RU2699225C1 - Protective layer catalyst and method of its use - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry, particularly to catalysts of protective layer for hydrofining of heavy oil fractions. Catalyst consists of three layers arranged with increase of total content of metal oxides in each next layer, wherein first along the motion protective layer consists of oxides of Ni-Co-Mo-V/Al₂O₃, with total pore volume of 1.0–1.2 cm³/g, with total content of metal oxides of total 1–3 wt%, molded in the form of hollow cylinders with diameter of 15 mm, second layer consists of oxides of Ni-Co-Mo-V/Al₂O₃ with total pore volume of 0.8–1.0 cm³/g, with granule diameter of 10 mm and content of metal oxides of total 5–9 wt%, and third layer consists of Ni-Co-Mo-V/Al₂O₃ oxides with total pore volume of 0.7–0.9 cm³/g, with granules diameter of 4.5–5.0 mm and content of metal oxides total 12–14 wt%. Invention also relates to a method of using the disclosed catalyst during hydrofining of heavy oil feedstock.

EFFECT: technical result is the creation of a new wide-porous catalyst protective layer for reducing deposits of asphaltenes, organometallic compounds, resins, polycyclic aromatic hydrocarbons and other coke precursors in the upper layer of the hydrotreating catalyst for heavy types of feedstock (fuel oil, or a mixture of vacuum gas oil and heavy gas oil of coking).

2 cl, 3 tbl, 6 ex

Description

The invention relates to the field of chemistry, in particular to catalysts for a protective layer for hydrotreating heavy oil fractions, and can be used in the oil refining and petrochemical industries.

Recently, there has been a growing demand for the production of motor fuels and low sulfur oils. In the coming years, the largest tonnage refining process will remain hydrotreating, and its role will increase due to the tightening of sulfur standards for gasoline, diesel, jet and marine fuels, as well as an increase in the depth of oil refining and the involvement of non-traditional hydrocarbon resources in oil refining. Due to the widespread use of the method of dense packing of fine-grained hydrotreating catalysts, which began to play the role of a kind of filter for mechanical impurities, the formation of a crust in the upper part of the catalyst layer became a fairly common problem. One of the crusting factors is the very high activity of modern hydrotreating catalysts. The hydrotreating feed may contain olefins, diolefins, resins, polycyclic aromatic hydrocarbons. Heavy raw materials (vacuum gas oil and fuel oil) also contain asphaltenes and organometallic compounds. All these compounds are extremely reactive under the conditions of hydrotreatment and form polymers (initial coke) with excellent adhesive properties. Polymers are an adhesive that bonds mechanical impurities and catalyst particles to form a hard crust.

The solution to the problem is a ranked loading of the upper part of the catalyst layer. In this case, ranking is required both by size and shape of particles, and by catalytic activity. Catalysts of the protective layer to prevent crusting in the upper part of the catalyst layer are currently used for all types of petroleum feedstocks.

Known [RU 2252243 C1, 2005] is a method for producing diesel fuel using layer-by-layer loading of catalysts. However, the use of these catalysts as protective for hydrotreating heavy oil fractions will not be effective, because the pore size of the catalyst of the protective layer is 4.0-14.0 nm, and they will be blocked by coke deposits [Berg GA, Khabibullin SG Catalytic hydrofining of oil residues. L. Chemistry, 1986 - 192 p.].

Closest to the proposed solution is a catalyst for hydrotreating the upper layer [RU 2235588 C2, 2004]. The essence of the invention lies in the fact that aluminum hydroxide with a moisture content of 50-80% of the mass. mixed with a ceramic mixture of a fractional composition of 0.01-0.1 mm, containing 65-76% of the mass, silicon oxide and 24-35% of the mass. alumina, molybdenum salt, cobalt or nickel salt are successively added, a solution of nitric acid in an amount sufficient to create an acidity of pH mass 3-4 is added to the resulting mixture, formed into hollow cylindrical granules, dried and calcined. The disadvantage of this catalyst is the need to use salts of molybdenum, cobalt and nickel, while the proposed method uses spent hydrotreating catalysts, the activity of which cannot be fully restored, and cheaper than vanadium salts of cobalt and molybdenum.

The objective of the invention is the creation of a new broad-porous catalyst for the protective layer to reduce deposits of asphaltenes, organometallic compounds, resins, polycyclic aromatic hydrocarbons and other coke precursors in the upper layer of the hydrotreating catalyst for heavy types of raw materials.

The problem is solved by creating a catalyst for the protective layer to reduce deposits of asphaltenes, organometallic compounds, resins, polycyclic aromatic hydrocarbons and other coke precursors in the upper layer of the heavy hydrotreating catalyst, which is characterized in that it is a wide-porous composite material consisting of Ni oxides, Co, Mo, V, Al, with an average pore diameter of 10 to 40 nm, with a total pore volume of 0.7 to 1.2 cm ³ / g, a particle size of 5 to 15 mm and various particle shapes.

The catalyst is a regenerated Ni-Mo / Al ₂ O ₃ and Co-Mo / Al ₂ O ₃ catalyst, crushed in a disintegrator to a particle size of less than 90 microns, mixed in an amount of 3.2-68.0% of the mass. based on the calcined mass of the demetallization catalyst with aluminum hydroxide peptized with concentrated HNO ₃ , ammonium metavanadate NH ₄ VO ₃ or vanadium oxide V ₂ O ₅ , and extruded, dried and calcined.

0.5-5.0 ml of triethylene glycol per 100 g of aluminum hydroxide is added to the mixture of ground catalyst and aluminum hydroxide, concentrated HNO _{3 is} added in an amount of 0.6-1.0 ml mol per 100 g of aluminum hydroxide, the extrusion molded composite material is dried at a temperature of 80-120 ° C for 6 hours and calcined at a temperature of 550 ° C for 2 hours, the amount of ammonium metavanadate NH ₄ VO ₃ or vanadium oxide V ₂ O ₅ is from 0.025 to 5% of the mass. in terms of V ₂ O ₅ .

When using a catalyst for the protective layer during the hydrotreating of heavy feedstocks, the gas-feed stream is passed through 3 catalytic layers located with an increase in the total content of metal oxides in each subsequent layer, while the first catalysts along the way with different pore diameters, granule sizes, granule shapes, and active components are arranged in layers, in 3 layers, with an increase in the total content of metal oxides in each subsequent layer, the first protective layer in the direction of the gas-feed stream rock-porous low-percentage catalyst Ni-Co-Mo-V / Al ₂ O ₃ , with a total pore volume of 1.0-1.2 cm ³ / g, with a total content of metal oxides in total 1-3% wt., molded in the form of hollow cylinders with a diameter of 15 mm, the second is a Ni-Co-Mo-V / Al ₂ O ₃ demetallization catalyst with a total pore volume of 0.8-1.0 cm ³ / g, with a granule diameter of 10 mm and a metal oxide content of 5-9% in total mass., the third-Ni-Co-Mo-V / Al ₂ O ₃ hydrogenation catalyst with a total pore volume of 0.7-0.9 cm ³ / g, with a diameter of granules of 4.5-5.0 mm and a content of metal oxides a total of 12-14% of the mass.

EFFECT: creation of a new broad-porous protective layer catalyst for reducing deposits of asphaltenes, organometallic compounds, resins, polycyclic aromatic hydrocarbons and other coke precursors in the upper layer of a hydrotreating catalyst for heavy types of raw materials.

Example 1

The catalyst 1 is prepared as follows: in 1000 g of aluminum hydroxide with a humidity of 80%, 6.65 g of crushed to a particle size less than 88 nm regenerated Ni-Mo / Al ₂ O ₃ and Co-Mo / Al ₂ O ₃ catalyst are added. Then a peptizing solution is prepared consisting of 6 ml of concentrated nitric acid with the addition of 3,600 g of vanadium (V) oxide. The resulting solution was poured into a mixture of aluminum hydroxide and a regenerated catalyst and the mixture was stirred until a homogeneous mass was obtained. Then add 50 ml of triethylene glycol and mix until a homogeneous paste. The catalyst mass is molded in the form of hollow cylinders with an extrudate diameter of 15.0 mm. Molded by extrusion, the composite material is dried at a temperature of 80-120 ° C for 6 hours and calcined at a temperature of 550 ° C for 2 hours. The resulting catalyst has the following composition: NiO-0.060 wt.%, CoO-0.065 wt.%, MoO ₃ -0.515 wt.%, V ₂ O ₅ -0.360 wt.%, Al ₂ O ₃ -99,000 wt.%, And properties : effective pore diameter -40 nm, pore volume -1.0 cm ^{3 /} g. (Table 1).

Catalyst 2 is prepared as follows: in 1000 g of aluminum hydroxide with a humidity of 80%, 15.49 g of regenerated Ni-Mo / Al ₂ O ₃ and Co-Mo / Al ₂ O ₃ catalyst, crushed to a particle size less than 40 nm, are added with stirring. Next, prepare a peptizing solution consisting of 8 ml of concentrated nitric acid with the addition of 61.85 g of ammonium metavanadate. The resulting solution was poured into a mixture of aluminum hydroxide and a regenerated catalyst and the mixture was stirred until a homogeneous mass was obtained. Then add 45 ml of triethylene glycol and mix until a homogeneous paste. The catalyst mass is formed into cylinders with an extrudate diameter of 10.0 mm. Molded by extrusion, the composite material is dried at a temperature of 80-120 ° C for 6 hours and calcined at a temperature of 550 ° C for 2 hours. The resulting catalyst has the following composition: NiO-0.145 wt.%, CoO-0.145 wt.%, MoO ₃ -1.150 wt.%, V ₂ O ₅ -3.640 wt.%, Al ₂ O ₃ -94.920 wt.%, And properties : effective pore diameter of -38 nm, pore volume of -0.8 cm ³ / g (tab. 1).

Catalyst 3 is prepared analogously to catalyst 1. The resulting catalyst 3 has the composition and properties shown in table 1.

The catalysts are arranged in layers, the first in the direction of movement of the feed is catalyst 1, the second is catalyst 2, and the third is catalyst 3.

Example 2

The catalyst 4 is prepared analogously to the catalyst 2 specified in example 1. The resulting catalyst 4 has the composition and properties indicated in the table. 1. The catalyst 5 is prepared analogously to the catalyst 1 specified in example 1. The resulting catalyst 5 has the composition and properties shown in table 1. The catalyst 6 is prepared analogously to the catalyst 2 specified in example 1. The resulting catalyst 6 has the composition and properties indicated in the table. one.

The catalysts are arranged in layers, the first in the direction of movement of the feed is catalyst 4, the second is catalyst 5, and the third is catalyst 6.

Example 3

The catalyst 7 is prepared analogously to the catalyst 1 specified in example 1. The resulting catalyst 7 has the composition and properties indicated in the table. 1. The catalyst 8 is prepared analogously to the catalyst 2 specified in example 1. The resulting catalyst 8 has the composition and properties indicated in the table. 1. The catalyst 9 is prepared analogously to the catalyst 1 specified in example 1. The resulting catalyst 9 has the composition and properties indicated in the table. one.

The catalysts are arranged in layers, the first in the direction of movement of the feedstock is catalyst 7, the second is catalyst 8, the third is catalyst 9.

Example 4

The catalyst 10 is prepared analogously to the catalyst 2 specified in example 1. The resulting catalyst 10 has the composition and properties indicated in the table. 1. The catalyst 11 is prepared analogously to the catalyst 1 specified in example 1. The resulting catalyst 11 has the composition and properties indicated in the table. 1. The catalyst 12 is prepared analogously to the catalyst 2 specified in example 1. The resulting catalyst 12 has the composition and properties indicated in the table. one.

The catalysts are arranged in layers, the first in the direction of movement of the feed is catalyst 10, the second is catalyst 11, and the third is catalyst 12.

Example 5

The catalyst 13 is prepared analogously to the catalyst 1 specified in example 1. The resulting catalyst 13 has the composition and properties shown in table 1. The catalyst 14 is prepared analogously to the catalyst 2 specified in example 1. The resulting catalyst 14 has the composition and properties indicated in the table. 1. The catalyst 15 is prepared analogously to the catalyst 1 specified in example 1. The resulting catalyst 15 has the composition and properties indicated in the table. one.

The catalysts are arranged in layers, the first in the direction of movement of the feed is catalyst 13, the second is catalyst 14, and the third is catalyst 15.

Example 6

The catalyst 16 is prepared analogously to the catalyst 2 specified in example 1. The resulting catalyst 16 has the composition and properties indicated in the table. 1. The catalyst 17 is prepared similarly to the catalyst 1 specified in example 1. The resulting catalyst 17 has the composition and properties shown in table 1. The catalyst 18 is prepared analogously to the catalyst 2 specified in example 1. The resulting catalyst 18 has the composition and properties shown in table. one.

The catalysts are arranged in layers, the first in the direction of movement of the raw materials is the catalyst 16, the second is the catalyst 17, the third is the catalyst 18.

The efficiency of the catalyst package was evaluated in the process of demetallization of fuel oil and a mixture of vacuum gas oil with heavy coking gas oil (10% wt.), With the characteristics indicated in table. 2, with the technological parameters indicated in the table. 1. The performance indicators of the use of catalyst packages are given in table. 3.

* - oxides of active metals, ** - demetallization catalyst

* - by layer KDM

Claims (2)

1. The catalyst of the protective layer to reduce deposits of asphaltenes, organometallic compounds, resins, polycyclic aromatic hydrocarbons and other coke precursors in the upper layer of the catalyst for hydrotreating heavy types of raw materials, characterized in that the catalyst consists of three layers located with increasing total content of metal oxides in each the next layer, while the first in the direction of travel the protective layer consists of oxides Ni-Co-Mo-V / Al ₂ O ₃ , with a total pore volume of 1.0-1.2 cm ³ / g, with a total content of metal oxides of Arno 1-3% wt., molded in the form of hollow cylinders with a diameter of 15 mm, the second layer consists of Ni-Co-Mo-V / Al ₂ O ₃ oxides with a total pore volume of 0.8-1.0 cm ³ / g, with a granule diameter of 10 mm and a metal oxide content of 5-9% by weight, and the third layer consists of Ni-Co-Mo-V / Al ₂ O ₃ oxides with a total pore volume of 0.7-0.9 cm ³ / g , with a diameter of granules of 4.5-5.0 mm and a content of metal oxides in total 12-14% of the mass. 2. The method of using the catalyst according to claim 1 in the process of hydrotreating heavy types of crude oil, characterized in that the gas stream is passed through the catalyst.