CN117181292A - Deep hydrogenation dearomatization catalyst for diesel oil and preparation method and application thereof - Google Patents

Deep hydrogenation dearomatization catalyst for diesel oil and preparation method and application thereof Download PDF

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CN117181292A
CN117181292A CN202210613300.1A CN202210613300A CN117181292A CN 117181292 A CN117181292 A CN 117181292A CN 202210613300 A CN202210613300 A CN 202210613300A CN 117181292 A CN117181292 A CN 117181292A
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molecular sieve
catalyst
hours
carrier
rare earth
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杨平
樊亚明
刘诗哲
任亮
毛以朝
许双辰
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The invention relates to a diesel oil deep hydrogenation dearomatization catalyst and a preparation method and application thereof, wherein the catalyst comprises a carrier and an active metal component loaded on the carrier; the active metal component comprises a VIII group metal element and a VIB group metal element; the carrier comprises a composite molecular sieve and a heat-resistant inorganic oxide matrix, the composite molecular sieve comprises a first molecular sieve and a second molecular sieve, the first molecular sieve is a Y molecular sieve, and the second molecular sieve is a molecular sieve with an N value larger than 1; wherein the definition of N value of a certain molecular sieve to be detected is the ratio of the adsorption quantity of the molecular sieve to be detected to the dicyclic arene and the derivative thereof to the adsorption quantity of a standard molecular sieve to the dicyclic arene and the derivative thereof, the standard molecular sieve is an HY molecular sieve, and the standard molecular sieve is SiO 2 And Al 2 The O molar ratio was 5.4 and the unit cell constant was 24.60 Angstrom. The catalyst disclosed by the invention can improve the conversion rate of polycyclic aromatic hydrocarbon in diesel oil fraction, is beneficial to deep dearomatization of diesel oil and improves the diesel oilDiesel quality.

Description

Deep hydrogenation dearomatization catalyst for diesel oil and preparation method and application thereof
Technical Field
The present disclosure relates to the field of catalysts, and in particular, to a deep hydrogenation dearomatization catalyst for diesel oil, and a preparation method and application thereof.
Background
Along with the gradual improvement of fuel oil quality standards, the reduction of the content of polycyclic aromatic hydrocarbons in diesel oil, especially in secondary processing diesel oil with higher polycyclic aromatic hydrocarbon content, is a focus of attention of oil refiners. The hydrotreating can convert polycyclic aromatic hydrocarbon in the diesel fraction into monocyclic aromatic hydrocarbon or naphthenic hydrocarbon through hydrogenation saturation and selective ring opening reaction, so as to realize the aim of reducing the content of polycyclic aromatic hydrocarbon; meanwhile, the cetane number of the diesel oil product can be improved, the density of the diesel oil product can be reduced, and the quality of the diesel oil can be further improved. Polycyclic aromatic hydrocarbon hydrogenation catalysis is a typical heterogeneous catalysis process, and diffusion and adsorption performance are one of key factors influencing the polycyclic aromatic hydrocarbon hydrogenation reaction activity and product distribution.
Chinese patent document 201610288646.3 discloses a modified Y/ZSM-48 composite molecular sieve, and a preparation method and application thereof. The modified Y/ZSM-48 composite molecular sieve has the following properties: the total pore volume is 0.46-0.85 mL/g, preferably 0.50-0 80mL/g; wherein the mesoporous volume is 0.35-0.65 mL/g, preferably 0.40-0.60 mL/g; the mesoporous volume accounts for 55-90%, preferably 60-80% of the total pore volume. The modified Y/ZSM-48 composite molecular sieve has larger mesoporous distribution, can provide more reaction space for macromolecules, and can realize the hydro-ring-opening conversion of polycyclic aromatic hydrocarbon in the hydrocracking process.
Chinese patent document 201610288647.8 discloses a modified Y-Beta composite molecular sieve, and a preparation method and application thereof. The modified Y-Beta composite molecular sieve has the following characteristics: the total pore volume is 0.56-1.25 mL/g, preferably 0.65-1.10 mL/g; wherein the mesoporous volume is 0.45-0.95 mL/g, preferably 0.550-0.85 mLg; the mesoporous volume is 55% -80%, preferably 60% -75% of the total pore volume. The modified molecular sieve can be used for the hydro-ring-opening conversion of polycyclic aromatic hydrocarbon in the hydrocracking process.
Chinese patent document 202110100233.9 discloses a catalyst for diesel oil hydro-upgrading, which adopts mesoporous amorphous silicon-aluminum with a pore volume of 0.51-0.70 mL/g and a range of 12-20 nm. The catalyst has certain polycyclic aromatic hydrocarbon reaction activity when processing poor-quality catalytic diesel oil raw materials.
The catalyst can realize hydrogenation ring opening of polycyclic aromatic hydrocarbon to a certain extent, but the effect is still not ideal.
Disclosure of Invention
The purpose of the present disclosure is to provide a catalyst for deep hydrotreating of diesel oil, thereby realizing hydrogenated ring opening of polycyclic aromatic hydrocarbons.
In order to achieve the above object, a first aspect of the present disclosure provides a diesel deep hydrodearomatization catalyst comprising a support and an active metal component supported on the support; the active metal component comprises a VIII group metal element and a VIB group metal element; the carrier comprises a composite molecular sieve and a heat-resistant inorganic oxide matrix, wherein the composite molecular sieve comprises a first molecular sieve and a second molecular sieve, the first molecular sieve is a Y molecular sieve, and the second molecular sieve is a molecular sieve with an N value larger than 1; wherein the definition of N value of a certain molecular sieve to be detected is the ratio of the adsorption quantity of the molecular sieve to be detected to the dicyclic arene and the derivative thereof to the adsorption quantity of a standard molecular sieve to the dicyclic arene and the derivative thereof, the standard molecular sieve is an HY molecular sieve, and the standard molecular sieve is SiO 2 And Al 2 The O molar ratio was 5.4 and the unit cell constant was 24.60 Angstrom.
Optionally, the second molecular sieve has an N value of 1 to 10, preferably, the second molecular sieve has an N value of 1 to 5; optionally, the second molecular sieve has a pore volume of 0.4 to 0.8cm 3 Per gram, acid density of 0.8-2.5 mu mol/m 2 。
Optionally, the weight ratio of the first molecular sieve to the second molecular sieve in the composite molecular sieve is 1:9-9:1, preferably 1:1-9:1.
Alternatively, the composite molecular sieve is present in the support in an amount of from 5 to 70 weight percent and the refractory inorganic oxide matrix is present in an amount of from 30 to 95 weight percent, based on the total weight of the support.
Alternatively, the catalyst contains, on an oxide basis, 50 to 85 wt.% of the support, 1.5 to 6 wt.% of a group VIII metal element, and 10 to 35 wt.% of a group VIB metal element, based on the total weight of the catalyst.
Optionally, the first molecular sieve is at least one selected from an HY molecular sieve, a rare earth type Y molecular sieve REY, a rare earth type HY molecular sieve REHY, an ultrastable Y molecular sieve USY, a partially amorphous USY, a rare earth type ultrastable Y molecular sieve REUSY, a titanium-containing Y molecular sieve, a phosphorus-containing Y, an ultrastable and HY type molecular sieve and a dealuminated Y type molecular sieve; preferably, the first molecular sieve is at least one selected from an HY molecular sieve, a rare earth Y molecular sieve, a rare earth HY molecular sieve, an ultrastable Y molecular sieve, a rare earth ultrastable Y molecular sieve, a partially amorphous Y molecular sieve, a titanium-containing Y molecular sieve and a phosphorus-containing Y-type molecular sieve; the second molecular sieve is selected from at least one of ITQ-40, ITQ-44, ITQ-37, ITQ-53, ITQ-54, OSB-1 and EMC-2; the refractory inorganic oxide matrix is selected from at least one of alumina, silica, and silica-alumina.
A second aspect of the present disclosure provides a method of preparing a catalyst, the method comprising:
s1, mixing a first molecular sieve, a second molecular sieve, a heat-resistant inorganic oxide matrix and an auxiliary agent, kneading and extruding to obtain an extruded strip; carrying out first drying and first roasting on the extruded strip to obtain a carrier; the auxiliary agent is at least one selected from inorganic binders and extrusion aids;
s2, impregnating the carrier by using an aqueous solution containing a compound of a VIII group metal and a compound of a VIB group metal to obtain an impregnated carrier; and carrying out second drying and activating treatment on the impregnated carrier.
Optionally, the weight ratio of the first molecular sieve, the second molecular sieve, and the refractory inorganic oxide matrix is 1-25:4-45:30-95.
Optionally, in step S1, the conditions of the first drying process include: the drying temperature is 80-300 ℃, preferably 100-200 ℃; the drying time is 1-12 hours, preferably 2-8 hours; the conditions of the first firing include: the roasting temperature is 350-850 ℃, preferably 450-650 ℃; the calcination time is 1 to 12 hours, preferably 2 to 6 hours; in step S2, the conditions of the impregnation include: the dipping temperature is between room temperature and 150 ℃ and the dipping time is between 1 and 6 hours; the second drying conditions include: the temperature is 100-300 ℃, preferably 100-150 ℃; the time is 2-8 hours; the activation treatment conditions include: the temperature is 100-350deg.C, preferably 120-250deg.C; the time is 1-12 hours, preferably 2-6 hours.
In a third aspect, the disclosure provides a method for deep hydrotreating diesel, contacting the diesel and hydrogen with the catalyst and performing hydrocracking reaction
Through the technical scheme, the method improves the diffusion and adsorption performance of the polycyclic aromatic hydrocarbon molecules in the diesel fraction on the catalyst and improves the removal and conversion of the polycyclic aromatic hydrocarbon in the diesel fraction by improving the pore channel structure and the size of the catalyst active component molecular sieve and the matching property of the polycyclic aromatic hydrocarbon reactant molecules. The catalyst disclosed by the invention can improve the conversion rate of polycyclic aromatic hydrocarbon in the diesel fraction, is beneficial to deep dearomatization of diesel and improves the quality of diesel.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present disclosure in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
A first aspect of the present disclosure provides a diesel deep hydrodearomatization catalyst comprising a support and an active metal component supported on the support; the active metal component comprises a VIII group metal element and a VIB group metal element; the carrier comprises a composite molecular sieve and a heat-resistant inorganic oxide matrix, wherein the composite molecular sieve comprises a first molecular sieve and a second molecular sieve, the first molecular sieve is a Y molecular sieve, and the second molecular sieve is a molecular sieve with an N value larger than 1; wherein the definition of N value of a certain molecular sieve to be detected is the absorption of the molecular sieve to be detected to the dicyclic arene and the derivative thereofThe ratio of the attached amount to the adsorption amount of the standard molecular sieve to the dicyclic arene and the derivative thereof, wherein the standard molecular sieve is HY molecular sieve, and the standard molecular sieve is SiO 2 And Al 2 The O molar ratio was 5.4 and the unit cell constant was 24.60 Angstrom.
The N value is obtained by an adsorption molar ratio test method, and is specifically as follows: the tetrahydronaphthalene solution (100 ml, room temperature) was accurately measured first, then the quantitative molecular sieve material (5 g) was added under an inert gas (N) 2 ) And (3) protecting, sealing and stirring for 10 hours at a constant temperature of 360 ℃ under 1 atmosphere, filtering, re-sizing the filtrate, cooling to room temperature, and measuring the volume of the solution by using a cylinder again to obtain the adsorption volume difference delta V test molecular sieve. The calculation formula of N is:
n= (Δv test molecular sieve x M test molecular sieve)/(Δvy type molecular sieve x MY type molecular sieve)
Wherein the DeltaV test molecular sieve and the DeltaVY molecular sieve are the volume difference of the tetrahydronaphthalene adsorption of the test molecular sieve and the standard molecular sieve respectively, and the M test molecular sieve and the MY molecular sieve are the molar mass of the test molecular sieve and the standard molecular sieve respectively.
The method realizes the screening of the catalyst acidic component molecular sieve through the N value, strengthens the matching degree of the molecular sieve pore channel structure and the polycyclic aromatic hydrocarbon reactant molecules, can improve the hydroconversion and removal of the polycyclic aromatic hydrocarbon, and can be used in the dearomatization process of deep hydrotreatment of diesel oil, especially low-grade diesel oil rich in the polycyclic aromatic hydrocarbon.
According to the present disclosure, the second molecular sieve may have an N value of 1 to 10, preferably, the second molecular sieve has an N value of 1 to 5; alternatively, the second molecular sieve may have a pore volume of 0.4 to 0.8cm 3 Per gram, the acid density can be 0.8-2.5 mu mol/m 2 。
According to the present disclosure, the weight ratio of the first molecular sieve to the second molecular sieve in the composite molecular sieve may be 1:9 to 9:1, preferably 1:1 to 9:1.
According to the present disclosure, the composite molecular sieve may be present in the support in an amount of 5 to 70 wt% and the refractory inorganic oxide matrix may be present in an amount of 30 to 95 wt% based on the total weight of the support.
According to the present disclosure, the catalyst may contain, on an oxide basis, 50 to 85 wt.% of the support, 1.5 to 6 wt.% of the group VIII metal element, and 10 to 35 wt.% of the group VIB metal element, based on the total weight of the catalyst.
According to the present disclosure, the first molecular sieve may be selected from at least one of an HY molecular sieve, a rare earth Y molecular sieve REY, a rare earth HY molecular sieve REY, an ultrastable Y molecular sieve USY, a partially amorphous USY, a rare earth ultrastable Y molecular sieve REUSY, a titanium-containing Y molecular sieve, a phosphorus-containing Y and ultrastable and HY-type molecular sieves, and a dealuminated Y-type molecular sieve; preferably, the first molecular sieve may be at least one selected from the group consisting of an HY molecular sieve, a rare earth Y molecular sieve, a rare earth HY molecular sieve, a ultrastable Y molecular sieve, a rare earth ultrastable Y molecular sieve, a partially amorphous Y molecular sieve, a titanium-containing Y molecular sieve, and a phosphorus-containing Y-type molecular sieve; the second molecular sieve may be selected from at least one of ITQ-40, ITQ-44, ITQ-37, ITQ-53, ITQ-54, OSB-1, and EMC-2.
In the present disclosure, the refractory inorganic oxide matrix may be selected from at least one of alumina, silica, and silica-alumina. The alumina is selected from one or more transition phase alumina of gamma, eta, theta, delta and chi, and can also be one or more transition phase alumina of gamma, eta, theta, delta and chi containing one or more additive components selected from silicon, titanium, magnesium, boron, zirconium, thorium, niobium and rare earth, preferably gamma-alumina and gamma-alumina containing one or more additive components selected from silicon, phosphorus, titanium, magnesium, boron, zirconium, thorium, niobium and rare earth. They may be commercially available or may be obtained by any of the existing methods. The silica-alumina is preferably a silica-alumina having a pseudo-boehmite structure, and may be commercially available or prepared by any of the prior art techniques. For example, siral series of commercial silica-aluminas manufactured by Condea, germany, having pseudo-boehmite structures, are useful in the present disclosure.
The catalyst provided in accordance with the present disclosure may be carried out in any reactor sufficient to contact the feedstock with the catalyst under hydrogenation reaction conditions, for example, in a fixed bed reactor, moving bed reactor or ebullated bed reactor. Other hydrocarbon oil feedstocks of various types may also be processed directly to hydrotreat them. The hydrocarbon oil raw material can also be various heavy mineral oil or synthetic oil or mixed distillate oil thereof, such as one or more selected from crude oil, distillate oil, solvent refined oil, cerate, oil under wax, fischer-Tropsch synthetic oil, coal liquefied oil, light deasphalted oil and heavy deasphalted oil. Is especially suitable for the hydrotreating dearomatization process of diesel oil, especially low-grade diesel oil rich in polycyclic aromatic hydrocarbon.
A second aspect of the present disclosure provides a method of preparing a catalyst, the method comprising:
s1, mixing a first molecular sieve, a second molecular sieve, a heat-resistant inorganic oxide matrix and an auxiliary agent, kneading and extruding to obtain an extruded strip; carrying out first drying and first roasting on the extruded strip to obtain a carrier; the auxiliary agent is at least one selected from inorganic binders and extrusion aids;
s2, impregnating the carrier by using an aqueous solution containing a compound of a VIII group metal and a compound of a VIB group metal to obtain an impregnated carrier; and carrying out second drying and activating treatment on the impregnated carrier.
According to the present disclosure, the weight ratio of the first molecular sieve, the second molecular sieve, and the refractory inorganic oxide matrix may be 1 to 25:4-45:30-95.
According to the present disclosure, in step S1, the conditions of the first drying process include: the drying temperature is 80-300 ℃, preferably 100-200 ℃; the drying time is 1-12 hours, preferably 2-8 hours; the conditions of the first firing include: the roasting temperature is 350-850 ℃, preferably 450-650 ℃; the calcination time is 1 to 12 hours, preferably 2 to 6 hours; in step S2, the conditions of the impregnation include: the dipping temperature is between room temperature and 150 ℃ and the dipping time is between 1 and 6 hours; the second drying conditions include: the temperature is 100-300 ℃, preferably 100-150 ℃; the time is 2-8 hours; the activation treatment conditions include: the temperature is 100-350deg.C, preferably 120-250deg.C; the time is 1-12 hours, preferably 2-6 hours.
The third aspect of the disclosure provides a method for deep hydrotreating of diesel, in which diesel, especially low-grade diesel rich in polycyclic aromatic hydrocarbon and hydrogen, are contacted with the catalyst of the disclosure under hydrogenation conditions, so that the hydroconversion and removal of polycyclic aromatic hydrocarbon can be improved, and the dearomatization process of deep hydrotreating of diesel is realized.
The present disclosure is further illustrated by the following examples, but the present disclosure is not limited thereby.
Example 1
200.0 g of pseudo-boehmite (catalyst Kaolin Co.) with a dry basis of 70%, 42.4 g of Y-type molecular sieve with a dry basis of 85% and 29.3 g of ITQ-37 molecular sieve with a dry basis of 82% are weighed, and a proper amount of auxiliary agent containing inorganic binder, extrusion aid and the like are added to be uniformly mixed, extruded into a butterfly-shaped carrier strip with a circumcircle diameter of 1.6 mm on a strip extruder, dried for 3 hours at 120 ℃, and baked for 4 hours at 600 ℃ to obtain a carrier Z1.
Taking 100 g of carrier Z1, and using 81 ml of carrier Z containing WO 3 271.6 g/l, niO 24.7 g/l, P 2 O 5 12.3 g/L of a mixed solution of ammonium metatungstate, basic nickel carbonate and phosphoric acid is immersed for 3 hours, dried for 3 hours at 120 ℃ and then activated for 3 hours at 200 ℃ to obtain a catalyst C1. The theoretical composition based on the catalyst is shown in Table 2.
Example 2
200.0 g of pseudo-boehmite (catalyst Kaolin Co.) with a dry basis of 70%, 28.2 g of Y-type molecular sieve with a dry basis of 85% and 43.9 g of ITQ-37 molecular sieve with a dry basis of 82% are weighed, a proper amount of auxiliary agent containing inorganic binder, extrusion aid and the like are added and uniformly mixed, a butterfly-shaped carrier strip with a circumcircle diameter of 1.6 mm is extruded on a strip extruder, and the carrier Z2 is obtained after drying at 120 ℃ for 3 hours and roasting at 600 ℃ for 4 hours.
100 g of carrier Z2 was taken and 81 ml of each of the carriers containing WO 3 271.6 g/l, niO 24.7 g/l, P 2 O 5 12.3 g/L of mixed solution of ammonium metatungstate, basic nickel carbonate and phosphoric acid is immersed for 3 hours, dried for 3 hours at 120 ℃ and then activated for 3 hours at 200 ℃ to obtain the catalyst C2. The theoretical composition based on the catalyst is shown in Table 2.
Example 3
200.0 g of pseudo-boehmite (catalyst Kaolin Co.) with a dry basis of 70%, 28.2 g of Y-type molecular sieve with a dry basis of 85% and 43.9 g of ITQ-37 molecular sieve with a dry basis of 82% are weighed, and a proper amount of auxiliary agent containing organic binder, extrusion aid and the like are added to be uniformly mixed, extruded into a butterfly-shaped carrier strip with a circumcircle diameter of 1.6 mm on a strip extruder, dried for 3 hours at 120 ℃, and baked for 4 hours at 600 ℃ to obtain a carrier Z3.
100 g of carrier Z3 was taken and 95ml of each of the carriers containing WO 3 231.6 g/l, niO 21.1 g/l, P 2 O 5 10.5 g/L of mixed solution of ammonium metatungstate, basic nickel carbonate and phosphoric acid is soaked for 3 hours, dried at 120 ℃ for 3 hours, and then activated at 200 ℃ for 3 hours, so as to obtain the catalyst C3. The theoretical composition based on the catalyst is shown in Table 2.
Example 4
100 g of carrier Z2 was taken and 81 ml of each of the carriers containing WO 3 92.6 g/l, niO 12.3 g/l, P 2 O 5 6.2 g/L of mixed solution of ammonium metatungstate, basic nickel carbonate and phosphoric acid is soaked for 3 hours, dried for 3 hours at 120 ℃ and then activated for 3 hours at 200 ℃ to obtain the catalyst C4. The theoretical composition based on the catalyst is shown in Table 2.
Example 5
100 g of carrier Z2 was taken and 81 ml of each of the carriers containing WO 3 543.2 g/l, niO 111.1 g/l, P 2 O 5 24.7 g/L of mixed solution of ammonium metatungstate, basic nickel carbonate and phosphoric acid is soaked for 3 hours, dried at 120 ℃ for 3 hours, and then activated at 200 ℃ for 3 hours, so as to obtain the catalyst C5. The theoretical composition based on the catalyst is shown in Table 2.
Example 6
Taking 100 g of carrier Z2, and respectively containing MoO by 81 ml 3 185.2 g/l, niO 24.7 g/l, P 2 O 5 12.3 g/L of mixed solution of molybdenum trioxide, basic nickel carbonate and phosphoric acid is immersed for 3 hours, dried for 3 hours at 120 ℃, and then activated and roasted for 3 hours at 200 ℃ to obtain the catalyst C6. The theoretical composition based on the catalyst is shown in Table 2.
Example 7
200.0 g of pseudo-boehmite (catalyst Kaolin Co.) with a dry basis of 70%, 28.2 g of Y-type molecular sieve with a dry basis of 85% and 44.4 g of OSB molecular sieve with a dry basis of 81% are weighed, and a proper amount of auxiliary agent containing inorganic binder, extrusion aid and the like are added to be uniformly mixed, extruded into a butterfly-shaped carrier strip with a circumscribed circle diameter of 1.6 mm on a strip extruder, dried for 3 hours at 120 ℃, and baked for 4 hours at 600 ℃ to obtain a carrier Z7.
The carrier Z7 was taken in an amount of 100 g and 83 ml of each of which contained WO 3 265.1 g/l, niO 24.1 g/l and P 2 O 5 The catalyst C7 was obtained by immersing a mixed solution of 12.0 g/L of ammonium metatungstate, basic nickel carbonate and phosphoric acid for 3 hours, drying at 120℃for 3 hours, and activating at 200℃for 3 hours. The theoretical composition based on the catalyst is shown in Table 2.
Example 8
114.3 g of pseudo-boehmite with a dry basis of 70 percent (catalyst Kaolin division Co.), 28.2 g of Y-type molecular sieve with a dry basis of 85 percent, 44.4 g of OSB molecular sieve with a dry basis of 81 percent and 78.9 g of amorphous silica alumina material with a dry basis of 76 percent (Siral 40 of Condea company, germany) are weighed, a proper amount of auxiliary agent containing inorganic binder, extrusion aid and the like are added and uniformly mixed, a butterfly-shaped carrier strip with a circumcircle diameter of 1.6 mm is extruded on a strip extruder, and is dried at 120 ℃ for 3 hours and baked at 600 ℃ for 4 hours to obtain a carrier Z8.
Taking carrier Z8 g and using 85ml to respectively contain WO 8 g 3 258.8 g/l, niO 23.5 g/l, P 2 O 5 11.8 g/L of mixed solution of ammonium metatungstate, basic nickel carbonate and phosphoric acid is immersed for 3 hours, dried for 3 hours at 120 ℃, and then activated and roasted for 3 hours at 200 ℃ to obtain the catalyst C8. The theoretical composition based on the catalyst is shown in Table 2.
Example 9
257.1 g of pseudo-boehmite (catalyst Kaolin Co.) with a dry basis of 70%, 9.4 g of Y-type molecular sieve with a dry basis of 85% and 14.8 g of OSB molecular sieve with a dry basis of 81% are weighed, and a proper amount of auxiliary agent containing inorganic binder, extrusion aid and the like are added to be uniformly mixed, and extruded into a butterfly-shaped carrier strip with a circumcircle diameter of 1.6 mm on a strip extruder, and dried for 3 hours at 120 ℃ and baked for 4 hours at 600 ℃ to obtain a carrier Z9.
Taking carrier Z9 to 100 g, using 80ml each containing WO 3 275.0 g/l, 25.0 g/l NiO,P 2 O 5 12.5 g/L of a mixed solution of ammonium metatungstate, basic nickel carbonate and phosphoric acid is immersed for 3 hours, dried for 3 hours at 120 ℃ and then activated for 3 hours at 200 ℃ to obtain a catalyst C9. The theoretical composition based on the catalyst is shown in Table 2.
Example 10
142.9 g of pseudo-boehmite with a dry basis of 70 percent (catalyst Kaolin division Co.), 47.1 g of Y-type molecular sieve with a dry basis of 85 percent (catalyst Kaolin division Co., unit cell constant of 24.60A) and 74.1 g of OSB molecular sieve with a dry basis of 81 percent are weighed, a proper amount of auxiliary agent containing inorganic binder, extrusion aid and the like are added and uniformly mixed, and the mixture is extruded into a butterfly-shaped carrier strip with a circumcircle diameter of 1.6 mm on a strip extruder, and is dried for 3 hours at 120 ℃, and baked for 4 hours at 600 ℃ to obtain a carrier Z10.
The carrier Z10 g was taken and 88 ml of each of the carriers containing WO 3 250.0 g/l, niO 22.7 g/l, P 2 O 5 11.4 g/L of a mixed solution of ammonium metatungstate, basic nickel carbonate and phosphoric acid is immersed for 3 hours, dried at 120 ℃ for 3 hours, and then activated at 200 ℃ for 3 hours, thus obtaining a catalyst C10. The theoretical composition based on the catalyst is shown in Table 2.
Comparative example 1
200.0 g of pseudo-boehmite (catalyst Kaolin Co., ltd.) with a dry basis of 70% and 70.6 g of Y-type molecular sieve (catalyst Kaolin Co., ltd., unit cell constant of 24.60A) with a dry basis of 85% are weighed, and a proper amount of auxiliary agent containing inorganic binder, extrusion aid and the like are added to be uniformly mixed, and extruded into a butterfly-shaped carrier strip with a circumscribed circle diameter of 1.6 mm on a strip extruder, and dried at 120 ℃ for 3 hours and baked at 600 ℃ for 4 hours to obtain a carrier DZ.
100 g of carrier DZ was taken and 78 ml of each of them contained WO 3 282.1 g/l, niO 25.6 g/l, P 2 O 5 12.8 g/L of mixed solution of ammonium metatungstate, basic nickel carbonate and phosphoric acid is immersed for 3 hours, dried for 3 hours at 120 ℃ and then activated for 3 hours at 200 ℃ to obtain the catalyst DC. The theoretical composition based on the catalyst is shown in Table 2.
TABLE 1
Molecular sieve numbering Pore volume/(cm) 3 /g) Acid density/(mmol/m) 2 ) N value
ITQ-37 0.501 2.122 1.79
OSB-1 0.611 1.711 1.45
Y 0.412 3.121 1.00
TABLE 2
Test case
At a density of 0.9561g/cm 3 A sulfur content of 9800ppm, a nitrogen content of 743ppm and a total aromatics content of 85.7%The performance of catalysts C1, C2, C3, C7 and DC was evaluated on a 30 ml fixed bed unit using catalytically cracked diesel as the feedstock. The specific method comprises the following steps: the upper part of the bed layer is filled with industrial refined catalyst, the lower part is filled with catalyst, and the loading amount of the catalyst is 15 milliliters. Pre-vulcanizing the catalyst before feeding the raw oil, wherein the vulcanization conditions are as follows: vulcanizing at 110 ℃ for 2 hours and vulcanizing at 300 ℃ for 4 hours, wherein the vulcanized oil is kerosene containing 6 weight percent of carbon disulfide. Reaction conditions in the hydrofining reaction zone: the reaction temperature is 350 ℃, the hydrogen partial pressure is 6.5MPa, and the liquid hourly space velocity is 1.5h -1 Hydrogen-oil volume ratio 800, hydrotreating reaction zone reaction conditions: the reaction temperature is 370 ℃, the hydrogen partial pressure is 6.5MPa, and the liquid hourly space velocity of the modifier is 1.2h -1 Hydrogen oil volume ratio 800.
The test results are shown in Table 3.
TABLE 3 Table 3
Catalyst C1 C2 C3 C7 DC
The removal rate of the arene with more than double rings is% 75％ 82％ 78％ 85％ 70％
Cetane index improvement value Benchmark +0.4 Benchmark +0.5 Benchmark +0.4 Benchmark +0.6 Datum
The test results in table 3 show that the catalyst of the present disclosure has a higher polycyclic aromatic hydrocarbon removal rate, and when the catalyst is applied to deep hydrogenation dearomatization of diesel oil, the polycyclic aromatic hydrocarbon content in the diesel oil product is lower, and the cetane number is higher.
The preferred embodiments of the present disclosure have been described in detail above, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present disclosure does not further describe various possible combinations.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.

Claims (10)

1. The deep hydrogenation dearomatization catalyst for diesel oil is characterized by comprising a carrier and an active metal component loaded on the carrier; the active metal component comprises a VIII group metal element and a VIB group metal element; the carrier comprises a composite molecular sieve and a heat-resistant inorganic oxide matrix, wherein the composite molecular sieve comprises a first molecular sieve and a second molecular sieve, the first molecular sieve is a Y molecular sieve, and the second molecular sieve is a molecular sieve with an N value larger than 1;
wherein the definition of N value of a certain molecular sieve to be detected is the ratio of the adsorption quantity of the molecular sieve to be detected to the dicyclic arene and the derivative thereof to the adsorption quantity of a standard molecular sieve to the dicyclic arene and the derivative thereof, the standard molecular sieve is an HY molecular sieve, and the standard molecular sieve is SiO 2 And Al 2 The O molar ratio was 5.4 and the unit cell constant was 24.60 Angstrom.
2. The catalyst of claim 1 wherein the second molecular sieve has an N value of 1 to 10, preferably the second molecular sieve has an N value of 1 to 5; optionally, the second molecular sieve has a pore volume of 0.4 to 0.8cm 3 Per gram, acid density of 0.8-2.5 mu mol/m 2 。
3. The catalyst according to claim 1, wherein the weight ratio of the first molecular sieve to the second molecular sieve in the composite molecular sieve is from 1:9 to 9:1, preferably from 1:1 to 9:1.
4. The catalyst according to claim 1, wherein the composite molecular sieve is contained in the carrier in an amount of 5 to 70% by weight and the heat-resistant inorganic oxide matrix is contained in an amount of 30 to 95% by weight, based on the total weight of the carrier.
5. The catalyst according to claim 1, wherein the catalyst comprises, on an oxide basis, 50 to 85 wt.% of the support, 1.5 to 6 wt.% of the group VIII metal element, 10 to 35 wt.% of the group VIB metal element, based on the total weight of the catalyst.
6. The catalyst according to claim 1, wherein,
the first molecular sieve is at least one selected from HY molecular sieve, rare earth type Y molecular sieve REY, rare earth type HY molecular sieve REHY, ultrastable Y molecular sieve USY, partially amorphous USY, rare earth type ultrastable Y molecular sieve REUSY, titanium-containing Y molecular sieve, phosphorus-containing Y, ultrastable and HY type molecular sieve and dealuminated Y type molecular sieve; preferably, the first molecular sieve is at least one selected from the group consisting of an HY molecular sieve, a rare earth Y molecular sieve, a rare earth HY molecular sieve, an ultrastable Y molecular sieve, a rare earth ultrastable Y molecular sieve, a partially amorphous Y molecular sieve, a titanium-containing Y molecular sieve, and a phosphorus-containing Y-type molecular sieve;
the second molecular sieve is at least one selected from an ITQ-40 molecular sieve, an ITQ-44 molecular sieve, an ITQ-37 molecular sieve, an ITQ-53 molecular sieve, an ITQ-54 molecular sieve, an OSB-1 molecular sieve and an EMC-2 molecular sieve;
the refractory inorganic oxide matrix is selected from at least one of alumina, silica, and silica-alumina.
7. A process for preparing the catalyst of any one of claims 1-6, comprising:
s1, mixing a first molecular sieve, a second molecular sieve, a heat-resistant inorganic oxide matrix and an auxiliary agent, kneading and extruding to obtain an extruded strip; carrying out first drying and first roasting on the extruded strip to obtain a carrier; the auxiliary agent is at least one selected from inorganic binders and extrusion aids;
s2, impregnating the carrier by using an aqueous solution containing a compound of a VIII group metal and a compound of a VIB group metal to obtain an impregnated carrier; and carrying out second drying and activating treatment on the impregnated carrier.
8. The method of claim 7, wherein the weight ratio of the first molecular sieve, the second molecular sieve, and the refractory inorganic oxide matrix is from 1 to 25:4-45:30-95.
9. The method of claim 7, wherein,
in step S1, the conditions of the first drying process include: the drying temperature is 80-300 ℃, preferably 100-200 ℃; the drying time is 1-12 hours, preferably 2-8 hours; the conditions of the first firing include: the roasting temperature is 350-850 ℃, preferably 450-650 ℃; the calcination time is 1 to 12 hours, preferably 2 to 6 hours;
in step S2, the conditions of the impregnation include: the dipping temperature is between room temperature and 150 ℃ and the dipping time is between 1 and 6 hours; the second drying conditions include: the temperature is 100-300 ℃, preferably 100-150 ℃; the time is 2-8 hours; the activation treatment conditions include: the temperature is 100-350deg.C, preferably 120-250deg.C; the time is 1-12 hours, preferably 2-6 hours.
10. A method for deep hydrotreating of diesel fuel, characterized in that the diesel fuel and hydrogen are contacted with the catalyst according to any one of claims 1 to 6 and subjected to a hydrocracking reaction.
CN202210613300.1A 2022-05-31 2022-05-31 Deep hydrogenation dearomatization catalyst for diesel oil and preparation method and application thereof Pending CN117181292A (en)

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