The prepared catalyst was then immersed in an ammonia solution of ammonium molybdate (Mo content: 8.0 m%) containing 5 g of ammonium fluoride for 1 h. After taking it out, wash it with deionized water. Dry at 120°C for 3h. After drying, it was calcined in air at 500°C for 2 hours to obta...

Embodiment 2

[0033] This example shows the preparation process of a graded combination of catalysts.

[0034] The catalyst gradation assembly scheme is adopted, and several catalysts are loaded in the reactor, and the bed is filled with hydrodemetallization agent, hydrodesulfurization agent and hydrodenitrogenation agent respectively from top to bottom, and the addition ratios are 45% and 20% respectively. , 35%.

[0035] Al 2 o 3 As a carrier, according to the method provided by CN 1102448C, a catalyst whose active metal components are Mo and Ni is prepared by the method of unsaturated spray immersion, low temperature drying and then air drying.

[0036] Weigh Al with a water absorption rate of 1.10mL / g 2 o 3 Carrier 150g, according to the volume ratio of the amount of immersion liquid and the amount of saturated absorption solution is 0.80, spray immersion containing 18.6g ammonium molybdate (containing MoO 3 82m%), 17.10g nickel nitrate (containing NiO 25.2m%) and 8g 85% phosphori...

Embodiment 3

[0042] This example shows the preparation process of a graded combination of catalysts.

[0043] Using the catalyst gradation assembly scheme, several catalysts are loaded in the reactor, and the bed is filled with hydrodemetallization agent, hydrodesulfurization agent and hydrodenitrogenation agent respectively from top to bottom, and the addition ratios are 35% and 20% respectively. , 45%.

[0044] The preparation of demetallization catalyst and hydrodesulfurization catalyst is the same as in Example 1.

[0045] The preparation method of denitrification catalyst is as follows:

[0046] With 2.0m% ZrO 2 Al 2 o 3 As a carrier, the water absorption rate is 1.10mL / g. Catalysts with active metal components of Mo and Ni were prepared by soaking method.

[0047] Weigh 150g of the carrier, pretreat it with water steam for 1h, and take out a solution containing 11.9g of ammonium molybdate (containing MoO 3 82m%), 10.5g nickel nitrate (containing NiO 25.2m%) and 2g 85% phospho...

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Abstract

The invention relates to a graded composition of heavy oil hydrogenation catalysts. 5 to 55 percent of hydrodemetallization catalyst, 5 to 55 percent of hydrodesulfurization catalyst and 5 to 55 percent of hydrodenitrogenation catalyst are filled into a reactor from the top to the bottom respectively; along the flow direction, the activity of the catalysts is gradually increased, the aperture is gradually reduced, the granularity is gradually reduced and the porosity is gradually reduced; the active metal ingredients and the acid aid concentrations of the demetallization catalyst and the desulfurization catalyst are in non-uniform distribution, the active metal ingredient and the acid aid concentration of the demetallization catalyst are in gradient reduction, and the active metal ingredient and the acid aid concentration of the denitrogenation catalyst are in gradient increment; the active metal ingredient and the acid aid concentration of the desulfurization catalyst are in uniform distribution; the demetallization catalyst, the desulfurization catalyst and the denitrogenation catalyst consist of one or more catalysts respectively; and the demetallization, carbon residue removal, desulfurization and denitrogenation activities and stability of the catalyst graded composition system are high, and the service life is long.

Description

technical field [0001] The invention relates to a graded combination of heavy oil hydrogenation catalysts, which is suitable for hydrofinishing and hydrotreating of heavy oil and residual oil. Background technique [0002] In the process of hydrotreating heavy distillate oil or residual oil, due to the high content of impurities in raw materials, especially the organic metal compounds such as oil-soluble nickel and vanadium, they have a strong poisoning effect on hydrodesulfurization and denitrogenation catalysts. The prior art proposes various methods to remove such impurities from the feed to protect the downstream highly active hydrodesulfurization and denitrogenation catalysts. For example, US Patent No. 4,447,314 proposes a process for hydrotreating residual oil with a dual-catalyst bed system. The first catalyst used in the process is a macroporous catalyst, and the second catalyst is a small-pore catalyst. During the hydrogenation process of residual oil, the raw oil...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G45/04C10G45/08
Inventor 赵愉生赵元生谭青峰崔瑞利程涛张上
Owner PETROCHINA CO LTD
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