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: 2012-07-18
PETROCHINA CO LTD
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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

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

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] This example shows the preparation process of a catalyst graded combination system. The catalyst gradation assembly scheme is adopted, the catalyst is loaded in the reactor, and the demetallization agent and the desulfurization agent are respectively loaded on the bed layer from top to top, and the addition ratios are 45% and 55% respectively.

[0026] The preparation method of demetallization catalyst is as follows:

[0027] 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 3The 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 ...

Embodiment 2

[0031] This example shows the preparation process of a catalyst graded combination system. The catalyst gradation assembly scheme is adopted, the catalyst is loaded in the reactor, and the demetallization agent and the desulfurization agent are respectively loaded on the bed layer from top to top, and the addition ratios are 35% and 65% respectively.

[0032] 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.

[0033] Weigh 150g of Al with a water absorption rate of 1.10mL / g 2 o 3 Carrier, 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%) and 17.10g nickel nitrate (containing NiO 25.2m%), 8g 85% phosphoric acid aqueous solution 132mL. After homogenizin...

Embodiment 3

[0038] This example shows the preparation process of a catalyst graded combination system. The catalyst gradation assembly scheme is adopted, the catalyst is loaded in the reactor, and the demetallization agent and the desulfurization agent are respectively loaded on the bed layer from top to top, and the addition ratios are 30% and 70% respectively.

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

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

[0041] With 2.0m% ZrO 2 Al 2 o 3 As a carrier, the catalyst whose active metal components are Mo and Ni was prepared by soaking method.

[0042] Weigh 150g with a water absorption rate of 1.10mL / g containing 2.0m% ZrO 2 Al 2 o 3 Carrier, through water vapor 1h, take out in 330mL containing 11.9g ammonium molybdate (containing MoO 3 82m%) and 10.5g of nickel nitrate (containing NiO 25.2m%) and 2g of 85% phosphoric acid in an aqueous solution soaked for 1h, then dried at 120°C for 3...

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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 present invention relates to a graded combination of hydrogenation catalysts for hydrorefining and hydrotreating of heavy distillates and residual oils. Background technique [0002] At present, the demand for light and medium oil products in the domestic and foreign oil product markets will continue to rise, while the demand for heavy oil products such as fuel oil will show a downward trend. In addition, due to the increasing pressure of environmental protection, countries have generally raised the quality standard requirements of petroleum products, especially gasoline and diesel products for vehicles. Under the above-mentioned market trend, the refining technology that can not only realize the lightening of heavy oil at a more economical and reasonable price, but also make the obtained products meet the increasingly stringent specifications of gasoline and diesel products has become a key technology developed by domestic and foreign refining tec...

Claims

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Application Information

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Patent Type & Authority Patents(China)
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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