Petroleum resin hydrogenation catalyst and preparation method and application thereof

Abstract

The present invention relates to a petroleum resin hydrogenation catalyst which is a heteropolyacid-salt-modified skeletal nickel catalyst, the catalyst comprises Ni-Al-M, a component M is one or two or more of Fe, Co, Mn and Zn, or one or two or more of phosphorus molybdenum heteropoly acid salts or phosphorus tungsten heteropoly acid salts, the weight percentages of solid powder Ni, Al and M are as follows: Ni is 30-90%, Al is 5-60 %, and M is 0.1-15%, and the sum of the weight percentage of the Ni, Al and M is 100%. An added cocatalyst can increase the skeletal nickel catalyst sulfur resistant properties, and can effectively increase the service life of the catalyst. The petroleum resin hydrogenation catalyst is used for petroleum resin hydrogenation, reaction conditions are mild, thermal stability of obtained hydrogenation resin is improved, and bromine number and Gardner chromaticity are decreased obviously.

Description

technical field

[0001] The invention relates to a petroleum resin hydrogenation catalyst and its preparation method and application, in particular to the technical field of hydrogenation application of petroleum resin catalyzed by heteropoly acid salt modified skeleton nickel. Background technique

[0002] Petroleum resin is a product obtained by polymerization of the by-product carbon five or carbon nine fractions during cracking to produce ethylene through a complex catalyst or by thermal polymerization. Its molecular weight is generally less than 2000, the softening point is 5-150°C, and it is thermoplastic viscous liquid or solid. Petroleum resin has tackifying properties, adhesiveness and compatibility with other resin products, so it is often mixed with other polymer materials to improve the performance of various products, which are mainly used in coatings, adhesives and inks and other fields . However, with the continuous development of technology, the requirements...

Examples

Embodiment 1

[0023] Preparation of framework nickel catalyst:

[0024] Gradually add 50g of 100 mesh Ni-Al alloy powder (1:1 mass ratio) into aqueous sodium hydroxide solution (30wt%) at 90°C, stir for 4h, wash with deionized water until the pH value is neutral, and obtain skeleton nickel Catalyst A (specific surface area is 67m 2 / g).

[0025] 50g of Ni-Al alloy powder (2:1 mass ratio) was gradually added to sodium hydroxide (40wt%) at 90°C, stirred for 4h, washed with deionized water until the pH value was neutral, and the skeleton nickel catalyst B ( The specific surface area is 61m 2 / g).

[0026] 50g of 100-mesh Ni-Al alloy powder (1:1 mass ratio) was gradually added to potassium hydroxide (20wt%) at 90°C, stirred for 4h, washed with deionized water until the pH value was neutral, and a skeleton nickel catalyst was prepared C (the specific surface area is 85m 2 / g).

Embodiment 2

[0028] Preparation of heteropolyacids:

[0029] Dissolve 10g of phosphomolybdenum heteropolyacid (H3PO4·12MoO3) in deionized water, then add 1.2g of cobalt carbonate, dry at 120°C for 4h after complete dissolution, and roast at 400°C for 3h to obtain heteropolyacid salt D.

[0030] Dissolve 10g of phosphomolybdenum heteropolyacid (H3PO4·12MoO3) in deionized water, then add 1.5g of zinc carbonate, dry at 120°C for 4h after complete dissolution, and roast at 400°C for 3h to obtain heteropolyacid salt E.

[0031] Dissolve 13.5g of phosphotungstic heteropolyacid (H3PO4·12WO3) in deionized water, then add 1.2g of manganese carbonate, dry at 120°C for 4h after complete dissolution, and roast at 400°C for 3h to obtain heteropolyacid salt F.

[0032] Dissolve 13.5g of phosphotungstic heteropolyacid (H3PO4·12WO3) in deionized water, then add 0.9g of iron carbonate, dry at 120°C for 4h after complete dissolution, and roast at 400°C for 3h to obtain heteropolyacid salt G.

Embodiment 3

[0034] Preparation of heteropoly acid salt modified framework nickel catalyst:

[0035]Get 4 parts of every part of 10g framework nickel catalyst A, add respectively in 1.5g heteropolyacid salt D, E, F, G solution (solution mass concentration is 3%), stir 12h under room temperature, make heteropolyacid respectively Salt-modified skeleton nickel catalysts A1, A2, A3, A4.

[0036] Under the same conditions as above, the skeleton catalysts were replaced with B and C to prepare modified skeleton catalysts B1-B4, C1-C4, respectively.

technical field

[0001] The invention relates to a petroleum resin hydrogenation catalyst and its preparation method and application, in particular to the technical field of hydrogenation application of petroleum resin catalyzed by heteropoly acid salt modified skeleton nickel. Background technique

[0002] Petroleum resin is a product obtained by polymerization of the by-product carbon five or carbon nine fractions during cracking to produce ethylene through a complex catalyst or by thermal polymerization. Its molecular weight is generally less than 2000, the softening point is 5-150°C, and it is thermoplastic viscous liquid or solid. Petroleum resin has tackifying properties, adhesiveness and compatibility with other resin products, so it is often mixed with other polymer materials to improve the performance of various products, which are mainly used in coatings, adhesives and inks and other fields . However, with the continuous development of technology, the requirements...

Examples

Embodiment 1

[0023] Preparation of framework nickel catalyst:

[0024] Gradually add 50g of 100 mesh Ni-Al alloy powder (1:1 mass ratio) into aqueous sodium hydroxide solution (30wt%) at 90°C, stir for 4h, wash with deionized water until the pH value is neutral, and obtain skeleton nickel Catalyst A (specific surface area is 67m 2 / g).

[0025] 50g of Ni-Al alloy powder (2:1 mass ratio) was gradually added to sodium hydroxide (40wt%) at 90°C, stirred for 4h, washed with deionized water until the pH value was neutral, and the skeleton nickel catalyst B ( The specific surface area is 61m 2 / g).

[0026] 50g of 100-mesh Ni-Al alloy powder (1:1 mass ratio) was gradually added to potassium hydroxide (20wt%) at 90°C, stirred for 4h, washed with deionized water until the pH value was neutral, and a skeleton nickel catalyst was prepared C (the specific surface area is 85m 2 / g).

Embodiment 2

[0028] Preparation of heteropolyacids:

[0029] Dissolve 10g of phosphomolybdenum heteropolyacid (H3PO4·12MoO3) in deionized water, then add 1.2g of cobalt carbonate, dry at 120°C for 4h after complete dissolution, and roast at 400°C for 3h to obtain heteropolyacid salt D.

[0030] Dissolve 10g of phosphomolybdenum heteropolyacid (H3PO4·12MoO3) in deionized water, then add 1.5g of zinc carbonate, dry at 120°C for 4h after complete dissolution, and roast at 400°C for 3h to obtain heteropolyacid salt E.

[0031] Dissolve 13.5g of phosphotungstic heteropolyacid (H3PO4·12WO3) in deionized water, then add 1.2g of manganese carbonate, dry at 120°C for 4h after complete dissolution, and roast at 400°C for 3h to obtain heteropolyacid salt F.

[0032] Dissolve 13.5g of phosphotungstic heteropolyacid (H3PO4·12WO3) in deionized water, then add 0.9g of iron carbonate, dry at 120°C for 4h after complete dissolution, and roast at 400°C for 3h to obtain heteropolyacid salt G.

Embodiment 3

[0034] Preparation of heteropoly acid salt modified framework nickel catalyst:

[0035]Get 4 parts of every part of 10g framework nickel catalyst A, add respectively in 1.5g heteropolyacid salt D, E, F, G solution (solution mass concentration is 3%), stir 12h under room temperature, make heteropolyacid respectively Salt-modified skeleton nickel catalysts A1, A2, A3, A4.

[0036] Under the same conditions as above, the skeleton catalysts were replaced with B and C to prepare modified skeleton catalysts B1-B4, C1-C4, respectively.