Preparation method of sulfurized type hydrogenation catalyst

Abstract

The invention discloses a preparation method of a sulfurized type hydrogenation catalyst. The method comprises the following steps: (1) preparing a solution containing a reactive metal complex, performing drying dehydration to obtain a reactive metal precursor, and preparing a semi-sulfurized material from the reactive metal precursor, a sulfurizing reagent and a sulfurizing aid by a mixed reaction; (2) uniformly mixing a peptizer, water and urea to obtain a liquid mixture; (3) adding an aluminum source to an acid aqueous solution, performing pulping, and then adding the semi-sulfurized material and the liquid mixture to the slurry; (4) performing rapid evaporation and concentration on the slurry to obtain concentrated slurry, and then performing slow drying treatment to obtain a semi-dried material; (5) performing rolling and extruding forming on the semi-dried material obtained in step (4), and performing roasting to obtain the sulfurized type hydrogenation catalyst. Catalyst preparation and sulfurization are finished simultaneously, pore size distribution of the catalyst is centralized, the preparation process is simple, and broader market application prospect is provided.

Description

technical field

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

[0002] Hydrofining, hydrotreating, hydrocracking and other oil refining catalytic hydrogenation production processes are environmentally friendly oil refining production processes, which can be widely used in the production of clean petroleum products such as gasoline, kerosene, diesel oil, lubricating oil, and paraffin. With the continuous upgrading of product quality, increasingly stringent environmental protection regulations, and increasingly inferior and heavy crude oil, hydrogenation technology has been widely valued and applied all over the world. The processing capacity of hydrogenation units in my country's oil refineries continues to grow, and the demand for hydrogenation catalysts is increasing year by year, and most of these catalysts can only obtain better performance after sulfidation. The presulfidation of catalysts (conversion o...

Examples

Embodiment 1

[0039] 1. Add 50ml of clean water into the preparation container, start the agitator, slowly add 57.2 g of molybdenum oxide, 22.4 g of basic nickel carbonate, and finally slowly add 1.27 g of phosphoric acid, to avoid carbon dioxide bumping due to the decomposition of basic carbonate by heating. Close the lid tightly, then heat up to >100°C, and keep the temperature constant for 1-2 hours until the molybdenum oxide and basic nickel carbonate are all dissolved, and the Mo-Ni-P solution is prepared. Mo-Ni-P solution concentration is MoO 3 , 57.1g / 100ml; NiO, 9.8 g / 100ml; P, 4.0 g / 100ml; take 70ml of Mo-Ni-P solution, and keep the temperature at 320°C for 150min to obtain the Mo-Ni active metal precursor;

[0040] 2. Mix the Mo-Ni active metal precursor, 10.9g of elemental sulfur, 2g of kerosene, and 22g of rapeseed oil for 15 minutes, and keep the temperature at 120°C for 25 minutes to obtain mixture I;

[0041] 3. Take 50ml of water, add 4.6ml of concentrated nitric acid to di...

Embodiment 2

[0047] 1. First, add 25ml of clean water into the preparation container, start the mixer, slowly add 9.8g of basic cobalt carbonate, 14g of citric acid, then heat up to >100°C, keep the temperature for 10-20min, and naturally cool to room temperature to obtain Co- Citric acid solution, the concentration is CoO 14.5g / 100ml; add Co-citric acid solution to ammonium heptamolybdate, 16.0g of ammonia solution (density 0.940) 67ml to obtain Co-Mo-ammonia citrate solution, and keep the temperature at 200℃ 240min to obtain the Mo-Co active metal precursor;

[0048] 2. Mix the Mo-Co active metal precursor, 15.6g of dimethyl disulfide, 2g of diesel oil, 22g of soybean oil, and 3g of glycerin for 5 minutes, and keep the temperature at 120°C for 25 minutes to obtain the mixture I;

[0049] 3. Take 50ml of water, add 4.6ml of concentrated nitric acid to dilute to obtain dilute nitric acid; then add 5g of citric acid and 4g of urea, and then add 20g of silica sol, stir well to obtain liquid ...

Embodiment 3

[0055]1. First add 25ml of clean water to the preparation container, start the agitator, slowly add 9.8g of basic cobalt carbonate, 14g of citric acid, then heat up to >100°C, keep the temperature for 10-20min, and naturally cool to room temperature, the solution volume is 35ml . A Co-citric acid solution was prepared. Add ammonium heptamolybdate 18.2g then, add ammoniacal liquor (0.94g / ml specific gravity) 50ml again, prepare Co-Mo citric acid solution concentration and be MoO 3 , 21.1g / 100ml; CoO, 3.90g / 100ml; take 30ml of Co-Mo citric acid solution, and keep the temperature at 270°C for 300min to obtain the Mo-Co active metal precursor;

[0056] 2. Mix the Mo-Co active metal precursor, 12.9g of elemental sulfur, 2.2g of white oil, and 24g of lard for 15 minutes; keep the temperature at 120°C for 25 minutes to obtain the mixture I;

[0057] 3. Take 52ml of water, then add 5g of citric acid and 4g of urea, stir well to obtain liquid mixture II;

[0058] 4. Take 200ml of wa...

technical field

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

[0002] Hydrofining, hydrotreating, hydrocracking and other oil refining catalytic hydrogenation production processes are environmentally friendly oil refining production processes, which can be widely used in the production of clean petroleum products such as gasoline, kerosene, diesel oil, lubricating oil, and paraffin. With the continuous upgrading of product quality, increasingly stringent environmental protection regulations, and increasingly inferior and heavy crude oil, hydrogenation technology has been widely valued and applied all over the world. The processing capacity of hydrogenation units in my country's oil refineries continues to grow, and the demand for hydrogenation catalysts is increasing year by year, and most of these catalysts can only obtain better performance after sulfidation. The presulfidation of catalysts (conversion o...

Examples

Embodiment 1

[0039] 1. Add 50ml of clean water into the preparation container, start the agitator, slowly add 57.2 g of molybdenum oxide, 22.4 g of basic nickel carbonate, and finally slowly add 1.27 g of phosphoric acid, to avoid carbon dioxide bumping due to the decomposition of basic carbonate by heating. Close the lid tightly, then heat up to >100°C, and keep the temperature constant for 1-2 hours until the molybdenum oxide and basic nickel carbonate are all dissolved, and the Mo-Ni-P solution is prepared. Mo-Ni-P solution concentration is MoO 3 , 57.1g / 100ml; NiO, 9.8 g / 100ml; P, 4.0 g / 100ml; take 70ml of Mo-Ni-P solution, and keep the temperature at 320°C for 150min to obtain the Mo-Ni active metal precursor;

[0040] 2. Mix the Mo-Ni active metal precursor, 10.9g of elemental sulfur, 2g of kerosene, and 22g of rapeseed oil for 15 minutes, and keep the temperature at 120°C for 25 minutes to obtain mixture I;

[0041] 3. Take 50ml of water, add 4.6ml of concentrated nitric acid to di...

Embodiment 2

[0047] 1. First, add 25ml of clean water into the preparation container, start the mixer, slowly add 9.8g of basic cobalt carbonate, 14g of citric acid, then heat up to >100°C, keep the temperature for 10-20min, and naturally cool to room temperature to obtain Co- Citric acid solution, the concentration is CoO 14.5g / 100ml; add Co-citric acid solution to ammonium heptamolybdate, 16.0g of ammonia solution (density 0.940) 67ml to obtain Co-Mo-ammonia citrate solution, and keep the temperature at 200℃ 240min to obtain the Mo-Co active metal precursor;

[0048] 2. Mix the Mo-Co active metal precursor, 15.6g of dimethyl disulfide, 2g of diesel oil, 22g of soybean oil, and 3g of glycerin for 5 minutes, and keep the temperature at 120°C for 25 minutes to obtain the mixture I;

[0049] 3. Take 50ml of water, add 4.6ml of concentrated nitric acid to dilute to obtain dilute nitric acid; then add 5g of citric acid and 4g of urea, and then add 20g of silica sol, stir well to obtain liquid ...

Embodiment 3

[0055]1. First add 25ml of clean water to the preparation container, start the agitator, slowly add 9.8g of basic cobalt carbonate, 14g of citric acid, then heat up to >100°C, keep the temperature for 10-20min, and naturally cool to room temperature, the solution volume is 35ml . A Co-citric acid solution was prepared. Add ammonium heptamolybdate 18.2g then, add ammoniacal liquor (0.94g / ml specific gravity) 50ml again, prepare Co-Mo citric acid solution concentration and be MoO 3 , 21.1g / 100ml; CoO, 3.90g / 100ml; take 30ml of Co-Mo citric acid solution, and keep the temperature at 270°C for 300min to obtain the Mo-Co active metal precursor;

[0056] 2. Mix the Mo-Co active metal precursor, 12.9g of elemental sulfur, 2.2g of white oil, and 24g of lard for 15 minutes; keep the temperature at 120°C for 25 minutes to obtain the mixture I;

[0057] 3. Take 52ml of water, then add 5g of citric acid and 4g of urea, stir well to obtain liquid mixture II;

[0058] 4. Take 200ml of wa...

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