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Full-cut fraction pyrolysis gasoline diolefin selective hydrogenation method

A pyrolysis gasoline and selective hydrogenation technology, which is applied in the field of selective hydrogenation treatment of low- and medium-distillate oils, can solve the problems of hydrogenation load and poor hydrogenation stability, and achieve good hydrogenation stability, strong resistance to impurities and The effect of anti-gelatin ability and excellent hydrogenation stability

Active Publication Date: 2010-04-21
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

CN1218822A has reported a kind of Ni / Al 2 o 3 A selective hydrogenation catalyst suitable for pyrolysis gasoline fractions. The catalyst is prepared by loading nickel on an alumina support containing lithium or alkaline earth metals. This catalyst is not good in hydrogenation load and hydrogenation stability.

Method used

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  • Full-cut fraction pyrolysis gasoline diolefin selective hydrogenation method
  • Full-cut fraction pyrolysis gasoline diolefin selective hydrogenation method

Examples

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Effect test

preparation example Construction

[0026] The preparation of catalyst 1~3:

[0027] Add 140ml of water, 5ml of nitric acid (content 60%), silica sol (containing 40% silicon dioxide) to 300g of pseudo-boehmite alumina powder, knead and extrude into strips, dry in the air at 120°C, 350~ Baking at 560°C for 3 to 6 hours. Take 100g of the roasted carrier, then dissolve magnesium nitrate and / or strontium nitrate in water according to the required amount, impregnate it on the carrier, dry it in the air at 120°C, and roast it at 800-1100°C to obtain the corresponding modified Al 2 o 3 carrier.

[0028] Add nickel nitrate to 20ml~30ml water and stir to dissolve, add cerium and / or lanthanum, soluble salt of VIB element while stirring according to the required amount, adjust the pH value to 4, then impregnate on 10g carrier, and age for 12 hours, Dry at 120°C and calcinate at 400°C for 4 hours to prepare the catalyst. The physical and chemical properties of the catalysts obtained can be shown in Table 2.

[0029] T...

Embodiment 1

[0032] Put catalyst 1 into a 100ml adiabatic bed hydrogenation reactor, raise the temperature of the bed to 240°C at a rate of 50°C / h under the pressure of 0.5MPa and maintain it for 5h, then raise the temperature to 360°C at a rate of 10°C / h ℃, maintained for 10h, and then raised to 410℃ at a rate of 15℃ / h, maintained for 5h; then cooled to 50℃, put into cyclohexane containing 1000ppm dimethyl disulfide, and continued to operate for 3h. with C 5 ~C 9 Whole distillate oil is used as raw material, reaction pressure: 2.8MPa, inlet temperature: 60°C, space velocity of fresh raw material oil: 3h -1 , Hydrogen to oil volume ratio: 200:1 (volume ratio is based on fresh oil) and run for 200h. The average diene of the hydrogenation product within 200 hours is 0.82 g iodine / 100 g oil, and the iodine value is 35.6 g iodine / 100 g oil.

Embodiment 2

[0034] Put catalyst 1 into a 100ml adiabatic bed hydrogenation reactor, raise the temperature of the bed to 260°C at a rate of 65°C / h under the pressure of 0.5MPa and maintain it for 6h, then raise the temperature to 350°C at a rate of 12°C / h ℃, maintained for 11h, then raised the temperature to 390°C at a rate of 12°C / h, and maintained for 4h; then cooled to 60°C, put in cyclohexane containing 2000ppm dimethyl disulfide, and continued to operate for 2h. with C 5 ~C 9 Whole distillate oil is used as raw material, reaction pressure: 2.8MPa, inlet temperature: 70°C, space velocity of fresh raw material oil: 2.8h -1 , Hydrogen to oil volume ratio: 200:1 (volume ratio is based on fresh oil) and run for 400h. The average diene of the hydrogenation product within 400 hours is 0.81 g iodine / 100 g oil, and the iodine value is 36.9 g iodine / 100 g oil.

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Abstract

The invention provides a selectivity hydrogenation method for diolefin of full-fraction pyrolysis gasoline, which comprises reduction and passivation of catalyst and application of technological conditions. The catalyst is nickel series hydrogenation catalyst which is used after being reduced or being subjected to reduction and passivation. The selectivity hydrogenation method is characterized inthat the hydrogenation technological conditions are as follows: the volume space velocity of a liquid is less than or equal to 4h<-1>, the inlet temperature of a reactor is between 40 and 130 DEG C, the reaction pressure is more than or equal to 2 MPa, and the hydrogen / oil ratio is between 100 and 500 (v / v); the nickel series catalyst takes alumina as a carrier, is prepared by the immersion method,and contains 14 to 20 percent of nickel oxide, 1 to 8 percent of lanthanum oxide and / or cerium oxide, 1 to 8 percent of 4B oxide auxiliary agent, 2 to 8 percent of silicon dioxide and 1 to 8 percento f alkaline earth oxide as calculated by 100 weight percent of the catalyst; and the specific surface of the catalyst is between 60 and 150 square meters per gram, and the pore volume of the catalystisbetween 0.4 and 0.6 milliliter per gram. The invention also provides a method for performing reduction and passivation on the catalyst on a hydrogenation unit. Under the conditions of the application method and the technological conditions, the nickel catalyst has good hydrogenation performance, and particularly has strong impurity and colloid resistance and good hydrogenation stability.

Description

technical field [0001] The invention relates to a method for selective hydrogenation of middle and low distillate oil, which is suitable for the selective hydrogenation of diolefinic unsaturated hydrocarbons, especially for the selective hydrogenation of diolefins in full-run cracking gasoline. Background technique [0002] Pyrolysis gasoline is a by-product of ethylene cracking, accounting for more than 50% of ethylene production capacity. It contains highly unsaturated hydrocarbons, such as diolefins, styrene, etc., which are converted into corresponding monoolefins through selective hydrogenation. With the continuous enhancement of my country's ethylene production capacity, pyrolysis gasoline hydrogenation has been developed in the direction of nickel-based catalysts for full-fraction hydrogenation. The variability of domestic pyrolysis gasoline raw materials, differences in cracking equipment and cracking methods have caused some manufacturers to deteriorate pyrolysis ga...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C10G45/36
Inventor 梁顺琴钱颖孙利民李晓艳吕龙刚曹凤霞吴杰王廷海郑云弟蒋彩兰滕彩梅王宗宝康宏敏
Owner PETROCHINA CO LTD
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