Preparation method of vulcanization type hydrogenation catalyst

Abstract

The invention relates to a method for preparing a vulcanized hydrogenation catalyst. A catalyst carrier adopts an impregnation method to load hydrogenation metal components; before, after or simultaneously loading the hydrogenation metal components, a vulcanizing agent is introduced, and the use level of the vulcanizing agent is 85 to 150 percent of theoretic sulfur demand of the hydrogenation metal components; and during loading the hydrogenation metal components and introducing the vulcanizing agent, the method comprises at least one step of low-temperature thermal treatment but does not comprise a roasting step. The method overcomes the defects that the conventional oxidation catalyst has high preparation cost, long vulcanizing time and high operating cost. The catalyst prepared by the method is suitable for a hydrogenation process of petroleum fractions, and the hydrogenation activity of the catalyst prepared by the method can reach or exceeds the effect of the conventional catalyst.

Description

technical field

[0001] The invention relates to a preparation method of a hydrogenation catalyst, in particular to a preparation method of a sulfurized hydrogenation catalyst. Background technique

[0002] In recent years, the trend of poor quality of crude oil in the world has become increasingly obvious, the content of sulfur, nitrogen and aromatics in petroleum products has been increasing, and the requirements for environmental protection in various countries have become more and more stringent. Therefore, ultra-deep desulfurization of distillate oil, nitrogen catalyst and technology are one of the key research contents in this field. At present, harsh operating conditions are generally required for ultra-deep desulfurization and nitrogen operations of hydrogenation catalysts, such as increasing the reaction temperature or reducing the volume space velocity. Raising the temperature will easily lead to carbon deposition and deactivation of the catalyst; reducing the spac...

Examples

Embodiment 1

[0036] The preparation of embodiment 1 catalyst carrier

[0037]Take by weighing 900g of pseudo-boehmite (produced by Tianjin Alumina Factory, dry basis is 73%), 19g of scallop powder, 32g of citric acid, 48ml of nitric acid (30%), 159ml of silica gel (containing 30% of silicon dioxide), and remove Mix 250ml of deionized water evenly, extrude into 1.2mm clover strips on the extruder, dry at 120°C for 4 hours, and roast at 600°C for 3 hours to obtain carrier A. The specific surface area of ​​carrier A is 324.5m 2 / g, the pore volume is 0.72cm 3 / g, the average pore diameter is 8.87nm, and the intensity is 186N / cm.

Embodiment 2

[0038] The preparation of embodiment 2 sulfurized catalyst B

[0039] Weigh 28.48g of molybdenum oxide, 8.9g of basic nickel carbonate, add 60ml of deionized water and mix well, add 4ml of 85% phosphoric acid, heat to 75°C, and keep the temperature for 1 hour to obtain a dark green clear and transparent solution, then add 30.2g of partial tungsten Stir the ammonium acid to obtain the impregnating solution 1 after dissolving. According to the water absorption rate of 74ml / 100g, take the impregnating solution 1, spray and impregnate the carrier A, and heat-treat at 160°C for 3 hours to obtain a low-temperature heat-treated sample. Take the same amount of ammonium sulfide and phosphoric acid (85%) as the impregnating solution and flow-spray the low-temperature heat-treated sample , (NH 4 ) 2 S and H 3 PO 4 The mass ratio of catalyst B is 10:1, heat treatment at 160°C for 3 hours to obtain catalyst B, the main physical properties are shown in Table 1.

Embodiment 3

[0040] The preparation of embodiment 3 sulfurized catalyst C

[0041] Get impregnating solution 1 and ammonium sulfide in Example 2 and spray and impregnate carrier A according to water absorption rate 74ml / 100g, the volume ratio of impregnating solution 1 and ammonium sulfide is 1: 1, heat treatment at 200 ℃ for 5 hours, obtains catalyst C, The main physical properties are listed in Table 1.

technical field

[0001] The invention relates to a preparation method of a hydrogenation catalyst, in particular to a preparation method of a sulfurized hydrogenation catalyst. Background technique

[0002] In recent years, the trend of poor quality of crude oil in the world has become increasingly obvious, the content of sulfur, nitrogen and aromatics in petroleum products has been increasing, and the requirements for environmental protection in various countries have become more and more stringent. Therefore, ultra-deep desulfurization of distillate oil, nitrogen catalyst and technology are one of the key research contents in this field. At present, harsh operating conditions are generally required for ultra-deep desulfurization and nitrogen operations of hydrogenation catalysts, such as increasing the reaction temperature or reducing the volume space velocity. Raising the temperature will easily lead to carbon deposition and deactivation of the catalyst; reducing the spac...

Examples

Embodiment 1

[0036] The preparation of embodiment 1 catalyst carrier

[0037]Take by weighing 900g of pseudo-boehmite (produced by Tianjin Alumina Factory, dry basis is 73%), 19g of scallop powder, 32g of citric acid, 48ml of nitric acid (30%), 159ml of silica gel (containing 30% of silicon dioxide), and remove Mix 250ml of deionized water evenly, extrude into 1.2mm clover strips on the extruder, dry at 120°C for 4 hours, and roast at 600°C for 3 hours to obtain carrier A. The specific surface area of ​​carrier A is 324.5m 2 / g, the pore volume is 0.72cm 3 / g, the average pore diameter is 8.87nm, and the intensity is 186N / cm.

Embodiment 2

[0038] The preparation of embodiment 2 sulfurized catalyst B

[0039] Weigh 28.48g of molybdenum oxide, 8.9g of basic nickel carbonate, add 60ml of deionized water and mix well, add 4ml of 85% phosphoric acid, heat to 75°C, and keep the temperature for 1 hour to obtain a dark green clear and transparent solution, then add 30.2g of partial tungsten Stir the ammonium acid to obtain the impregnating solution 1 after dissolving. According to the water absorption rate of 74ml / 100g, take the impregnating solution 1, spray and impregnate the carrier A, and heat-treat at 160°C for 3 hours to obtain a low-temperature heat-treated sample. Take the same amount of ammonium sulfide and phosphoric acid (85%) as the impregnating solution and flow-spray the low-temperature heat-treated sample , (NH 4 ) 2 S and H 3 PO 4 The mass ratio of catalyst B is 10:1, heat treatment at 160°C for 3 hours to obtain catalyst B, the main physical properties are shown in Table 1.

Embodiment 3

[0040] The preparation of embodiment 3 sulfurized catalyst C

[0041] Get impregnating solution 1 and ammonium sulfide in Example 2 and spray and impregnate carrier A according to water absorption rate 74ml / 100g, the volume ratio of impregnating solution 1 and ammonium sulfide is 1: 1, heat treatment at 200 ℃ for 5 hours, obtains catalyst C, The main physical properties are listed in Table 1.

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