CN117181294A - Diesel oil hydro-upgrading catalyst and preparation method and application thereof - Google Patents

Diesel oil hydro-upgrading catalyst and preparation method and application thereof Download PDF

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CN117181294A
CN117181294A CN202210616065.3A CN202210616065A CN117181294A CN 117181294 A CN117181294 A CN 117181294A CN 202210616065 A CN202210616065 A CN 202210616065A CN 117181294 A CN117181294 A CN 117181294A
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molecular sieve
catalyst
hours
carrier
value
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杨平
樊亚明
杨清河
任亮
胡志海
张奎
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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 present disclosure relates to a diesel hydro-upgrading catalyst, a preparation method and applications 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 0.6 and a Db value larger than 1; the N value is defined as the ratio of the adsorption quantity of the molecular sieve to the dicyclic arene and the derivative thereof to the adsorption quantity of the standard molecular sieve to the dicyclic arene and the derivative thereof; the Db value is defined as the ratio of the square of the adsorption of molecular sieve to butylbenzene to the product of the adsorption of molecular sieve to methyl indane and the adsorption of benzene. The catalyst disclosed by the invention can realize the directional hydrogenation ring opening of polycyclic aromatic hydrocarbon in diesel oil fraction, thereby improving the cetane number of diesel oil products.

Description

Diesel oil hydro-upgrading catalyst and preparation method and application thereof
Technical Field
The present disclosure relates to the field of catalysts, and in particular, to a diesel hydro-upgrading catalyst, and a preparation method and application thereof.
Background
As fuel oil quality standards are becoming more stringent, diesel quality requirements are also becoming more stringent with respect to sulfur content, polycyclic aromatic hydrocarbon content, cetane number, density, and other metrics. The existing diesel pool has higher occupation ratio of catalytic diesel, but the catalytic diesel is rich in aromatic hydrocarbon and mainly contains polycyclic aromatic hydrocarbon, and has low cetane number and high density; and the quality of the catalytic diesel is continuously reduced under the influence of the heavy (inferior) quality of the crude oil and the increase of the causticity of the catalytic cracking device. Therefore, under the double pressures of poor quality of raw materials and high quality of products, the efficient conversion of polycyclic aromatic hydrocarbon in catalytic diesel oil into high cetane number components is a key for producing diesel oil blending components by catalytic diesel oil quality improvement.
The hydrogenation modification technology can convert non-ideal components of polycyclic aromatic hydrocarbon with high density and low cetane number in diesel oil into ideal components of long side chain alkylbenzene with high cetane number through the combination of selective hydrogenation saturation and selective ring-opening reaction, and can also meet the aim of reducing the content and density of polycyclic aromatic hydrocarbon in high-quality diesel oil. The hydrogenation ring opening of the polycyclic aromatic hydrocarbon is a complex process comprising a series of parallel sequential reactions such as hydrogenation, isomerization, ring opening, cracking, polymerization and the like, and the precise control of the reaction process and the ring opening reaction of deep and directional reinforced polycyclic aromatic hydrocarbon is a key difficult problem in the hydrogenation modification process. The hydro-upgrading process is a heterogeneous catalysis process, and reactants need to undergo diffusion, adsorption, reaction, desorption, diffusion and other processes. The diffusion, absorption and desorption properties of reactants, reaction intermediates and product molecules are effectively regulated and controlled from the reaction time and the reaction space scale, and the high-activity and high-selectivity conversion of the polycyclic aromatic hydrocarbon into a ring-opening product, namely long side chain alkylbenzene or long side chain alkyl cycloalkane, is the core for accurately controlling the hydrogenation ring-opening reaction process of the polycyclic aromatic hydrocarbon.
Chinese patent document 201210194486.8 discloses a diesel hydrogenation catalyst, which also comprises a rare earth modified USY molecular sieve, amorphous silicon aluminum, macroporous aluminum oxide and hydrogenation active components. Wherein the catalyst is used as a reference, the content of the rare earth modified USY molecular sieve is 5-60%, the amorphous silicon-aluminum is 5-80%, and the content of the VIII group metal is 0.1-10%. The catalyst can improve the cetane number of diesel under the condition of mild hydrogenation.
Chinese patent document 201210109193.5 discloses a catalyst for hydrogenating and modifying diesel oil by cracking diesel oil, which comprises a hydrogenation active metal component, a modified Y molecular sieve, amorphous silicon-aluminum and a carrier of alumina, wherein the content of the Y molecular sieve is 5-20%, the amorphous silicon-aluminum accounts for 10-20% by counting the catalyst, and the SiO in the amorphous silicon-aluminum 2 The content is 20-75%, the pore volume is 0.25-0.80 mL/g, and the specific surface area is 150-500 m 2 The average grain size of the Y molecular sieve is less than 100nm and SiO 2 /Al 2 O 3 The molar ratio is 9-20:1, the relative crystallinity is more than 75 percent, and the specific surface area is 500-800 m 2 And/g. The catalyst can be used for improving cetane number while maintaining high diesel oil yield when catalyzing diesel oil hydrogenation modification.
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 is used in the hydrocracking process and is favorable for the hydro-ring-opening conversion of polycyclic aromatic hydrocarbon.
The catalyst provided in the above patent document can raise the cetane number of the diesel oil product to some extent, but the hydrogenation modification effect on the whole diesel oil is still not ideal.
Disclosure of Invention
The purpose of the present disclosure is to provide a diesel hydro-upgrading catalyst to realize directional hydro-ring opening of polycyclic aromatic hydrocarbons in diesel fractions, thereby improving the cetane number of diesel products and simultaneously reducing density and polycyclic aromatic hydrocarbon content.
To achieve the above object, the present disclosure is a firstAspects provide a diesel hydro-upgrading 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 0.6 and a Db 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 SiO in the standard molecular sieve 2 And Al 2 The O molar ratio was 5.4 and the unit cell constant was 24.60 Angstrom; the Db value of a certain molecular sieve to be detected is defined as the ratio of the square of the adsorption quantity of the molecular sieve to be detected on butylbenzene to the product of the adsorption quantity of the molecular sieve to be detected on methyl indane and the adsorption quantity of the molecular sieve to be detected on benzene.
Optionally, the second molecular sieve has a Db value of 1 to 10 and an n value of 1 to 10, preferably, the second molecular sieve has a Db value of 1 to 8 and 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.
Optionally, the composite molecular sieve is present in the support in an amount of from 5 to 60 wt% and the refractory inorganic oxide matrix is present in an amount of from 40 to 95 wt% based on the total weight of the support.
Alternatively, the catalyst contains 40-75 wt.% of a support, 1.5-6 wt.% of a group VIII metal element, and 10-35 wt.% of a group VIB metal element, on an oxide basis.
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 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 ITQ-33 molecular sieve, UCR-20 molecular sieve and ITQ-40 molecular sieve; 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 1-20:4-40:40-95.
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. .
A third aspect of the present disclosure provides a method of hydro-upgrading diesel, the method comprising: diesel oil and hydrogen are contacted with the hydrocracking catalyst to carry out hydrocracking reaction.
Through the technical scheme, the catalyst disclosed by the invention can realize the directional hydrogenation ring opening of the polycyclic aromatic hydrocarbon in the diesel fraction, so that the cetane number of a diesel product is improved, and the density and the polycyclic aromatic hydrocarbon content are reduced.
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 hydro-upgrading 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 0.6 and a Db 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 SiO in the standard molecular sieve 2 And Al 2 The O molar ratio was 5.4 and the unit cell constant was 24.60 Angstrom; the Db value of a certain molecular sieve to be detected is defined as the ratio of the square of the adsorption quantity of the molecular sieve to be detected on butylbenzene to the product of the adsorption quantity of the molecular sieve to be detected on methyl indane and the adsorption quantity of the molecular sieve to be detected on benzene.
The N value and the Db value are obtained by an adsorption molar ratio test method, wherein the test method of the N value 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 ) Protection deviceAnd (3) protecting the solution, 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 test method of the Db value is specifically as follows: methyl indane, butylbenzene, benzene (100 ml, room temperature) were accurately measured separately, then quantitative molecular sieve material (5 g) was added, and the mixture was purified under inert gas (N 2 ) Protecting, sealing and stirring at 360 deg.C under 1 atm for 10 hr, filtering, re-sizing filtrate, cooling to room temperature, and measuring solution volume with a measuring cylinder to obtain adsorption volume difference DeltaV Test molecular sieve methyl indane 、ΔV Test molecular sieve-butylbenzene 、ΔV Test molecular sieve-benzene . The calculation formula of the Db value is as follows:
Db＝ΔV test molecular sieve-butylbenzene 2 /(ΔV Test molecular sieve methyl indane *ΔV Test molecular sieve-benzene )
Wherein DeltaV Test molecular sieve methyl indane 、ΔV Test molecular sieve-benzene Must be about 0.
The catalyst disclosed by the invention can effectively regulate and control the diffusion and adsorption performance of the polycyclic aromatic hydrocarbon molecules on the catalyst from the reaction time and space angle by improving the pore channel structure and size of the catalyst active component molecular sieve and the matching property of the reactant molecules, reaction intermediates and product molecular structures and sizes in the polycyclic aromatic hydrocarbon hydrogenation ring-opening process, and can precisely control the directional hydrogenation ring-opening process of the polycyclic aromatic hydrocarbon. Specifically, the molecular sieve of the catalyst acidic component is screened rationally through the N value and the Db value, the matching degree of the pore channel structure of the molecular sieve and the reactant, the reaction intermediate and the product molecules in the hydrogenation ring-opening process of the polycyclic aromatic hydrocarbon is enhanced, the directional hydrogenation ring-opening of the polycyclic aromatic hydrocarbon is realized, and the catalyst can be used in the process of improving the cetane number through the hydrogenation modification of diesel oil, especially the poor diesel oil rich in the polycyclic aromatic hydrocarbon.
In a preferred embodiment of the present disclosure, the second molecular sieve has a Db value of 1 to 10 and an n value of 1 to 10, and further preferably, the second molecular sieve has a Db value of 1 to 8 and 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 。
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 60 wt% and the refractory inorganic oxide matrix may be present in an amount of 40 to 95 wt% based on the total weight of the support.
According to the present disclosure, the catalyst may contain 40 to 75 wt.% of a support, 1.5 to 6 wt.% of a group VIII metal element, and 10 to 35 wt.% of a group VIB metal element, on an oxide basis.
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 selected from at least one 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 can be at least one selected from ITQ-33 molecular sieve, UCR-20 molecular sieve and ITQ-40 molecular sieve; 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 hydro-upgrading or hydrocracking 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.
Alternatively, the weight ratio of the first molecular sieve, the second molecular sieve, and the refractory inorganic oxide matrix may be from 1 to 20:4-40:40-95.
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.
A third aspect of the present disclosure provides a method of hydro-upgrading diesel, the method comprising: diesel oil and hydrogen are contacted with the hydrocracking catalyst to carry out hydrocracking reaction. The catalyst disclosed by the invention can be applied to the hydro-upgrading of diesel oil, so that the quality of the diesel oil can be effectively improved. The hydrocracking reactions described in this disclosure are carried out using a fixed bed sheet section tandem process. In a preferred embodiment of the present disclosure, the single-stage tandem process comprises a hydrofinishing reaction zone and a hydrocracking reaction zone; further preferably, the temperature of the hydrofining reaction zone can be 250-450 ℃, the reaction pressure can be 4.0-16.0MMPa, the hydrogen-oil volume ratio can be 200-1500, and the volume space velocity can be 0.5-2.5h -1 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the hydrocracking reaction can be 300-450 ℃, the reaction pressure can be 4.0-16.0MPa, the hydrogen-oil volume ratio can be 200-1500, and the volume airspeed can be 0.5-2.5h -1 。
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-33 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.
100 g of the carrier Z was taken and 79 ml of each of which contained WO 3 278.5 g/l, niO 25.3 g/l, P 2 O 5 12.7 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 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-33 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 79 ml of each of which contained WO 3 278.5 g/l, niO 25.3 g/l, P 2 O 5 12.7 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 C2. The 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-33 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.
Taking 100 g of carrier Z3, using 91 ml of carrier Z containing WO 3 241.8 g/l, niO 22.0 g/l, P 2 O 5 11.0 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 C3. Based on the catalyst, the composition is shown in the table2.
Example 4
100 g of carrier Z2 was taken and 79 ml of each of which contained WO 3 94.9 g/l, niO 12.7 g/l, P 2 O 5 6.3 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 composition based on the catalyst is shown in Table 2.
Example 5
100 g of carrier Z2 was taken and 79 ml of each of which contained WO 3 557.0 g/l, niO 113.9 g/l and P 2 O 5 25.3 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 composition based on the catalyst is shown in Table 2.
Example 6
Taking carrier Z2 g and using 79 ml to respectively contain MoO 3 189.9 g/l, niO 25.3 g/l, P 2 O 5 12.7 g/L of a mixed solution of molybdenum trioxide, 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 to obtain a catalyst C6. The 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 UCR-20 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 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 Z7.
Taking carrier Z7 to 100 g, using 81 ml each 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 C7. The 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 UCR-20 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 mixed uniformly, a butterfly-shaped carrier strip with a circumcircle diameter of 1.6 mm is extruded on a strip extruder, and the carrier Z8 is obtained after drying at 120 ℃ for 3 hours and roasting at 600 ℃ for 4 hours.
Taking carrier Z8 g and using 83 ml to respectively contain WO 8 g 3 265.1 g/l, niO 24.1 g/l and P 2 O 5 The catalyst C8 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 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 UCR-20 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 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 Z9.
Taking carrier Z9 to 100 g, using 78 ml each containing WO 3 282.1 g/l, niO 25.6 g/l, P 2 O 5 12.8 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 composition based on the catalyst is shown in Table 2.
Example 10
142.9 g of pseudo-boehmite (catalyst Kaolin Co.) with a dry basis of 70%, 47.1 g of Y-type molecular sieve with a dry basis of 85% and 74.1 g of UCR-20 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 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 Z10.
Taking 10 g of carrier Z and using 85ml of carrier Z respectively containing WO 3 258.8 g/l, niO 23.5 g/l, P 2 O 5 11.8 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 composition based on the catalyst is shown in Table 2.
Comparative example 1
200.0 g of pseudo-boehmite (catalyst Kaolin Co.) with a dry basis of 70% and 70.6 g of Y-type molecular sieve with a dry basis of 85% are weighed, a proper amount of auxiliary agent containing inorganic binder, extrusion aid and the like are added and mixed uniformly, a butterfly-shaped carrier strip with a circumscribed circle diameter of 1.6 mm is extruded on a strip extruder, and the carrier DZ is obtained after drying for 3 hours at 120 ℃ and roasting for 4 hours at 600 ℃.
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 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 Db value
ITQ-33 0.497 1.723 0.97 2.33
UCR-20 0.399 2.291 2.20 2.10
Y 0.412 3.121 1.00 0.65
TABLE 2
Test case
At a density of 0.9561 g/cm 3 Catalytic cracking diesel oil with a sulfur content of 9800ppm, a nitrogen content of 743ppm and a total aromatics content of 85.7% was used as a feedstock and the performance of catalysts C1, C2, C3, C7 and DC were evaluated on a 30 ml fixed bed unit. 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 D1
Cetane number increase value Benchmark +1.2 Benchmark +0.9 Benchmark +0.4 Benchmark +0.7 Datum
Density reduction value Benchmark +0.001 Benchmark +0.005 Benchmark +0.002 Benchmark +0.003 Datum
The test results in table 3 show that the catalyst provided by the present disclosure has higher hydrodearomatization performance, lower content of polycyclic aromatic hydrocarbon in diesel oil product, and higher cetane number increase value.
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. A diesel hydro-upgrading catalyst, which 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 0.6 and a Db 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 SiO in the standard molecular sieve 2 And Al 2 The O molar ratio was 5.4 and the unit cell constant was 24.60 Angstrom; the Db value of a certain molecular sieve to be detected is defined as the ratio of the square of the adsorption quantity of the molecular sieve to be detected on butylbenzene to the product of the adsorption quantity of the molecular sieve to be detected on methyl indane and the adsorption quantity of the molecular sieve to be detected on benzene.
2. The catalyst of claim 1, wherein the second molecular sieve has a Db value of 1 to 10 and an n value of 1 to 10, preferably wherein the second molecular sieve has a Db value of 1 to 8 and 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 60% by weight and the refractory inorganic oxide matrix is contained in an amount of 40 to 95% by weight, based on the total weight of the carrier.
5. The catalyst according to claim 1, wherein the catalyst comprises 40 to 75 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, calculated as oxides, 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 selected from at least one of ITQ-33 molecular sieve, UCR-20 molecular sieve and ITQ-40 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 20:4-40:40-95.
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 hydro-upgrading diesel oil, which is characterized by comprising the following steps: the hydrocracking reaction is carried out by contacting diesel oil and hydrogen with the hydrocracking catalyst as claimed in any one of claims 1 to 6.
CN202210616065.3A 2022-05-31 2022-05-31 Diesel oil hydro-upgrading catalyst and preparation method and application thereof Pending CN117181294A (en)

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