Method for grading catalysts for hydrofining of inferior distillate oil

A hydrofining preparation and hydrofining technology, which is applied in the field of oil refining, can solve the problems of affecting the desulfurization and denitrification effect of the lower catalyst, the decline of catalyst activity, and the shortening of the operation cycle, and achieve high ring-opening and fracture efficiency, moderate surface acidity, and mechanical strong effect

Active Publication Date: 2015-02-11
CNOOC TIANJIN CHEM RES & DESIGN INST +1
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Problems solved by technology

This method can produce clean diesel oil with sulfur content meeting the Euro IV standard, but the reaction temperature is high, the device consumes a lot of energy, and for the high-nitrogen naphthenic low-quality distillate oil provided by the CNOOC refinery, the cobalt-molybdenum in the upper layer The desulfurization performance of the type hydrotreating catalyst will be inhibited, the catalyst activity will decrease, and the operation cycle will be shortened, which will affect the desulfurization and denitrification effect of the lower catalyst, resulting in a decrease in the overall catalyst activity

Method used

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  • Method for grading catalysts for hydrofining of inferior distillate oil
  • Method for grading catalysts for hydrofining of inferior distillate oil
  • Method for grading catalysts for hydrofining of inferior distillate oil

Examples

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preparation example Construction

[0021] Preparation of hydrogenation protecting agent:

[0022] Mix 250g of a macroporous aluminum hydroxide dry rubber powder with 6g of scallop powder, 9g of 66% concentrated nitric acid and 10g of oxalic acid, add deionized water, knead and mix in a kneader, and then extrude into strips through an extruder , to obtain clover strips with a diameter of 3 mm. After drying in an oven at 120°C for 12 hours and calcining in a muffle furnace at 500°C for 4 hours, the carrier ZT-0 was obtained, and its properties are shown in Table 1.

[0023] Take 60mL of ammonia water, add 30g of ammonium metatungstate and 3.5g of basic nickel carbonate, heat and stir, and after it is completely dissolved, set the volume to 100mL to obtain a metal co-immersion solution, and put it aside for later use. Take 120 g of the carrier strips prepared in the previous step in the dipping tank, add the above-mentioned co-impregnation solution, and uniformly soak for 3 hours, then dry the wet strips in an ov...

Embodiment 1

[0034] The reaction is carried out in a 200mL hydrogenation reactor, and the hydrogenation protection agent, hydrofinishing preparation A, and hydrofinishing preparation B are filled sequentially along the flow direction. Fill 40mL, fill 60mL of hydrofinishing preparation B, and fill the rest with inert ceramic balls.

[0035] The raw material oil A used in this evaluation reaction is a low-quality distillate oil provided by a refinery of CNOOC. The raw material oil is a high-sulfur and high-nitrogen naphthenic oil. 12% of coked gasoline and 31% of coked diesel are mixed, and their properties are shown in Table 3. The operating conditions used to evaluate the reaction 1: pressure 8.0MPa, reaction temperature 340 ℃, hydrogen oil volume ratio 600:1, volume space velocity 1.0h -1 .

[0036] The product properties are shown in Table 3. It can be seen from Table 3 that after the hydrorefining reaction of raw material oil A under this process condition, the sulfur content of the ...

Embodiment 2

[0038] The reaction is carried out in a 200mL hydrogenation reactor, and the hydrogenation protection agent, hydrofinishing preparation A, and hydrofinishing preparation B are filled sequentially along the flow direction. Fill 50mL, fill 50mL of hydrofinishing preparation B, and fill the rest with inert ceramic balls.

[0039] Raw material oil A was used as raw material for this evaluation reaction. The operating conditions used in the evaluation reaction 2: pressure 6.5MPa, reaction temperature 340°C, hydrogen-oil volume ratio 400:1, volume space velocity 1.5h -1 .

[0040] The product properties are shown in Table 4. It can be seen from Table 4 that after the hydrorefining reaction of raw material oil A under this process condition, the sulfur content of the separated product diesel oil is 48.2 μg / g (less than 50 μg / g), and the nitrogen content is 79.5 μg / g, which can be seen in this patent The provided catalyst graded packing system achieves the purpose of ultra-deep des...

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Abstract

The invention relates to a method for grading catalysts for hydrofining of inferior distillate oil. A hydrogenation reactor is divided into three sections of reaction regions sequentially from top to bottom, wherein a hydrogenating protective agent is filled in the first section of reaction region; a hydrofining agent A is filled in the second section of reaction region and is characterized in that the catalyst adopts Al2O3-TiO2-SiO2-ZrO2 quaternary composite oxide as a carrier, W-Mo-Ni ternary metal as an active metal component and P as an aid; and a hydrofining agent B is filled in the third section of reaction and is characterized in that the catalyst adopts Al2O3-SiO2-ZrO2 ternary composite oxide as a carrier, W-Mo-Ni ternary metal as an active metal component and P and F as aids. The method is used for grading different systems of catalysts reasonably, wherein due to combination of the hydrofining agent A with large pore volume, large specific surface area and high surface acid quantity and the ternary metal component with high activity, certain desulfuration and deep denitrogenation effects are achieved, and the influence of azacyclo compounds on the desulfurization activity of the catalyst in the next step is reduced; and due to the hydrofining agent B and the deep desulfurization performance of the catalyst, ultralow sulfur diesel oil with the sulfur content meeting the European IV standard is obtained finally.

Description

technical field [0001] The invention belongs to the field of oil refining, and in particular relates to a method for grading catalysts for hydrorefining of inferior distillate oil. Background technique [0002] At present, the heavy and inferior quality of crude oil is becoming more and more serious. The output of sour crude oil (0.5%-2.0% sulfur content) and high sulfur crude oil (more than 2.0% sulfur content) in the world has accounted for more than 75% of the world's total crude oil output. Among them, crude oil with a sulfur content of more than 1% exceeds 55% of the world's total crude oil production, and crude oil with a sulfur content of more than 2% also accounts for more than 30%. The standards for tail gas discharged into the atmosphere are becoming more and more stringent, and the requirements for the quality standards of petroleum products are also getting higher and higher, that is, the allowable sulfur content is getting lower and lower. On January 1, 2009, Eu...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C10G65/04
Inventor 刘红光杨建国张国辉石芳于海斌肖寒李佳
Owner CNOOC TIANJIN CHEM RES & DESIGN INST
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