Preparation method of sulfurization type hydro-cracking catalyst

A hydrocracking and catalyst technology, applied in the direction of physical/chemical process catalysts, molecular sieve catalysts, chemical instruments and methods, etc., can solve the problems of low metal utilization, toxicity, and delayed start-up time, so as to achieve flexible active metal content and avoid Effect of low solubility and improved hydrogenation performance

Active Publication Date: 2014-05-07
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Conventional catalyst vulcanization methods use "in-vessel" vulcanization or "in-situ" vulcanization, that is, the catalyst in the oxidized state is first loaded into the hydrogenation reactor, and then hydrogen and sulfurizing agent are introduced into the reactor during the process of continuous heating. Pre-sulfurization, this method brings the following problems: (1) special pre-sulfurization equipment should be set up on the hydrogenation unit; (2) the vulcanizing agent added during the vulcanization process and the water and hydrogen sulfide generated by the reaction can easily cause high pressure Corrosion of reactors and related equipment, resulting in equipment damage and potential safety hazards; (3) The vulcanization process is longer, delaying the start-up time
(4) The vulcanizing agent used is flammable and toxic, and pollutes the environment during the vulcanization process; (5) The cost of pre-vulcanization in the device is relatively high
The above-mentioned methods all carry out pre-sulfurization treatment to the ready-made oxidized catalyst, so there are following deficiencies in the preparation process: the oxide MoO of hydrocracking catalyst active metal Mo, W, Co, Ni 3 、WO 3 , CoO, NiO have a strong interaction with the surface of the support, resulting in difficult and incomplete sulfidation of the active metal component, reducing the hydrogenation activity of the catalyst, and causing serious environmental pollution during the sulfidation process
The process is simple and the degree of sulfidation is high, so that the prepared sulfide hydrocracking catalyst has high activity and selectivity, but the catalyst prepared by kneading method has poor metal dispersion uniformity and low metal utilization rate, which affects the activity of the catalyst. and product properties

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] The catalyst catA involved in the present invention.

[0031] Prepare 500 ml of ammonium tetrathiomolybdate slurry (a), the slurry contains 5g molybdenum / 100ml, prepares 40ml of nickel nitrate solution (b), contains 5g nickel / 100ml in the slurry, weighs 120g of amorphous silica-alumina dry rubber powder, 30gY molecular sieve powder (SiO 2 / Al 2 o 3 The molar ratio is 40, the unit cell constant is 2.432nm, the infrared acidity is 0.19mmol / g, and the specific surface area is 866m 2 / g, pore volume 0.52ml / g), was added into 1500g water to make a slurry (c), slowly added (a) and (b) into the slurry (c), and stirred evenly. Filter, wash, and dry the obtained material at 100° C. for 6 hours under the protection of an inert gas to obtain a catalyst intermediate. Put the catalyst intermediate into the rolling machine and mix evenly, then add 180g of adhesive made by peptizing nitric acid and SB alumina, knead, and roll to make a paste that can be extruded, and extruded into...

Embodiment 2

[0033] The catalyst catB involved in the present invention.

[0034] Prepare 200 ml of tetramethylammonium thiomolybdate slurry (a), the slurry contains 10g molybdenum / 100ml, prepare 15ml of nickel nitrate solution (b), the slurry contains 10g nickel / 100ml, weigh 110g of amorphous silica-alumina dry glue powder, 28gβ molecular sieve powder (SiO 2 / A1 2 o 3 =28 (molar ratio), the unit cell constant is 1.198nm,

[0035] The relative crystallinity is 95%, the infrared acidity is 0.174mmol / g, and the specific surface area is 894m 2 / g, pore volume 0.54ml / g), was added into 1500g water to make a slurry (c), slowly added (a) and (b) into the slurry (c), and stirred evenly. Filter, wash, and dry the obtained material at 110° C. for 6 hours under the protection of an inert gas to obtain a catalyst intermediate. Put the catalyst intermediate into the rolling machine and mix evenly, then add 180g of adhesive made by peptizing nitric acid and SB alumina, knead, and roll to make a pa...

Embodiment 3

[0037] The catalyst catC involved in the present invention.

[0038] Prepare 500 ml of ammonium tetrathiotungstate slurry (a), the slurry contains 5g tungsten 100ml, prepare nickel nitrate solution 40ml (b), the slurry contains 5g nickel / 100ml, weigh 120g amorphous silica aluminum dry rubber powder, 30gY Molecular sieve powder (SiO 2 / Al 2 o 3 The molar ratio is 40, the unit cell constant is 2.432nm, the infrared acidity is 0.19mmol / g, and the specific surface area is 866m 2 / g, pore volume 0.52ml / g), was added into 1500g water to make a slurry (c), slowly added (a) and (b) into the slurry (c), and stirred evenly. Filter, wash, and dry the obtained material at 100° C. for 6 hours under the protection of an inert gas to obtain a catalyst intermediate. Put the catalyst intermediate into the rolling machine and mix evenly, then add 180g of adhesive made by peptizing nitric acid and SB alumina, knead, and roll to make a paste that can be extruded, and extruded into strips . ...

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Abstract

The invention discloses a preparation method of a sulfurization type hydro-cracking catalyst. The preparation method comprises the following steps: selecting a hydro-cracking catalyst carrier component, wherein the carrier component at least comprises an acidic cracking component; adding water into the carrier component powder, pulping so as to obtain slurry (c), then adding sulfo-molybdate and/or sulfo-tungstate slurry (a) and a nickel salt and/or cobalt salt solution (b) into the slurry (c), evenly stirring, filtering, washing, drying in the protection of inert gas, adding an adhesive, kneading, forming, and finally drying and burning in the protection of inert gas so as to obtain the sulfurization type hydro-cracking catalyst. The preparation method makes the active metal be evenly distributed on the carrier so as to generate more II type Ni(Co)Mo(W)S active phases with a higher activity; thus the catalyst has a high sulfurization degree and a high utilization rate of active metal, so that the hydrogenation performance of the catalyst is improved.

Description

technical field [0001] The invention relates to a preparation method of a hydrocracking catalyst, in particular to a preparation method of a sulfurized hydrocracking catalyst. Background technique [0002] In recent years, with the decrease of oil reserves, the rising international oil price, and the trend of heavy and inferior crude oil becoming more and more serious, the market demand for high-quality middle distillate products continues to increase. Therefore, it is particularly important to increase the production of middle distillates, increase the ratio of diesel to gasoline, and improve the contradiction between supply and demand. The key to solving this contradiction lies in the development of hydrocracking catalysts with high selectivity for middle distillates. Most of the metal active components of the current industrialized hydrocracking catalysts exist in the form of oxides, but in actual use, the active metal oxides on the catalyst need to be converted into sulf...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/16B01J29/78C10G47/20C10G47/12
Inventor 孙晓艳樊宏飞王占宇
Owner CHINA PETROLEUM & CHEM CORP
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