Operation method of vulcanized catalyst

Abstract

The invention relates to an operation method of a vulcanized catalyst, which comprises steps of loading the vulcanized catalyst into a reactor, introducing inert gas to replace air in the reactor and air in pipes in front of and behind the reactor, gradually raising the temperature to the activation temperature, switching hydrogen, adjusting pressure and temperature to reaction pressure and reaction temperature after airflow is stable, and introducing raw oil to carry out hydrogenation reaction, wherein a sulfide precursor containing metal Mo or W, Ni or Co, and a catalyst carrier required by the dipping of the dipping solution of an organic assistant are adopted by the vulcanized catalyst, and can be dried to obtain the vulcanized catalyst. The operation method solves the disadvantages of high preparation cost, long prevulcanization time and high operating cost of the traditional oxidation state catalyst. The catalyst prepared by the method does not need to be pre-vulcanized, and the preparation process and the operation method are simple, and are suitable for preparing the petroleum distillate hydrogenation catalyst. The hydrogenation activity of the catalyst prepared by the operation method is better than that of the traditional catalyst.

Description

technical field

[0001] The invention relates to a start-up method of a sulfurized catalyst, in particular to a start-up method for preparing a sulfurized hydrogenation catalyst with a solution containing a metal sulfide precursor. Background technique

[0002] Conventional hydrogenation catalysts are in an oxidized state, but the active substances are in a sulfurized state in actual use, so they need to be sulfurized in the reactor before use. Patent CN1171430A describes a typical in-vehicle pre-sulfurization method, wherein the vulcanizing agent is selected from carbon disulfide or dimethyl disulfide, etc., the volume ratio of the vulcanizing agent gas to the catalyst is generally 300-600, and the vulcanization is carried out under normal pressure or high pressure. The general heating and constant temperature program is vulcanization at 200-240°C for 2-6 hours, and then vulcanization at 320-360°C for 8-12 hours. This not only increases the production cost, but also the vul...

Examples

preparation example Construction

[0028] 1. Preparation of catalyst carrier: Prepare the catalyst carrier by conventional methods, and select the carrier type according to the number of acid sites required by the catalyst, such as silica-alumina, silica with additives, alumina with additives, or molecular sieves. The carrier powder is mixed with binder, pore-enlarging agent and extrusion aid, extruded on an extruder, dried and calcined to make a catalyst carrier. The catalyst carrier preparation method is well known to those skilled in the art.

[0029] 2. Configuration of impregnation solution: the sulfide precursors of Group VIB metals Mo and W, inorganic salts of Group VIII metal Ni or Co, and organic additives are prepared into a solution.

[0030] 3. Impregnate the catalyst carrier with the impregnating solution: load the impregnating solution on the catalyst carrier by impregnating method, and dry at 20°C-200°C for 1-10 hours to obtain a vulcanized catalyst.

Embodiment 1

[0033] a) Preparation of sulfurized catalyst A

[0034] Take by weighing pseudo-boehmite (produced by Shandong Alumina Plant, 73% by weight on a dry basis) 900g, 19g of scallop powder, 32g of citric acid, 48ml of nitric acid (30% by weight), silica gel (containing two by weight) Silica 30%) 159ml, deionized water 250ml mix evenly, extrude into 1.2mm clover strips on extruder, after drying, bake at 600 ℃ for 3 hours, obtain the required catalyst carrier 1.

[0035] Dissolve cobalt nitrate and ATMP (aminotrimethylene phosphonic acid) in deionized water to obtain a transparent solution, and mix tetraethylammonium thiomolybdate solution with it to form a solution. The amount of active components in the solution is determined according to the data in Table 1. The mixed solution was spray-soaked into carrier 1, and dried at 120°C for 3 hours to obtain catalyst A. The main physical properties are shown in Table 1.

[0036] b) Catalyst start-up method and evaluation

[0037] After i...

Embodiment 2

[0039] a) Preparation of sulfurized catalyst B

[0040] Dissolve nickel nitrate and nitrilotriacetic acid in deionized water to obtain a transparent solution, and then dissolve ammonium thiomolybdate in the solution to form an impregnation solution. The amount of active components in the impregnation solution is determined according to the data in Table 1. The impregnating solution was sprayed and impregnated with carrier 1, and dried at 120°C for 3 hours to obtain catalyst B. The main physical properties are shown in Table 1.

[0041] b) The catalyst start-up method and evaluation are the same as in Example 1. See Table 2 for the evaluation results.

technical field

[0001] The invention relates to a start-up method of a sulfurized catalyst, in particular to a start-up method for preparing a sulfurized hydrogenation catalyst with a solution containing a metal sulfide precursor. Background technique

[0002] Conventional hydrogenation catalysts are in an oxidized state, but the active substances are in a sulfurized state in actual use, so they need to be sulfurized in the reactor before use. Patent CN1171430A describes a typical in-vehicle pre-sulfurization method, wherein the vulcanizing agent is selected from carbon disulfide or dimethyl disulfide, etc., the volume ratio of the vulcanizing agent gas to the catalyst is generally 300-600, and the vulcanization is carried out under normal pressure or high pressure. The general heating and constant temperature program is vulcanization at 200-240°C for 2-6 hours, and then vulcanization at 320-360°C for 8-12 hours. This not only increases the production cost, but also the vul...

Examples

preparation example Construction

[0028] 1. Preparation of catalyst carrier: Prepare the catalyst carrier by conventional methods, and select the carrier type according to the number of acid sites required by the catalyst, such as silica-alumina, silica with additives, alumina with additives, or molecular sieves. The carrier powder is mixed with binder, pore-enlarging agent and extrusion aid, extruded on an extruder, dried and calcined to make a catalyst carrier. The catalyst carrier preparation method is well known to those skilled in the art.

[0029] 2. Configuration of impregnation solution: the sulfide precursors of Group VIB metals Mo and W, inorganic salts of Group VIII metal Ni or Co, and organic additives are prepared into a solution.

[0030] 3. Impregnate the catalyst carrier with the impregnating solution: load the impregnating solution on the catalyst carrier by impregnating method, and dry at 20°C-200°C for 1-10 hours to obtain a vulcanized catalyst.

Embodiment 1

[0033] a) Preparation of sulfurized catalyst A

[0034] Take by weighing pseudo-boehmite (produced by Shandong Alumina Plant, 73% by weight on a dry basis) 900g, 19g of scallop powder, 32g of citric acid, 48ml of nitric acid (30% by weight), silica gel (containing two by weight) Silica 30%) 159ml, deionized water 250ml mix evenly, extrude into 1.2mm clover strips on extruder, after drying, bake at 600 ℃ for 3 hours, obtain the required catalyst carrier 1.

[0035] Dissolve cobalt nitrate and ATMP (aminotrimethylene phosphonic acid) in deionized water to obtain a transparent solution, and mix tetraethylammonium thiomolybdate solution with it to form a solution. The amount of active components in the solution is determined according to the data in Table 1. The mixed solution was spray-soaked into carrier 1, and dried at 120°C for 3 hours to obtain catalyst A. The main physical properties are shown in Table 1.

[0036] b) Catalyst start-up method and evaluation

[0037] After i...

Embodiment 2

[0039] a) Preparation of sulfurized catalyst B

[0040] Dissolve nickel nitrate and nitrilotriacetic acid in deionized water to obtain a transparent solution, and then dissolve ammonium thiomolybdate in the solution to form an impregnation solution. The amount of active components in the impregnation solution is determined according to the data in Table 1. The impregnating solution was sprayed and impregnated with carrier 1, and dried at 120°C for 3 hours to obtain catalyst B. The main physical properties are shown in Table 1.

[0041] b) The catalyst start-up method and evaluation are the same as in Example 1. See Table 2 for the evaluation results.

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