Method for preparing macroporous vulcanization-type hydrogenation catalyst through one-step molding

Abstract

The invention provides a method for preparing a macroporous vulcanization-type hydrogenation catalyst through one-step molding. The method comprises (1) uniformly mixing a vulcanization agent, a vulcanization aid and additive granules, keeping the mixture at the constant temperature of 90-150 DEG C for 5-50min, adding an aqueous solution containing a hydrogenation active metal into the mixture, carrying out a reaction process at a temperature of 100-140 DEG C for 5-60min, and separating to remove the additive granules so that a liquid mixture I is obtained, (2) uniformly mixing a peptizing agent, water and urea to obtain a liquid mixture II, (3) carrying out mixing kneading on the liquid mixture I, the liquid mixture II and an aluminum source and extruding the mixture to obtain a wet material, and (4) carrying out ammonia treatment on the wet material, and then freezing, drying and calcining the treated wet material to obtain the vulcanization-type hydrogenation catalyst. The method realizes synchronization of catalyst preparation and vulcanization. The pore distribution of the catalyst is concentrated, the preparation process is simple, the catalytic activity of the catalyst is improved, the preparation cost of the catalyst is reduced, and the application prospect in the market is relatively broad.

Description

technical field

[0001] The invention relates to a preparation method of a one-time molding macroporous vulcanization type 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 the increasingly inferior and heavy crude oil, hydrogenation technology has been widely valued and applied all over the world. The demand for hydrogenation catalysts is increasing year by year, and most of these catalysts are sulfurized to obtain better performance. The presulfidation of catalysts (conversion of active metals from oxide state to sulfide state) in the hydrogenati...

Examples

Embodiment 1

[0039] 1. Prepare Mo-Ni-P solution: first add 50ml of clean water to 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 basic carbonic acid The salt is heated and decomposed to produce carbon dioxide bump. After adding the materials, cover 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 completely 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;

[0040] 2. Mix 10.9 g of elemental sulfur, 2 g of kerosene, and 22 g of rapeseed oil for 15 minutes; add 5 g of Mo-Ni type EPRES external presulfurization catalyst UDS-6 (Φ3.0), heat up to 100-120 ° C, and keep the temperature for 5-15 min ; Then, add 64ml of the above-mentioned Mo-Ni-P solution, and keep the temperature at 120°C f...

Embodiment 2

[0048] 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 solution concentration is CoO, 14.5 g / 100ml;

[0049] 2. Mix 10.9g of elemental sulfur, 2g of diesel oil, 22g of soybean oil, and 3g of glycerin for 5 minutes; add 5g of Co-Mo type EPRES external presulfurization catalyst FH-40B (Φ3.0), heat up to 100-120°C, and keep the temperature for 25 minutes ; Then, add 65ml of the above-mentioned Co-citric acid solution, and keep the temperature at 120°C for 25min. Then, cool and separate and remove the external presulfided catalyst FH-40B to obtain liquid mixture I;

[0050] 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,...

Embodiment 3

[0057] 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;

[0058] 2. Take 12.9 g of elemental sulfur, 2.2 g of white oil, and 24 g of lard and mix for 15 minutes; add 5.0 g of oxidized Co-Mo catalyst UDS-5 (Φ3.0), raise the temperature to 100-120 ° C, and keep the temperature for 5-15 minutes; Then, add 66ml of the above-mentioned Co-Mo citric acid solution, and keep the temperature at 120°C for 25min, then cool and separate the catalyst UDS-5 to obtain liquid mixture I;

[0059] 3. Take 52ml of water, add 4.7ml of conce...

technical field

[0001] The invention relates to a preparation method of a one-time molding macroporous vulcanization type 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 the increasingly inferior and heavy crude oil, hydrogenation technology has been widely valued and applied all over the world. The demand for hydrogenation catalysts is increasing year by year, and most of these catalysts are sulfurized to obtain better performance. The presulfidation of catalysts (conversion of active metals from oxide state to sulfide state) in the hydrogenati...

Examples

Embodiment 1

[0039] 1. Prepare Mo-Ni-P solution: first add 50ml of clean water to 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 basic carbonic acid The salt is heated and decomposed to produce carbon dioxide bump. After adding the materials, cover 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 completely 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;

[0040] 2. Mix 10.9 g of elemental sulfur, 2 g of kerosene, and 22 g of rapeseed oil for 15 minutes; add 5 g of Mo-Ni type EPRES external presulfurization catalyst UDS-6 (Φ3.0), heat up to 100-120 ° C, and keep the temperature for 5-15 min ; Then, add 64ml of the above-mentioned Mo-Ni-P solution, and keep the temperature at 120°C f...

Embodiment 2

[0048] 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 solution concentration is CoO, 14.5 g / 100ml;

[0049] 2. Mix 10.9g of elemental sulfur, 2g of diesel oil, 22g of soybean oil, and 3g of glycerin for 5 minutes; add 5g of Co-Mo type EPRES external presulfurization catalyst FH-40B (Φ3.0), heat up to 100-120°C, and keep the temperature for 25 minutes ; Then, add 65ml of the above-mentioned Co-citric acid solution, and keep the temperature at 120°C for 25min. Then, cool and separate and remove the external presulfided catalyst FH-40B to obtain liquid mixture I;

[0050] 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,...

Embodiment 3

[0057] 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;

[0058] 2. Take 12.9 g of elemental sulfur, 2.2 g of white oil, and 24 g of lard and mix for 15 minutes; add 5.0 g of oxidized Co-Mo catalyst UDS-5 (Φ3.0), raise the temperature to 100-120 ° C, and keep the temperature for 5-15 minutes; Then, add 66ml of the above-mentioned Co-Mo citric acid solution, and keep the temperature at 120°C for 25min, then cool and separate the catalyst UDS-5 to obtain liquid mixture I;

[0059] 3. Take 52ml of water, add 4.7ml of conce...

Images