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Hydrorefining method of middle and low distillate oil

A technology for hydrorefining and distillate oil, which is applied in the petroleum industry, processing hydrocarbon oil, refining to remove heteroatoms, etc. The effect of good chemical stability and thermal stability, strong anti-coking performance

Active Publication Date: 2014-04-02
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] CN1267187C discloses a silica-alumina containing pseudo-boehmite structure, the carrier silica content is high, and the silicon-containing compound solution is directly or co-currently introduced into the pseudo-boehmite slurry, the purpose It is to increase the content of four-coordinated aluminum to increase the acid strength and acid amount of alumina. The prepared silicon-containing alumina has high cracking activity. However, the higher cracking activity is used as a hydrogenation catalyst carrier, which reduces the liquid yield.
However, the composite oxide prepared by this method has a large number of micropores, which is not suitable for being used as a carrier for hydrotreating catalysts of low and medium distillate oils.

Method used

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  • Hydrorefining method of middle and low distillate oil
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  • Hydrorefining method of middle and low distillate oil

Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0049] Embodiment uses the preparation of catalyst 1~7:

[0050] Preparation of Catalyst 1:

[0051] Configure 2L concentration of 120gAl 2 o 3 / L of sodium metaaluminate solution is placed in the glue tank, the temperature of the glue tank is controlled at 45°C, and 65v% CO is introduced under stirring conditions. 2 Mixed gas of +35v% air, the flow rate of carbon dioxide in the mixed gas is 3Nm 3 / h. When the pH value reaches 10.0, stop feeding the mixed gas, and then age for 20 minutes to obtain pseudo-boehmite slurry.

[0052] Configure 2L concentration of 120gAl 2 o 3 / L sodium metaaluminate solution is placed in the gel tank, and then add 2L 80gSiO 2 / L of sodium silicate solution, control the temperature of the glue tank at 30°C, and feed 60v% CO 2 Mixed gas of +40v% air, CO in the mixed gas 2 The flow rate is 3Nm 3 / h, the pH at the end point was controlled to be 10.0, and the amorphous silicon-aluminum slurry was obtained by aging for 15 minutes.

[0053] Un...

Embodiment 1

[0088] Put the fresh catalyst 1 into a 100ml adiabatic bed reaction device, and first carry out the sulfuration of the catalyst: add carbon disulfide to cyclohexane to make sulfurized oil with a sulfur content of about 1000μg / g, and the reactor is heated to 240°C to start adding sulfurized oil. Pressure 2.5Mpa, vulcanized oil volume space velocity 3.0h -1 , the hydrogen / sulfurized oil volume ratio is 300:1, and then the temperature is raised to 350°C at a heating rate of 10°C / h and maintained for 25h to complete the sulfurization treatment of the catalyst.

[0089] After the vulcanization treatment is completed, use the raw material oil 1 as the raw material, at the inlet temperature of 220°C, the reaction pressure of 2.4MPa, and the liquid volume space velocity: 4h -1 , and run for 200h under the condition of hydrogen to oil volume ratio of 300. The bromine value and sulfur content in the product were sampled and analyzed every 24h, and the results are shown in Table 3.

Embodiment 2

[0091] The fresh catalyst 2 was loaded into a 100ml adiabatic bed reactor, and the catalyst sulfidation treatment method was the same as in Example 1.

[0092] After the vulcanization treatment, use the raw material oil 2 as the raw material, at the inlet temperature of 240°C, the reaction pressure of 2.6MPa, the liquid volume space velocity: 4.5h -1 , the hydrogen to oil volume ratio of 350 operating conditions of 200h. The bromine value and sulfur content in the product were sampled and analyzed every 24h, and the results are shown in Table 3.

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Abstract

The invention provides a hydrorefining method of middle and low distillate oil. The hydrorefining method is characterized in that a used catalyst is a molybdenum nickel hydrogenation catalyst; hydrogenation process conditions are as follows: an inlet temperature is 200-300 DEG C, an operation pressure is larger than or equal to 2.4MPa, the volume space speed of a liquid is 1-5 h<-1>, and the volume ratio of hydrogen to oil is 100-500; in the molybdenum nickel catalyst, silicon-containing alumina is a carrier, molybdenum and nickel are active components, and phosphorus and alkali metals are auxiliaries; and the precursor of the silicon-containing alumina carrier is pseudoboehmite containing amorphous silicon and aluminum and is obtained by the steps of firstly preparing an amorphous silicon and aluminum slurry and a pseudoboehmite slurry, mixing the slurries and then ageing, and then carrying out post-treatment processes such as filtering, washing and drying. By using the method, hydrorefining is carried out on a first-section hydrogenation product of cracked gasoline containing middle and low distillates, wherein the bromine value of the hydrogenation product is less than 1.0*10<-2>g / g, and the sulfur content of the hydrogenation product is less than 1.0mu g / g, thereby meeting the second-section hydrogenation requirement of cracked gasoline.

Description

technical field [0001] The invention relates to a hydrofinishing method for middle and low distillate oil, which is especially suitable for the second stage hydrofinishing of middle and low distillate pyrolysis gasoline. Background technique [0002] Pyrolysis gasoline is a by-product in the ethylene production process, and its output is more than 50% to 80% of the ethylene production capacity, of which the aromatic content is as high as 50%, which is an important aromatic resource, which contains highly unsaturated hydrocarbons, such as: diolefins, Styrene, etc., are generally used as raw materials for aromatics extraction after two-stage hydrogenation. In recent years, the ethylene industry has achieved unprecedented development, and the production capacity of ethylene has been increasing year by year. The output of pyrolysis gasoline, which is an important by-product of ethylene, is bound to increase significantly. The hydrogenation technology with pyrolysis gasoline hyd...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C10G45/08C10G49/04B01J27/19
Inventor 郑云弟向永生康宏敏马好文颉伟王书峰王廷海吕龙刚李平智蒋彩兰孙利民王宗宝吴杰潘曦竹柏介军
Owner PETROCHINA CO LTD
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