Diesel oil hydrogenation pour point depressing method

Abstract

The invention discloses a diesel oil hydrogenation pour point depressing method. A series flow of hydrofining and hydrogenation pour point depressing is adopted in the method, wherein a hydrogenation pour point depressing catalyst is modified by metal auxiliary agent and silicon, effectively regulates the acidity and orifice shape of the inner surface and the outer surface of a shape-selective cracking molecular sieve, is favorable for dispersing wax molecules in a diesel oil raw material into pore canals of the molecular sieve to perform shape-selective cracking reaction, and has high catalytic activity and selectivity of a target product; and because the acidity of the outer surface of the molecular sieve is weak, side reactions such as secondary cracking and the like are reduced, the pour point depressing effect of the diesel oil is good, and the fraction yield of the diesel oil is high.

Description

technical field

[0001] The invention relates to a method for hydrogenation of diesel oil, in particular to a method for hydrogenation and decondensation of waxy diesel oil. Background technique

[0002] Diesel products mainly come from straight-run diesel and secondary processed diesel. The raw materials not only contain impurities such as sulfur and nitrogen, but also contain wax components. The usual dewaxing method is the use of hydrogenation pour point depressing technology, which has attracted much attention because of its advantages of low investment, low operating cost, strong adaptability to raw materials, mild operating conditions, and large freezing point depression.

[0003] Diesel hydrodecondensation means that in the presence of hydrogen, the content of wax molecules in waxy diesel raw materials is reduced on the surface of a suitable catalyst. The principle of dewaxing is that under certain operating conditions, the raw material is mixed with hydrogen and con...

Examples

Embodiment 1

[0032] Will be made of small hole alumina (specific surface 238m 2 g -1 , pore volume 0.48mL·g -1 ) is added to HZSM-5 molecular sieve (97wt% on a dry basis, manufacturer: Tianjin Nankai University Catalyst Factory, SiO 2 / Al 2 o 3 molar ratio 38), mixed evenly, extruded, dried at 130°C for 4 hours, and calcined at 580°C for 4 hours to obtain a carrier.

[0033] The above-mentioned support is added to an aqueous zinc nitrate solution with a weight content of 6% zinc oxide and impregnated by equal volume for 5 hours. After filtering, the obtained solid phase is dried at 120° C. for 4 hours to obtain a zinc-modified support.

[0034] Add cyclohexane to dimethyl silicone oil to obtain a silicone oil-organic mixed solution with a silicon oxide weight concentration of 15%, and then add the zinc-modified carrier to the above-mentioned silicone oil-organic mixed solution to impregnate in equal volume for 3 hours . After filtration, it was dried at 100° C. for 4 hours and calcin...

Embodiment 2

[0037] Will be made of small hole alumina (specific surface 238m 2 g -1 , pore volume 0.48mL·g -1 ) was added to HZSM-5 molecular sieve (same as Example 1), mixed evenly, extruded, dried at 130°C for 4 hours, and calcined at 580°C for 4 hours to obtain a carrier.

[0038] The above-mentioned carrier is added to the aqueous solution of 3% copper nitrate and 3% magnesium nitrate with the content of copper oxide and immersion in the aqueous solution of magnesium nitrate with a volume ratio of 1: 1.5. The immersion time is 4 hours. After filtering, the solid phase obtained is subjected to 120 °C for 5 hours to obtain a copper- and magnesium-modified support.

[0039] Add solvent gasoline to ethyl silicone oil to obtain a silicone oil-organic mixed solution with a silicon oxide weight concentration of 20%, and then add the copper and magnesium-modified carrier to the above-mentioned silicone oil-organic mixed solution at a volume ratio of 1:1.5 for impregnation, The soaking time...

Embodiment 3

[0042] Will be made of small hole alumina (specific surface 238m 2 g -1 , pore volume 0.48mL·g -1 ) was added to HZSM-5 molecular sieve (same as Example 1), mixed evenly, extruded, dried at 130°C for 4 hours, and calcined at 580°C for 4 hours to obtain a carrier.

[0043] Add the above carrier to an aqueous solution with a lanthanum oxide content of 9% lanthanum nitrate and impregnate it at a volume ratio of 1:1.5 for 4 hours. After filtering, the obtained solid phase is dried at 120°C for 5 hours to obtain lanthanum-modified carrier.

[0044] Add solvent gasoline to ethyl silicone oil to obtain a silicone oil-organic mixed solution with a silicon oxide weight concentration of 20%, then add the lanthanum-modified carrier to the above-mentioned silicone oil-organic mixed solution for immersion at a volume ratio of 1:1.5, and the immersion time for 3 hours. After filtration, it was dried at 120° C. for 4 hours and calcined at 500° C. for 8 hours to obtain a carrier S3 modifi...

technical field

[0001] The invention relates to a method for hydrogenation of diesel oil, in particular to a method for hydrogenation and decondensation of waxy diesel oil. Background technique

[0002] Diesel products mainly come from straight-run diesel and secondary processed diesel. The raw materials not only contain impurities such as sulfur and nitrogen, but also contain wax components. The usual dewaxing method is the use of hydrogenation pour point depressing technology, which has attracted much attention because of its advantages of low investment, low operating cost, strong adaptability to raw materials, mild operating conditions, and large freezing point depression.

[0003] Diesel hydrodecondensation means that in the presence of hydrogen, the content of wax molecules in waxy diesel raw materials is reduced on the surface of a suitable catalyst. The principle of dewaxing is that under certain operating conditions, the raw material is mixed with hydrogen and con...

Examples

Embodiment 1

[0032] Will be made of small hole alumina (specific surface 238m 2 g -1 , pore volume 0.48mL·g -1 ) is added to HZSM-5 molecular sieve (97wt% on a dry basis, manufacturer: Tianjin Nankai University Catalyst Factory, SiO 2 / Al 2 o 3 molar ratio 38), mixed evenly, extruded, dried at 130°C for 4 hours, and calcined at 580°C for 4 hours to obtain a carrier.

[0033] The above-mentioned support is added to an aqueous zinc nitrate solution with a weight content of 6% zinc oxide and impregnated by equal volume for 5 hours. After filtering, the obtained solid phase is dried at 120° C. for 4 hours to obtain a zinc-modified support.

[0034] Add cyclohexane to dimethyl silicone oil to obtain a silicone oil-organic mixed solution with a silicon oxide weight concentration of 15%, and then add the zinc-modified carrier to the above-mentioned silicone oil-organic mixed solution to impregnate in equal volume for 3 hours . After filtration, it was dried at 100° C. for 4 hours and calcin...

Embodiment 2

[0037] Will be made of small hole alumina (specific surface 238m 2 g -1 , pore volume 0.48mL·g -1 ) was added to HZSM-5 molecular sieve (same as Example 1), mixed evenly, extruded, dried at 130°C for 4 hours, and calcined at 580°C for 4 hours to obtain a carrier.

[0038] The above-mentioned carrier is added to the aqueous solution of 3% copper nitrate and 3% magnesium nitrate with the content of copper oxide and immersion in the aqueous solution of magnesium nitrate with a volume ratio of 1: 1.5. The immersion time is 4 hours. After filtering, the solid phase obtained is subjected to 120 °C for 5 hours to obtain a copper- and magnesium-modified support.

[0039] Add solvent gasoline to ethyl silicone oil to obtain a silicone oil-organic mixed solution with a silicon oxide weight concentration of 20%, and then add the copper and magnesium-modified carrier to the above-mentioned silicone oil-organic mixed solution at a volume ratio of 1:1.5 for impregnation, The soaking time...

Embodiment 3

[0042] Will be made of small hole alumina (specific surface 238m 2 g -1 , pore volume 0.48mL·g -1 ) was added to HZSM-5 molecular sieve (same as Example 1), mixed evenly, extruded, dried at 130°C for 4 hours, and calcined at 580°C for 4 hours to obtain a carrier.

[0043] Add the above carrier to an aqueous solution with a lanthanum oxide content of 9% lanthanum nitrate and impregnate it at a volume ratio of 1:1.5 for 4 hours. After filtering, the obtained solid phase is dried at 120°C for 5 hours to obtain lanthanum-modified carrier.

[0044] Add solvent gasoline to ethyl silicone oil to obtain a silicone oil-organic mixed solution with a silicon oxide weight concentration of 20%, then add the lanthanum-modified carrier to the above-mentioned silicone oil-organic mixed solution for immersion at a volume ratio of 1:1.5, and the immersion time for 3 hours. After filtration, it was dried at 120° C. for 4 hours and calcined at 500° C. for 8 hours to obtain a carrier S3 modifi...

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