Heavy oil hydrogenating and modifying method

A heavy oil hydrogenation and heavy oil technology, which is applied in the fields of hydrotreating process, petroleum industry, and hydrocarbon oil treatment, can solve the problems of low catalyst concentration, expensive catalyst cost, and easy deactivation of catalyst, so as to promote hydrocracking reaction, Promotes fast mixing and uniformity, increasing the effect of storage

Active Publication Date: 2014-05-14
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] In the prior art, the use of high-concentration catalysts is expensive, and because the existing catalysts are easily deactivated, even if the concentration is increased, the improvement of the overall catalytic effect is limited. Therefore, in the prior art, whether it is a solid powder catalyst It is still a homogeneous catalyst, and the concentration of the catalyst in the hydrogenation reactor is relatively low, generally 200-3000μg / g

Method used

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  • Heavy oil hydrogenating and modifying method
  • Heavy oil hydrogenating and modifying method

Examples

Experimental program
Comparison scheme
Effect test

preparation example 1

[0040] 5.7g ammonium tungstate (H 18 N 2 o 9 W), 3.6g nickel carbonate (NiCO 3 ), 2.9g vanadyl sulfate (VOSO 4 ), 300mL of water, 5.4g of vulcanizing agent (sublimed sulfur) and 90g of carbon black were sequentially added into a 500mL autoclave, and vulcanized at 320°C, 6.0MPa (hydrogen initial pressure), and high-speed stirring (500rpm) for 120min. Catalyst A was obtained after filtration and vacuum drying. The elemental composition of catalyst A is listed in Table 1.

[0041] Observed under an electron microscope, the average particle diameter of the catalyst A is 100 μm, and the average particle diameter of the metal element sulfide is 30 nm.

preparation example 2

[0043] 30.4g tungsten naphthenate (W content is 8.78% by weight), 30.4g nickel tetracarbonyl (Ni content is 33.73% by weight), 6.5g vanadium hexacarbonyl (V content is 23.29% by weight), 4.5g vulcanizing agent (sublimation sulfur), 200mL solvent oil (hydrogenated diesel oil) and 60g heavy oil asphaltene (Qingchuan 3# natural asphalt, C content 88.9 wt%, H content 7.2 wt%, S content 5.8 wt%, N content 1.1 wt%) in order Put it into a 500mL autoclave, and vulcanize for 210min under the conditions of 350°C, 8.0MPa (hydrogen initial pressure), and high-speed stirring (500rpm). The product is centrifuged, extracted with toluene, and vacuum-dried to obtain catalyst B. in Table 1.

[0044] Observed under the electron microscope, the average particle diameter of the catalyst B is 1 μm, and the average particle diameter of the metal element sulfide is 12 nm.

preparation example 3

[0046] Preparation of Fe-based catalysts conventionally used in heavy oil hydro-upgrading process.

[0047] Add 100g of diesel oil, 50g of iron naphthenate (Fe content is 12% by weight), and 8.2g of sulfur into a 500mL autoclave in sequence, and vulcanize for 60min under the conditions of 350°C, 8.0MPa (hydrogen initial pressure), and 500rpm stirring speed , the product was filtered and vacuum-dried to obtain catalyst C, the active component of the catalyst was Fe-containing sulfide, and the elemental composition of the catalyst was listed in Table 1.

[0048] The element composition of the catalyst that each preparation example of table 1 makes

[0049]

Catalyst preparation example 1

Catalyst preparation example 2

Catalyst preparation example 3

Element content / %

Catalyst A

Catalyst B

Catalyst C

Fe

-

-

20.5

W

2.8

3.2

0

Ni

1.8

2.4

0

V

0.9

1.8...

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Abstract

The invention relates to a heavy oil hydrogenating and modifying method, which is characterized in that a heavy oil raw material, heavy cycle oil and a catalyst are uniformly mixed in a premixing device, and are introduced with hydrogen in a liquid phase fluid bed reactor, a hydrotreatment reaction is carried out under the heavy oil hydrotreatment condition, the hydrogenation products is fractionated to light distillate oil and heavy distillate oil in a distillation column, the light distillate oil leads out the apparatus, the heavy distillate oil is circulated to the premixing device and is mixed with the heavy oil raw material; by taking total weight of the catalyst as a reference, the catalyst comprises 2-18wt% of metallic element and 82-98wt% of non metallic element, wherein, by taking the weight of the metallic element as a reference, more than 95wt% of metallic element is V, Ni and VI B family metallic element; by taking the weight of the non metallic element as the reference, more than 95% of non metallic element is C and S, and at least a part of S and the metallic element are existed with a sulfide form of the metallic element. The heavy oil hydrogenating and modifying method is suitable for hydrogenation and conversion of the heavy oil, and is especially suitable for hydrotreatment of inferior heavy oil with high metal, high charcoal residue and high condensed ring substance.

Description

technical field [0001] The invention relates to a method for hydrogenation upgrading of heavy oil, especially inferior heavy oil. Background technique [0002] With the continuous increase of crude oil production, the increasing market demand for light fuel oil and the increasing environmental protection requirements, refineries are paying more and more attention to the technology of residual oil lightening, among which heavy / residual oil slurry bed hydrogenation Upgrading is one of the important ways to lighten heavy / residual oil, so major oil companies are competing to research and develop heavy / residual oil slurry bed hydrogenation technology. [0003] The slurry bed hydrogenation process uses a fine powder or liquid homogeneous catalyst (or additive) mixed with raw oil and then enters the reactor together with hydrogen in an upflow form to complete the hydrothermal cracking reaction. The difference lies in the used Catalysts are different. The early slurry bed hydrogen...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G67/02
Inventor 龙军侯焕娣董明王子军
Owner CHINA PETROLEUM & CHEM CORP
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