CN111632620A - Medium oil type hydrocracking catalyst - Google Patents

Medium oil type hydrocracking catalyst Download PDF

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Publication number
CN111632620A
CN111632620A CN202010550141.6A CN202010550141A CN111632620A CN 111632620 A CN111632620 A CN 111632620A CN 202010550141 A CN202010550141 A CN 202010550141A CN 111632620 A CN111632620 A CN 111632620A
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molecular sieve
oil type
medium oil
hydrocracking catalyst
type hydrocracking
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CN111632620B (en
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范文青
徐琳
张黎
刘长坤
肖文灿
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Sinochem Quanzhou Petrochemical Co Ltd
Sinochem Quanzhou Energy Technology Co Ltd
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Sinochem Quanzhou Petrochemical Co Ltd
Sinochem Quanzhou Energy Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • B01J35/695—Pore distribution polymodal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a medium oil type hydrocracking catalyst and a preparation method thereof, wherein the medium oil type hydrocracking catalyst is prepared by adopting a modified Y molecular sieve subjected to simple hydrothermal treatment, so that the problems of low selectivity of middle distillate oil and low yield of liquid products of the existing catalyst are solved, and the output benefit of a medium oil type hydrocracking process is remarkably improved.

Description

Medium oil type hydrocracking catalyst
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a medium oil type hydrocracking catalyst.
Background
The hydrocracking process is an oil refining process for converting high-boiling raw material into low-boiling naphtha, kerosene and diesel oil. Compared with catalytic cracking, the method has the advantages of high raw material adaptability, high yield of middle distillate and good quality. With the decline of the high-sulfur fuel oil market and the increasing demand of society for clean transportation fuel oil, the hydrocracking process becomes the core process of modern refineries.
Hydrocracking catalysts are typically bifunctional catalysts, generally comprising a bifunctional center: the first is a metal center, generally consists of VIB group metals or VIB and VIII group binary metal systems, has the hydrogenation/dehydrogenation function, and can also saturate aromatic hydrocarbon; the second is an acid center with cracking function, provided by amorphous silica-alumina or molecular sieve (most commonly Y molecular sieve), for cracking long-chain macromolecules.
When the hydrocracking catalyst prepared by the conventional Y molecular sieve is used in a hydrocracking process, middle distillate oil molecules, particularly kerosene fractions, are easy to undergo deep cracking reaction in microporous pore channels of the molecular sieve to generate C1-C4 gaseous light hydrocarbons with low value, so that the selectivity of the middle distillate oil in the product is low, and the yield of liquid products is low. Therefore, there is a need to develop new hydrocracking catalysts with higher selectivity for middle distillates, in particular diesel distillates.
The pore channel structure of the hydrocracking catalyst is reformed to form more mesoporous pore channels, so that the primary cracking product can be rapidly diffused from the microporous pore channels, the probability of deep cracking reaction is reduced, the generation of low-value C1-C4 gaseous hydrocarbons is reduced, and the selectivity of middle distillate oil and the yield of liquid products are improved. Since the cracking reaction usually occurs in the microporous pore channels of the molecular sieve, forming mesoporous pores on the Y molecular sieve is the best way to modify the pore channel structure of the catalyst. Usually, a chemical method, such as strong acid, strong base or complexing agent, is used to remove silicon or aluminum on the framework of the Y molecular sieve part, and then high temperature heat treatment is carried out to form mesopores on the molecular sieve. The existing ultrastable Y molecular sieve used for a hydrocracking catalyst is generally subjected to dealuminization treatment to adjust the strength and concentration of acid centers, and further strong chemical treatment is easy to cause further reduction of the number of the acid centers and influence the activity of the catalyst; meanwhile, the further desiliconization of the molecular sieve framework or the reduction of the crystallinity is easily caused by aluminum, so that the thermal stability of the molecular sieve is reduced, and the catalyst is quickly inactivated in the operation process.
Disclosure of Invention
Aiming at the problems of low selectivity of middle distillate and low yield of liquid products in the conventional middle oil type hydrocracking catalyst, the invention provides a novel middle oil type hydrocracking catalyst and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the objects of the present invention is to provide a medium oil type hydrocracking catalyst, which comprises the following components:
(a) a metal of group VIII element or an oxide thereof;
(b) a metal of group VIB element or an oxide thereof;
(c) amorphous silicon aluminum;
(d) alumina;
(e) and (3) modifying the Y molecular sieve.
In the technical scheme, the component (a) is 0.1-35 parts by weight, preferably 15-25 parts by weight.
In the technical scheme, the component (b) is 0.1-10 parts by weight, preferably 4-8 parts by weight.
In the above technical scheme, the component (c) is 1 to 60 parts by weight, preferably 20 to 40 parts by weight.
In the above technical scheme, the component (d) is 1 to 80 parts by weight, preferably 20 to 50 parts by weight.
In the technical scheme, the component (e) is 0.1-30 parts by weight, preferably 1-10 parts by weight.
In the above technical solution, the group VIII element is selected from at least one of Co or Ni.
In the above technical solution, the group VIB element is selected from at least one of Mo or W.
In the technical scheme, the amorphous silicon-aluminum is obtained by roasting at 500 ℃ for 4 hours in the air atmosphere in advance; the specific surface area is 200-600 m2A pore volume of 0.5 to 1.5 cm/g3Preferably 1.1 to 1.5 cm/g3(ii)/g; in percent by weight, SiO2The content is 20-80%.
In the technical scheme, the aluminum oxide is obtained by roasting pseudo-boehmite for 4 hours at 500 ℃ in an air atmosphere; the specific surface area is 150-400 m2A pore volume of 0.3 to 0.8 cm3The Na element content is less than or equal to 0.2 percent in percentage by weight.
In the technical scheme, the modified Y molecular sieve is prepared by adding the Y molecular sieve and an ionic surfactant into ammonia water, fully stirring at room temperature, placing the mixture into a high-pressure reaction kettle for hydrothermal treatment, and then filtering and drying the mixture.
Wherein the Y molecular sieve is a hydrogen type molecular sieve, and the specific surface area of the Y molecular sieve is 400-900 m2Preferably 500 to 800 m/g2(ii)/g; the total pore volume is 0.30-0.80 cm3Per g, wherein the mesoporous volume is less than 0.15 cm3A Si/Al molar ratio of 5 to 30, and a unit cell size of 24.25 to 24.45
Figure 100002_DEST_PATH_IMAGE002
。
The mass ratio of the used Y molecular sieve to the ionic surfactant is 1: (0.1 to 3); the ionic surfactant is a cationic surfactant, preferably an ammonium salt or amine salt type cationic surfactant, and more preferably at least one of cetyltrimethylammonium chloride (CTAC) and cetyltrimethylammonium bromide (CTAB).
The mass ratio of the used Y molecular sieve to ammonia water is 1: (1-500); ammonia monohydrate (NH) in the ammonia water in percentage by weight4OH) content of 0.5 to 5%.
The temperature of the hydrothermal treatment is 100-200 ℃, and the time is 1-48 h; the drying temperature is 80-200 ℃, and the drying time is 1-24 hours.
It is another object of the present invention to provide a method for preparing the middle-oil type hydrocracking catalyst, which comprises the steps of:
(1) uniformly mixing pseudo-boehmite, amorphous silicon-aluminum and a modified Y molecular sieve, adding an acid solution, fully kneading, forming, drying, heating to a roasting target temperature under a nitrogen atmosphere, and then, switching to an air atmosphere for roasting to obtain a catalyst carrier;
(2) and (2) dispersing a VIB group element-containing compound and a VIII group element-containing compound in a solvent, impregnating the catalyst carrier obtained in the step (1), and then drying and roasting to obtain the medium oil type hydrocracking catalyst.
In the above technical solution, the acid solution in step (1) may be inorganic acid such as sulfuric acid, hydrochloric acid, and nitric acid, or organic acid such as formic acid, acetic acid, and citric acid; the concentration of the acid solution is 0.5wt% to 5wt%, preferably 1wt% to 3 wt%.
In the technical scheme, the size and shape of the formed product in the step (1) are preferably similar to those of a traditional hydrocracking commercial catalyst, and the product is more preferably prepared into an extrudate with a diameter of 1.5-3.5 nm and a length of 3-12 nm and a circular or clover section.
In the technical scheme, the drying temperature in the step (1) is 80-200 ℃, and the drying time is 2-24 hours; the heating rate under the nitrogen atmosphere is 1-20 ℃/min, the target temperature is 400-650 ℃, and the roasting time under the air atmosphere is 3-12 h.
In the above technical scheme, the group VIB element-containing compound and the group VIII element-containing compound in step (2) are not particularly limited, and may be reasonably selected by those skilled in the art.
In the above technical solution, the solvent used in step (2) is not particularly limited as long as the impregnation loading operation can be achieved, and the solvent may be directly dissolved, or dissolved by adjusting pH, or may be those capable of forming a colloid or forming a colloid by adjusting pH, and may be a single solvent or a mixed solvent.
In the technical scheme, the drying temperature in the step (2) is 80-200 ℃, and the drying time is 2-24 hours; the roasting temperature is 400-600 ℃, and the roasting time is 2-12 h.
The invention modifies the Y molecular sieve under the mild hydrothermal condition, and can be directly used for preparing the catalyst only by simple filtration and separation and without high-temperature heat treatment. Therefore, the improvement of the pore channel structure of the molecular sieve can be realized under the condition of not damaging the framework structure of the molecular sieve, more mesoporous channels are formed in the prepared hydrocracking catalyst, the rapid diffusion of a primary cracking product from the microporous channels is facilitated, the probability of deep cracking reaction is reduced, the generation of low-value C1-C4 gaseous hydrocarbons is reduced, and the selectivity of middle distillate oil and the yield of liquid products are improved.
Compared with the existing hydrocracking catalyst, the medium oil type hydrocracking catalyst prepared by using the modified Y molecular sieve can improve the selectivity of the middle distillate oil on the basis of improving the activity of the catalyst, and the yield of liquid products is improved accordingly. The output benefit can be obviously improved for producing the medium oil type hydrocracking unit.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
The amorphous silicon-aluminum is roasted for 4 hours at 500 ℃ in advance in the air atmosphere; the specific surface area is 200-600 m2A pore volume of 0.5 to 1.5 cm/g3(ii)/g; in percent by weight, SiO2The content is 20-80%.
Example 1
15.0 g of Y molecular sieve powder and 10.0g of CTAC were added to 1000 g of aqueous ammonia (NH)4OH content of 1 wt%), stirring thoroughly at room temperature for 30 min, placing in a high pressure reactor, hydrothermal treating at 170 ℃ for 24h, filtering and drying at 120 ℃ for 12h to obtain modified Y molecular sieve powder Y-1.
Example 2
15.0 g of Y molecular sieve powder and 20.0g of CTAC were added to 350 g of aqueous ammonia (NH)4OH content 2 wt%), stirring thoroughly at room temperature for 60 min, and then reacting under high pressureAnd performing hydrothermal treatment at 180 ℃ for 20 h in a kettle, filtering and drying at 140 ℃ for 30h to obtain modified Y molecular sieve powder Y-2.
Comparative example 1
15.0 g of Y molecular sieve powder and 20.0g of CTAC were added to 350 g of aqueous ammonia (NH)4OH content of 2 wt%), stirring thoroughly at room temperature for 60 minutes, then filtering and drying at 140 ℃ for 30 hours to obtain modified Y molecular sieve powder Y-3.
Table 1 shows the pore volume comparison results of the Y molecular sieve and the prepared modified Y molecular sieves Y-1, Y-2 and Y-3 (before measuring the pore volume, Y, Y-1, Y-2 and Y-3 are heated to 560 ℃ under a nitrogen atmosphere and then are switched to an air atmosphere for calcination for 6 hours).
TABLE 1 pore volume comparison of Y molecular sieves
Figure DEST_PATH_IMAGE004
As can be seen from Table 1, compared with the Y molecular sieve, the mesoporous pore volume of the modified Y-1 and Y-2 molecular sieves is increased, particularly, the increase of pores of 2-10 nm is most obvious, and the pore volume of the Y-3 molecular sieve modified by only adopting the surfactant is slightly increased.
Example 3
10.0g of the modified Y molecular sieve powder Y-1 prepared in example 1, 10.0g of amorphous silica-alumina powder and 12.0 g of pseudo-boehmite powder were uniformly mixed, then 1.5wt% of nitric acid solution was added, after sufficient kneading, the mixture was extruded into cloverleaf-shaped particles 3 to 10 mm long and 2 mm in diameter, the cloverleaf-shaped particles were dried at 140 ℃ for 10 hours, and then the mixture was heated to 560 ℃ in a nitrogen atmosphere and then calcined in an air atmosphere for 6 hours, thereby obtaining a catalyst carrier S-1.
Example 4
Nickel nitrate (Ni (NO)) that will provide sufficient nickel oxide (NiO) in the final catalyst3)2·6H2O) and sufficient tungsten trioxide (WO)3) Ammonium metatungstate ((NH)4)10W12O41·xH2O) was dispersed in deionized water and then used to impregnate the catalyst support S-1 obtained in example 3, followed by 12Drying at 0 deg.C for 10 hr, and calcining at 550 deg.C for 6 hr to obtain catalyst C-1.
Example 5
10.0g of the modified Y molecular sieve powder Y-2 prepared in example 2, 10.0g of amorphous silica-alumina powder and 12.0 g of pseudo-boehmite powder were mixed uniformly, then 1.5wt% of nitric acid solution was added, after sufficient kneading, cloverleaf particles 3-10 mm long and 2 mm in diameter were extruded, dried at 140 ℃ for 10 hours, then heated to 560 ℃ in a nitrogen atmosphere and calcined in an air atmosphere for 6 hours, to obtain a catalyst carrier S-2.
Example 6
Nickel nitrate (Ni (NO)) that will provide sufficient nickel oxide (NiO) in the final catalyst3)2·6H2O) and sufficient tungsten trioxide (WO)3) Ammonium metatungstate ((NH)4)10W12O41·xH2O) is dispersed in deionized water and then used for impregnating the catalyst carrier S-2 obtained in example 5, and then dried at 120 ℃ for 10 hours, and finally calcined at 550 ℃ for 6 hours to obtain the catalyst C-2.
Comparative example 2
(1) Uniformly mixing 10.0g of Y-3 powder prepared in comparative example 1, 10.0g of amorphous silica-alumina powder and 12.0 g of pseudo-boehmite powder, then adding 1.5wt% of nitric acid solution, fully kneading and extruding into cloverleaf-shaped particles with the length of 3-10 mm and the diameter of 2 mm, drying for 10 hours at 140 ℃, then heating to 560 ℃ in nitrogen atmosphere, and then switching to air atmosphere for roasting for 6 hours to obtain the catalyst carrier S-3.
(2) Nickel nitrate (Ni (NO)) that will provide sufficient nickel oxide (NiO) in the final catalyst3)2·6H2O) and sufficient tungsten trioxide (WO)3) Ammonium metatungstate ((NH)4)10W12O41·xH2O) is dispersed in deionized water, then used for dipping the catalyst carrier S-3, then dried for 10 hours at the temperature of 120 ℃, and finally roasted for 6 hours at the temperature of 550 ℃ to obtain the catalyst C-3.
Comparative example 3
(1) Uniformly mixing 10.0g Y molecular sieve powder, 10.0g amorphous silica-alumina powder and 12.0 g pseudo-boehmite powder, then adding 1.5wt% nitric acid solution, fully kneading and extruding into cloverleaf particles with the length of 3-10 mm and the diameter of 2 mm, drying for 10 hours at 140 ℃, then heating to 560 ℃ under nitrogen atmosphere and then switching to air atmosphere for roasting for 6 hours to obtain the catalyst carrier S-4.
(2) Nickel nitrate (Ni (NO)) that will provide sufficient nickel oxide (NiO) in the final catalyst3)2·6H2O) and sufficient tungsten trioxide (WO)3) Ammonium metatungstate ((NH)4)10W12O41·xH2O) is dispersed in deionized water, and then used for dipping the carrier S-3 obtained in the step (1), and then dried for 10 hours at the temperature of 120 ℃, and finally roasted for 6 hours at the temperature of 550 ℃ to obtain the catalyst C-4.
Comparative example 4
(1) Uniformly mixing 10.0g Y molecular sieve powder, 10.0g amorphous silica-alumina powder and 12.0 g pseudo-boehmite powder, then adding 1.5wt% nitric acid solution, fully kneading and extruding into cloverleaf particles with the length of 3-10 mm and the diameter of 2 mm, drying for 10 hours at 140 ℃, then heating to 560 ℃ in air atmosphere and roasting for 6 hours to obtain the catalyst carrier S-5.
(2) Nickel nitrate (Ni (NO)) that will provide sufficient nickel oxide (NiO) in the final catalyst3)2·6H2O) and sufficient tungsten trioxide (WO)3) Ammonium metatungstate ((NH)4)10W12O41·xH2O) is dispersed in deionized water, and then used for dipping the carrier S-4 obtained in the step (1), and then dried for 10 hours at the temperature of 120 ℃, and finally roasted for 6 hours at the temperature of 550 ℃ to obtain the catalyst C-5.
The pore volume results for the catalyst supports obtained in examples 3 and 5 and comparative examples 2 to 4 are shown in Table 2.
TABLE 2 pore volume of catalyst support
Figure DEST_PATH_IMAGE006
As can be seen from Table 2, compared with the carriers S-3, S-4 and S-5 prepared in the comparative ratio, the mesoporous volume of the carriers S-1 and S-2 is increased, and particularly, the increase of pores of 2-10 nm is most obvious.
Example 7
The catalyst performance was evaluated using a 50 mL small hydrogenation evaluation apparatus with one pass. H of 5% by volume was used before evaluation2S and 95% H2The catalyst is presulfurized by the formed mixed gas. The raw material used for evaluating the performance of the catalyst is hydrocracking cycle oil, and the properties and reaction process conditions thereof are shown in tables 3 and 4. The reaction temperature was adjusted as needed to ensure that the conversion was maintained at 68% by mass over 100 hours. The results of comparing the reaction properties of the respective catalysts are shown in Table 5.
TABLE 3 Properties of the feed oils
Figure DEST_PATH_IMAGE008
TABLE 4 reaction Process conditions
Figure DEST_PATH_IMAGE010
TABLE 5 catalyst evaluation results
Figure DEST_PATH_IMAGE012
As can be seen from Table 5, under the same conversion rate, the activity of the catalysts C-1 and C-2 is slightly better than that of the comparative example, the difference is small, but the selectivity of middle distillate oil, particularly the selectivity of diesel oil fraction, is obviously improved (by 3-4 percentage points), the generation of C1-C4 is reduced, and the liquid yield is also improved.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (10)

1. A medium oil type hydrocracking catalyst is characterized in that: comprises the following components:
(a) a metal of group VIII element or an oxide thereof;
(b) a metal of group VIB element or an oxide thereof;
(c) amorphous silicon aluminum;
(d) alumina;
(e) modifying a Y molecular sieve;
the modified Y molecular sieve is prepared by adding the Y molecular sieve and an ionic surfactant into ammonia water, fully stirring at room temperature, placing in a high-pressure reaction kettle for hydrothermal treatment, and then filtering and drying.
2. The medium oil type hydrocracking catalyst according to claim 1, characterized in that: the adhesive comprises, by weight, 0.1-35 parts of a component (a), 0.1-10 parts of a component (b), 1-60 parts of a component (c), 1-80 parts of a component (d) and 0.1-30 parts of a component (e).
3. The medium oil type hydrocracking catalyst according to claim 1, characterized in that: the VIII group element is at least one selected from Co or Ni.
4. The medium oil type hydrocracking catalyst according to claim 1, characterized in that: the VIB group element is at least one of Mo or W.
5. The medium oil type hydrocracking catalyst according to claim 1, characterized in that: the amorphous silicon-aluminum is obtained by roasting at 500 ℃ for 4 hours in air atmosphere in advance; the specific surface area is 200-600 m2A pore volume of 0.5 to 1.5 cm/g3In% by weight, SiO2The content is 20-80%.
6. The medium oil type hydrocracking catalyst according to claim 1, characterized in that: the alumina is obtained by roasting pseudo-boehmite for 4 hours at 500 ℃ in an air atmosphere; it is composed ofThe specific surface area is 150-400 m2A pore volume of 0.3 to 0.8 cm3The Na element content is less than or equal to 0.2 percent in percentage by weight.
7. The medium oil type hydrocracking catalyst according to claim 1, characterized in that: the Y molecular sieve used for preparing the modified Y molecular sieve is a hydrogen type molecular sieve, and the specific surface area of the Y molecular sieve is 400-900 m2(ii) a total pore volume of 0.30 to 0.80 cm3Per g, wherein the mesoporous volume is less than 0.15 cm3A Si/Al molar ratio of 5 to 30, and a unit cell size of 24.25 to 24.45
Figure DEST_PATH_IMAGE002
；
The mass ratio of the used Y molecular sieve to the ionic surfactant is 1: (0.1 to 3); wherein the ionic surfactant is a cationic surfactant;
the mass ratio of the used Y molecular sieve to ammonia water is 1: (1-500); the content of the ammonia monohydrate in the ammonia water is 0.5-5% by weight percentage;
the temperature of the hydrothermal treatment is 100-200 ℃, and the time is 1-48 h;
the drying temperature is 80-200 ℃, and the drying time is 1-24 hours.
8. A process for preparing the medium oil type hydrocracking catalyst according to claim 1, characterized by: the method comprises the following steps:
(1) uniformly mixing pseudo-boehmite, amorphous silicon-aluminum and a modified Y molecular sieve, adding an acid solution, fully kneading, forming, drying, heating to a roasting target temperature under a nitrogen atmosphere, and then, switching to an air atmosphere for roasting to obtain a catalyst carrier;
(2) and (2) dispersing a VIB group element-containing compound and a VIII group element-containing compound in a solvent, impregnating the catalyst carrier obtained in the step (1), and then drying and roasting to obtain the medium oil type hydrocracking catalyst.
9. The process for producing a medium oil type hydrocracking catalyst according to claim 8, characterized in that: the drying temperature in the step (1) is 80-200 ℃, and the drying time is 2-24 hours; the heating rate under the nitrogen atmosphere is 1-20 ℃/min, the target temperature is 400-650 ℃, and the roasting time under the air atmosphere is 3-12 h.
10. The process for producing a medium oil type hydrocracking catalyst according to claim 8, characterized in that: the drying temperature in the step (2) is 80-200 ℃, and the drying time is 2-24 hours; the roasting temperature is 400-600 ℃, and the roasting time is 2-12 h.
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CN112221535A (en) * 2020-10-27 2021-01-15 中化泉州石化有限公司 Medium oil type hydrocracking catalyst and preparation method thereof

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