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Grading composition of hydrogenation catalyst

A hydrogenation catalyst and gradation combination technology, applied in refining to remove heteroatoms, etc., can solve the problems of large cold hydrogen demand, pore size limitation, poor hydrogenation saturation capacity of polycyclic aromatic hydrocarbons, etc., to extend the operation cycle and slow down Inactivation speed, effect of temperature rise control

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

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Problems solved by technology

Tests have proved that the disadvantage of this graded filling method is that the temperature rise of the desulfurization and denitrification catalyst bed is too large, the demand for cold hydrogen is large, and the processing capacity cannot be increased.
[0006] CN1054393C discloses a large-pore catalyst for hydrogenation of residual oil, which is more suitable for the hydrodemetallization process of residual oil. Its hydrogenation active component content is low, the hydrogenation saturation ability of polycyclic aromatic hydrocarbons is poor, the acidity is weak, and the hydrogenation conversion ability is not strong
[0007] CN 104213 SC discloses a catalyst for hydrogenation treatment of residual oil, which has relatively strong hydrogenation saturation and hydrogenation conversion capabilities of polycyclic aromatic hydrocarbons, but limited by its pore size, it cannot convert macromolecular components such as asphaltenes and heavy colloids Wait
[0008] In general, the main disadvantage of the existing technology is that the catalyst utilization rate in the grading system is not high, and the existing catalyst grading combination system needs to be further optimized

Method used

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  • Grading composition of hydrogenation catalyst
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  • Grading composition of hydrogenation catalyst

Examples

Experimental program
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Effect test

Embodiment 1

[0025] This example shows the preparation process of a catalyst gradation combination system. The catalyst gradation assembly scheme is adopted, the reactor is filled with catalyst, and the bed is filled with demetalizing agent and desulfurizing agent from top to top, and the adding ratios are 45% and 55%, respectively.

[0026] The preparation method of the metal removal catalyst is as follows:

[0027] Take Al 2 O 3 As a carrier, according to the stepwise and multiple impregnation method provided by European Patent 0204314, a catalyst with active metal components of Mo, Co and Ni is prepared. Take 500g Al 2 O 3 The carrier was immersed in 750 mL of Co-Ni hydrochloric acid solution with Co and Ni contents of 4.0% and 3.0% respectively at room temperature for 4 hours, and then immersed in deionized water for 30 minutes after being taken out. It was then dried at 120°C for 3 hours, and then calcined in air at 500°C for 2 hours. The prepared catalyst is then immersed in an aqueous ...

Embodiment 2

[0031] This example shows the preparation process of a catalyst gradation combination system. The catalyst gradation assembly scheme is adopted, the reactor is filled with catalyst, and the bed is filled with demetalizing agent and desulfurizing agent from top to top, and the addition ratios are 35% and 65%, respectively.

[0032] Demetallization catalyst with Al 2 O 3 As a carrier, according to the method provided by CN 1102448C, a catalyst with active metal components of Mo and Ni is prepared by the method of unsaturated spray immersion and low-temperature drying and air drying.

[0033] Weigh 150g of Al with a water absorption rate of 1.10mL / g 2 O 3 The carrier, according to the volume ratio of the immersion liquid volume to the saturated absorption solution volume, is 0.80, and spray dipping contains 18.6g ammonium molybdate (containing MoO 3 82m%), 17.10g nickel nitrate (containing 25.2m% NiO), 8g 85% phosphoric acid in 132mL. After homogenizing for 5 minutes in a spray dippi...

Embodiment 3

[0038] This example shows the preparation process of a catalyst gradation combination system. The catalyst gradation assembly scheme is adopted, the reactor is filled with catalyst, and the bed is filled with demetalizing agent and desulfurizing agent from top to top, and the addition ratios are 30% and 70%, respectively.

[0039] The demetalization catalyst is the same as in Example 1.

[0040] The preparation method of the desulfurization catalyst is as follows:

[0041] To contain 2.0m% ZrO 2 Al 2 O 3 As a carrier, a immersion method is used to prepare a catalyst with active metal components of Mo and Ni.

[0042] Weigh 150g water absorption rate 1.10mL / g containing 2.0m% ZrO 2 Al 2 O 3 The carrier, passed through water vapor for 1h, was taken out in 330mL containing 11.9g ammonium molybdate 3 82m%) and 10.5g nickel nitrate (containing 25.2m% NiO) and 2g 85% phosphoric acid in an aqueous solution soaked for 1 hour, then dried at 120°C for 3 hours, and then calcined in air at 500°C...

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Abstract

The invention relates to a grading composition of a hydrogenation catalyst. From top to bottom, a reactor is filled with hydrodemetallization and a hydrodesulfurization catalyst; raw materials flow from top to bottom, and along with the flowing direction of raw materials, the activity of the catalyst gradually increases, the pore size gradually decreases, the grain size gradually decreases and the porosity gradually decreases; the hydrodemetallization catalyst and the hydrodesulfurization catalyst are both formed by one or more demetallization catalysts; concentrations of active metal components and acid auxiliary agents are in nonuniform distribution, and from the surface to the center of catalyst grains, the concentrations of the active metal components and acid auxiliary agents of the hydrodemetallization catalyst are of gradient increase, and the concentrations of the active metal components and acid auxiliary agents of the hydrodesulfurization catalyst are of gradient decrease; and based on weight content, the demetallization catalyst accounts for 15 to 80 percent, and the desulfurization catalyst accounts for 20 to 85 percent. The grading composition of the invention is applied to hydrogenation catalysis of oil and residual oil of heavy ends and has the advantages of possessing better activity and stability of demetallization, residual carbon removal and desulfurization, controlling temperature rise of a catalyst bed and degreasing the deactivation speed of the catalyst.

Description

Technical field [0001] The invention relates to a gradation combination of a hydrogenation catalyst used for the hydrorefining and hydroprocessing of heavy distillate oil and residual oil. Background technique [0002] At present, the demand for light and medium-quality oil products in the domestic and foreign oil products market will continue to increase, while the demand for heavy oil products such as fuel oil will be on the decline. In addition, due to the increasing pressure of environmental protection, countries have generally increased the quality standards of petroleum products, especially gasoline and diesel products for automobiles. Under the above-mentioned market trend, the refining technology that can not only realize the light weight of heavy oil at a more economical and reasonable price, but also make the obtained products meet the increasingly demanding gasoline and diesel product specifications has become the key technology developed by domestic and foreign refini...

Claims

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Application Information

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IPC IPC(8): C10G45/04C10G45/08
Inventor 赵愉生赵元生张上崔瑞利程涛谭青峰
Owner PETROCHINA CO LTD
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