CN111672534A - Hydrocracking catalyst, preparation method and application thereof - Google Patents

Hydrocracking catalyst, preparation method and application thereof Download PDF

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CN111672534A
CN111672534A CN202010521157.4A CN202010521157A CN111672534A CN 111672534 A CN111672534 A CN 111672534A CN 202010521157 A CN202010521157 A CN 202010521157A CN 111672534 A CN111672534 A CN 111672534A
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hydrocracking catalyst
alumina
type zeolite
catalyst
ammonium
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CN111672534B (en
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申宝剑
曾鹏晖
孙发民
李海岩
郭巧霞
谢方明
姜维
张铁珍
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China University of Petroleum Beijing
China National Petroleum Corp
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China National Petroleum Corp
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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
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • 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
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • B01J35/69—Pore distribution bimodal
    • 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
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions

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  • Chemical Kinetics & Catalysis (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a hydrocracking catalyst, a preparation method and application thereof. The hydrocracking catalyst comprises a carrier, a hydrogenation metal component and an auxiliary agent, wherein the hydrogenation metal component and the auxiliary agent exist in the form of metal oxides, the metal components comprise VIB group metal oxides and VIII group metal oxides, the carrier is prepared from an ammonium fluosilicate modified Y-type zeolite/alumina composite material, and the ammonium fluosilicate modified Y-type zeolite/alumina composite material is prepared by mixing active alumina, a guiding agent, a silicon source and water, performing hydrothermal crystallization and modifying ammonium fluosilicate. The invention also provides a preparation method of the hydrocracking catalyst. The invention further provides the application of the hydrocracking catalyst in heavy oil hydrocracking. The hydrocracking catalyst provided by the invention has high hydrogenation activity, moderate acidity and gradient pore distribution, and can reduce secondary cracking of a cracking product.

Description

Hydrocracking catalyst, preparation method and application thereof
Technical Field
The invention relates to the field of hydrocracking catalysis, in particular to a hydrocracking catalyst and a preparation method and application thereof.
Background
As crude oil is upgraded and degraded, the feed to the hydrocracking apparatus becomes heavier, which causes problems such as higher hydrogen consumption of the apparatus, lower yield, lower product quality, and shorter operation cycle. In the secondary processing technology of crude oil, the distillate oil hydrocracking technology has the characteristics of strong raw material adaptability, large flexibility of production operation and product scheme, good product quality and the like, can directly convert various heavy and poor raw materials into high-quality jet fuel, diesel oil, lubricating oil base stock, chemical naphtha and tail oil steam cracking ethylene raw materials and the like which are urgently needed by the market, plays a role of a product distribution and product quality regulator in the whole plant production process, is the core of 'oil-chemical-fiber' combination, and becomes one of the most important heavy oil deep processing technologies in modern oil refining and petrochemical industry. The development of high-level hydrocracking catalysts is the key to the advancement of hydrocracking technology.
The hydrogenation process is the only way to realize the heavy oil lightening and cleaning process, and the technology thereof depends on the improvement of the catalyst performance, namely the core is the research and development of the hydrogenation catalyst. The hydrocracking catalyst is a bifunctional catalyst which has both an acidic function and a hydrogenation function, wherein the cracking function is provided by an acidic carrier, particularly a molecular sieve, and the hydrogenation function is provided by an active metal component. The innovation of the molecular sieve is a source for improving the flexibility of the hydrocracking catalyst, the improvement of the performance of the hydrocracking catalyst in the aspects of activity, selectivity, temperature sensitivity and the like is realized mainly through the innovation of the preparation and modification modes of the molecular sieve, the improvement of the surface acidity of a catalyst carrier, the expansion and preparation of multilevel pore channels and the improvement of the dispersion degree of active metals on the surface of the carrier are effective methods for improving the activity of the catalyst, and particularly the structure of the pores of the catalyst carrier has great influence on the service life and the catalytic effect of the catalyst.
The acid function of the hydrocracking catalysts referred to in US5536687, US5447623 and EP0028938a1 is provided mainly by molecular sieves, and the hydrogenation component is Mo-Ni or W-Ni. The catalyst related to CN1389545A contains 20-40% of Y zeolite, 5-20% of phosphotungstic heteropoly acid or silicotungstic heteropoly acid, 5-10% of nickel oxide and 40-60% of alumina. The hydrocracking catalyst containing the molecular sieve has the advantages of strong acidity and large specific surface, but has the defect that the pore diameter of the molecular sieve is small, so that the diffusion resistance of reactants and products is increased, and the probability of secondary cracking reaction is increased.
Cn201110350796.x discloses a hydrocracking catalyst and a preparation method thereof. The catalyst comprises an acidic component, a hydrogenation component and a carrier, wherein the acidic component is heteropolyacid alkali metal salt, the hydrogenation component is nickel, and the carrier is silicon oxide; the catalyst comprises 10-20% of acid component, 3-8% of hydrogenation component and the balance of carrier according to mass percentage. The method is characterized in that a catalyst carrier is prepared by adopting a sol-gel method, a hydrogenation metal component and an alkali metal salt are introduced in the preparation process of the carrier, the carrier is immersed in a heteropoly acid solution, and the catalyst is obtained after drying. The catalyst of the invention has the advantages that the heteropolyacid salt is uniformly dispersed in the carrier, and the catalyst shows high liquid hydrocarbon selectivity due to weak acidity and low content, but the activity is relatively low.
In summary, the bifunctional hydrocracking catalyst and the dehydrogenation function are mainly provided by hydrogenation metals, the hydrogenation metals generally comprise conventional non-noble metal components, such as W, Mo, Ni, Co, and the like, and the noble metals are generally selected from Pt and Pa. Typically the cracking function is provided by an acidic support component, comprising mainly molecular sieves and amorphous oxides. The hydrocracking catalyst carrier is mainly an acidic component and plays an important role in the activity, selectivity and product quality of the catalyst. For hydrocracking catalysts, the activity of the catalyst is regarded as important, and the selectivity of the target product must be considered, so that a relatively reasonable balance must be found in the contradiction between the activity of the catalyst and the selectivity of the target product to better exert the performance of the catalyst. The Y-type molecular sieve is a commonly used hydrocracking catalyst carrier. The current method for industrially producing the Y-type molecular sieve is basically prepared by adopting a guide agent method proposed by American GRACE company in USP 3639099 and USP 4166099. The pore diameter of the raw powder pore channel of the Y-type molecular sieve is 0.74nm multiplied by 0.74nm, and the micropore volume of the pore channel accounts for more than 95 percent of the total pore volume. The molecular diameter of polycyclic heavy components in the hydrocracking raw material is usually more than 1nm, for the cracking reaction of heavy component macromolecules, the ideal pore aperture range suitable for the reaction and the product diffusion is the mesoporous range of 2 nm-10 nm, more contactable acid centers can be exposed, the adsorption and the reaction of the raw material macromolecules and the desorption and the diffusion of target products are facilitated, and the hydrocracking selectivity of the molecular sieve is improved. In order to improve the condition that the pore volume content of mesoporous pores of the Y-type molecular sieve is low and unfavorable for raw oil macromolecule reaction, modified Y-type molecular sieve with different pore channel structures and acid distributions can be obtained by modifying raw powder of the Y-type molecular sieve.
The total pore volume and the mesoporous pore volume of the molecular sieve prepared by the conventional modification method are small, which is not beneficial to the conversion of raw material macromolecules, the acidity distribution is unreasonable, the heavy oil cracking performance of the catalyst is still relatively poor, and zeolite components dispersed in the catalyst can be gradually enclosed and embedded in the catalyst in a harsh multiple reaction-regeneration cycle, so that the due catalytic action is lost.
Disclosure of Invention
In order to solve the above problems, the present invention aims to provide a hydrocracking catalyst, a preparation method and an application thereof. The hydrocracking catalyst has high hydrogenation activity, moderate acidity and gradient pore distribution through the mutual matching among a carrier prepared from the ammonium fluosilicate modified Y-type zeolite/alumina composite material, a hydrogenation metal component and an auxiliary agent, so that a primary cracking product is more subjected to hydrogenation saturation and isomerization on a hydrogenation activity center, and the secondary cracking of the cracking product is reduced.
In order to achieve the above object, the present invention provides a hydrocracking catalyst comprising: the catalyst comprises a carrier, a hydrogenation metal component and an auxiliary agent, wherein the hydrogenation metal component and the auxiliary agent exist in the form of metal oxides, and the metal components comprise oxides of VIB group metals and oxides of VIII group metals; the catalyst comprises the following components in percentage by weight based on 100 percent of the total weight of the catalyst: 55-88% of carrier, 10-25% of VIB group metal oxide, 1-10% of VIII group metal oxide and 1-10% of assistant;
wherein the carrier is prepared from an ammonium fluosilicate modified Y-type zeolite/alumina composite material; the ammonium fluosilicate modified Y-type zeolite/alumina composite material is prepared by mixing active alumina, a directing agent, a silicon source and water, performing hydrothermal crystallization and modifying ammonium fluosilicate, wherein the dosage ratio of the active alumina, the directing agent, the silicon source and the water is Na2O：Al2O3：SiO2：H2O ═ 0.1 to 1.5: 1: (0.1-5): (2-100), the activated alumina is obtained by roasting one of kaolin, expanded perlite and gamma-alumina.
In a specific embodiment of the invention, the ammonium fluorosilicate modified Y-type zeolite/alumina composite is a composite formed by the intimate association of activated alumina and a Y-type molecular sieve. The ammonium fluorosilicate-modified Y-type zeolite/alumina composite material not only has the characteristic gradient pore distribution formed by compounding the activated alumina and the Y-type molecular sieve, but also has the characteristics that the single activated alumina or the Y-type molecular sieve does not have, for example, the ammonium fluorosilicate-modified Y-type zeolite/alumina composite material has good heat conduction capability in practical application, and has good reaction performance and stability.
In the above hydrocracking catalyst, preferably, the SiO of the hydrocracking catalyst support2/Al2O3The molar ratio is 4-50.
In a particular embodiment of the invention, the specific surface area of the support is generally 650m or less2A/g, preferably 500m or less2/g。
In the hydrocracking catalyst, the auxiliary agent can improve the carrier of the hydrocracking catalyst and the pore structure of the hydrocracking catalyst, and can effectively improve the surface acidity of the catalyst. Preferably, the metal element in the auxiliary agent comprises one or a combination of more than two of Zn, Ga, B, Ti and Zr.
In the above hydrocracking catalyst, preferably, the group VIB metal comprises W and/or Mo.
In the above hydrocracking catalyst, preferably, the group VIII metal includes Ni and/or Co.
According to a specific embodiment of the present invention, in the preparation of the ammonium fluorosilicate modified Y-type zeolite/alumina composite, the gamma-alumina preferably comprises pseudo-boehmite and/or alumina trihydrate.
According to a specific embodiment of the present invention, the silicon source may include water glass and/or silica sol during the preparation of the ammonium fluorosilicate modified Y-type zeolite/alumina composite.
According to a specific embodiment of the present invention, during the preparation of the ammonium fluorosilicate modified Y-type zeolite/alumina composite material, the directing agent can be obtained according to the preparation method of the directing agent disclosed in CN1785808A (application No. CN200410097108.3, title of the invention: preparation method of a high silica alumina ratio small crystal NaY molecular sieve, published: 20060614), which is incorporated herein in its entirety as part of the present invention.
In a specific embodiment of the present invention, during the preparation of the ammonium fluorosilicate-modified Y-type zeolite/alumina composite, the activated alumina, which is used as an aluminum source for preparing the Y-type zeolite, has high thermal stability, good pore characteristics and surface properties. The activated alumina is mixed with a guiding agent, a silicon source and water, and then crystallized to generate Y-type zeolite, and then modified by ammonium fluosilicate to finally form the ammonium fluosilicate modified Y-type zeolite/alumina composite material. In the crystallization process, the specific pore property of the activated alumina is retained to the maximum extent; the crystallization of the Y-type zeolite is used as the active component of the composite material, which can greatly improve the acidity of the obtained composite material, and the acidity of the composite material is far higher than that of a catalyst carrier formed by pure active alumina or an active alumina matrix modified by impregnation. Meanwhile, the Y-type zeolite contained in the composite material can reduce the dosage of the expensive molecular sieve and reduce the cost.
According to a specific embodiment of the present invention, in the ammonium fluorosilicate-modified Y-type zeolite/alumina composite, the Y-type zeolite may include one or a combination of two or more of HY-type zeolite, ultrastable Y-type zeolite, and rare-earth ultrastable Y-type zeolite.
According to the embodiment of the present invention, in the preparation of the activated alumina, the time for calcining one of kaolin, expanded perlite and gamma-alumina is generally controlled to be 4-10 hours, and the temperature for calcining is generally controlled to be 450-.
According to the specific embodiment of the invention, during the preparation process of the ammonium fluosilicate modified Y-type zeolite/alumina composite material, the crystallization temperature is generally controlled to be 70-120 ℃, and the crystallization time is generally controlled to be 0.5-72h, preferably 2-16 h.
According to a specific embodiment of the present invention, the method for modifying ammonium fluorosilicate may comprise: adding (slowly dropwise adding) ammonium fluosilicate solution (preferably with the concentration of 0.1-1.0mol/L) into slurry formed by the Y-type zeolite/alumina composite material and water, stirring (the time can be controlled to be 1-2h), carrying out suction filtration, washing and drying to obtain the ammonium fluosilicate modified Y-type zeolite/alumina composite material. In some embodiments, the above-described ammonium fluorosilicate modification process may be performed at a temperature of 90 ℃.
According to a specific embodiment of the present invention, in the above method for modifying ammonium fluorosilicate, the amount ratio of the ammonium fluorosilicate to the Y-type zeolite/alumina composite may be controlled to be 0.05 to 0.4 mol: 100 g.
According to a specific embodiment of the present invention, the preparation process of the ammonium fluorosilicate modified Y-type zeolite/alumina composite may further comprise: and (3) carrying out post-treatment on the crystallized product before modification of the ammonium fluosilicate, wherein the post-treatment can comprise ion exchange, roasting and other post-treatments on the crystallized product. In particular embodiments, the ion exchange may be an ammonium ion exchange or a combination of an ammonium ion + rare earth ion exchange (i.e., "ammonium + rare earth" ion exchange), and the rare earth ions used may be from a single rare earth element or from a combination of two or more rare earth elements. After ion exchange, Na-type Y zeolite in the Y-type zeolite can be converted into one or the combination of more than two of HY-type zeolite, ultrastable Y-type zeolite and rare earth ultrastable Y-type zeolite. In the post-treatment process, the roasting temperature is generally controlled to be 300-900 ℃, and the roasting time is generally controlled to be 1-6 h.
According to an embodiment of the present invention, the carrier may be prepared by mixing ammonium fluorosilicate modified Y-type zeolite/alumina composite with a binder (e.g., alumina sol), sesbania powder.
According to a specific embodiment of the present invention, the preparation process of the carrier may specifically include:
step 1, roasting one of kaolin, expanded perlite and gamma-alumina to obtain activated alumina;
step 2, mixing active alumina, a directing agent, a silicon source and water, and performing hydrothermal crystallization to obtain the Y-type zeolite/alumina composite material, wherein the dosage ratio of the active alumina, the directing agent, the silicon source and the water is Na2O：Al2O3：SiO2：H2O ═ 0.1 to 1.5: 1: (0.1-5): (2-100) determining a molar ratio; carrying out ammonium fluosilicate modification on the Y-type zeolite/alumina composite material to obtain an ammonium fluosilicate modified Y-type zeolite/alumina composite material;
and 3, mixing the ammonium fluosilicate modified Y-type zeolite/alumina composite material with an adhesive and sesbania powder to obtain the hydrocracking catalyst carrier.
In a specific embodiment of the present invention, in the preparation process of the above-mentioned carrier, step 3 may further include: and grinding, extruding, forming, drying and roasting the mixture of the ammonium fluosilicate modified Y-type zeolite/alumina composite material, the adhesive and sesbania powder to obtain the hydrocracking catalyst carrier. In some embodiments, the binder used to prepare the hydrocracking catalyst support may be a conventional binder, such as an alumina sol.
In a specific embodiment of the invention, the mass ratio of the ammonium fluorosilicate modified Y-type zeolite/alumina composite, the binder and the sesbania powder can be controlled to be 20: 18: 3 during the preparation of the carrier.
The invention also provides a preparation method of the hydrocracking catalyst, which comprises the following steps:
preparing a metal salt co-impregnation solution containing a metal element in an auxiliary agent and a metal element in a hydrogenation metal component;
and step two, immersing the carrier into the metal salt co-impregnation solution, drying and roasting to obtain the hydrocracking catalyst.
In the above preparation method of the hydrocracking catalyst, the metal salt co-impregnation solution preferably includes one or a combination of two or more of nitrates, sulfates and chlorides of metals.
In the above preparation method of the hydrocracking catalyst, the concentration of the metal salt co-impregnation solution is preferably 1 to 100g/100 mL.
In the preparation method of the hydrocracking catalyst, preferably, in the second step, the roasting temperature is 450-1000 ℃, and the roasting time is 2-10 h. More preferably, the roasting temperature is 500-600 ℃, and the roasting time is 4-6 hours.
The invention further provides the application of the hydrocracking catalyst in heavy oil hydrocracking. The catalyst can be used as a hydrocracking catalyst for treating heavy oil, such as: under the conditions that the total reaction pressure is 15MPa, the volume ratio of hydrogen to oil is 1500: 1, liquid hourly space velocity of 1.5h-1Under the condition, a one-stage series one-pass process flow is adopted, the hydrocracking catalyst is adopted to treat vacuum distillate oil (VGO), and the selectivity of the middle distillate oil of the catalyst can reach 84.5 percent.
The invention has the beneficial effects that:
1. the carrier, the hydrogenation active component and the auxiliary agent in the hydrocracking catalyst provided by the invention are mutually matched, and the hydrocracking catalyst has high hydrogenation activity, moderate acidity and gradient pore distribution, so that a primary cracking product is more subjected to hydrogenation saturation and isomerization on a hydrogenation activity center, and secondary cracking of the cracking product is reduced.
2. The hydrocracking catalyst provided by the invention has the advantages that the activity of the catalyst and the selectivity of the catalyst to a target product are both considered, the pore distribution and the acidity of the hydrocracking catalyst can be modulated and controlled, and the hydrocracking catalyst is favorable for better exerting the performance of the catalyst.
3. When the hydrocracking catalyst provided by the invention is used for hydrocracking heavy oil, particularly heavy wax oil (VGO, CGO and DAO) is treated under a high pressure condition (12-20 MPa), and poor diesel oil (such as coker diesel oil and catalytic diesel oil) can also be added, so that the hydrocracking catalyst has high catalytic activity and middle distillate oil selectivity, the condensation point of diesel oil fraction is greatly reduced, the product property of middle distillate oil is improved, and the hydrocracking catalyst can meet the requirements of increasing the operation flexibility of a refinery, increasing the treatment capacity of a device and further increasing the yield of the middle distillate oil.
Drawings
FIG. 1 is an XRD spectrum of sample A-1 of example 1, scanned over a range of 5-70 degrees 2 θ.
FIG. 2 is an XRD spectrum of sample A-1 of example 1, scanned over a range of 2 θ from 15 ° to 35 °.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
In the following examples, pseudo-boehmite was converted by 450-900 ℃ heat to obtain activated alumina. The pseudoboehmite can be selected from industrial products such as Shanxi pseudoboehmite produced by Shanxi aluminum works; or pseudo-boehmite synthesized by a pH swing method.
The directing agent used in the following examples is obtained according to the preparation method of the directing agent disclosed in CN1785808A (application number: CN200410097108.3, title of the invention: preparation method of high silica alumina ratio small crystal grain NaY molecular sieve, published as 20060614), and specifically, the directing agent is prepared by uniformly mixing a silicon source, an aluminum source, an alkali liquor and water according to a certain molar ratio, stirring and aging.
The silicon source used in the following examples was water glass (from landau petrochemical catalyst plants).
In the following examples and comparative examples, the relative crystallinity was measured by XRD, produced by Panaco instruments of the Netherlands, under the conventional analysis conditions of CuK α radiation (wavelength: Palytic EMPYREAN)
Figure BDA0002532123840000071
) Tube voltage 40kV and tube current 40 mA.
The silica to alumina ratio was determined according to SH/T0339-92 standard method (see "chemical industry standards Association", China standards Press, published 2000) and the unit cell constant a of the NaY molecular sieve was calculated according to the following formula:
Figure BDA0002532123840000072
wherein, lambda is the radiation wavelength of CuK α, h2+k2+l2Is the square of the X-ray diffraction miller index.
Then, the silicon-aluminum ratio of the NaY molecular sieve is calculated according to a Breck-Flanigen formula:
SiO2/Al2O32 × (25.858-a)/(a-24.191), a being the unit cell constant of NaY molecular sieve.
The specific surface area was measured by an ASAP2020 model automatic physical adsorption apparatus (Micromeritics, USA) and the specific surface area was measured by BET method and the mesoporous volume and pore size distribution were measured by BJH method.
The catalysts prepared in examples and comparative examples were evaluated for reaction performance on a fixed bed hydrogenation test apparatus.
Example 1
This example provides a method for preparing a hydrocracking catalyst, comprising:
firstly, preparing an ammonium fluosilicate modified Y-type zeolite/alumina composite material:
1. 200.06g of industrial pseudo-boehmite is put into a muffle furnace, heated to 600 ℃ at the speed of 4 ℃/min and roasted for 4 hours to obtain the activated alumina.
2. 120.51g of water glass is placed in a beaker, the temperature in the beaker is controlled at 60 ℃, 80g of guiding agent and 220.23g of deionized water are added, 100g of activated alumina is added, and the raw materials are mixed uniformly to obtain a raw material mixture, wherein the guiding agent is prepared according to the method provided in embodiment 1 in CN 1785808A.
3. And (3) putting the raw material mixture into a stainless steel reaction kettle, crystallizing for 4 hours at 100 ℃, and then filtering, washing and drying to obtain the Y-type zeolite/alumina composite material.
4. The zeolite/alumina composite material type 300gY was weighed out and added to 3000g ammonium nitrate solution (concentration 0.1mol/L) and ion exchanged in a water bath at 90 ℃ for 1 h. Filtering, washing, drying at 120 deg.C for 10 hr, and calcining at 540 deg.C for 4 hr.
5. 0.5mol/L ammonium fluosilicate solution is prepared, 100gY type zeolite/alumina composite material is added into 1L deionized water to form slurry, and the slurry is stirred in a constant temperature water bath at 90 ℃. And (3) dropwise adding the prepared 500mL of ammonium fluosilicate solution into the slurry of the Y-type zeolite/alumina composite material within 2h, and continuously stirring for 1h after dropwise adding is finished. And (4) carrying out suction filtration, washing and drying at 120 ℃ for 12h to obtain the ammonium fluosilicate modified Y-type zeolite/alumina composite material.
Secondly, preparing a carrier:
6. weighing the ammonium fluosilicate modified Y-type zeolite/alumina composite material, the adhesive and sesbania powder according to the mass ratio of 20: 18: 3, mixing, grinding, extruding and forming. And then drying at room temperature for 10h, drying at 120 ℃ for 10h, and roasting at 550 ℃ for 4h to obtain the carrier, namely the hydrocracking catalyst carrier, which is marked as an A-1 sample.
XRD characterization was performed on sample A-1 with scanning ranges 2 θ of 5 ° -70 ° and 15 ° -35 °, respectively, and the XRD diffraction patterns obtained are shown in FIGS. 1 and 2. As can be seen from FIGS. 1 and 2, sample A-1 has a characteristic peak of the Y-type molecular sieve.
According to the result of XRD scanning, the crystallinity of sample A-1 was measured to be 15%, SiO2/Al2O3The molar ratio is 10.51; the specific surface area of sample A-1 measured by the BET method was 309m2(ii)/g, total pore volume 0.565cm3The mesoporous pore volume of the sample A-1 is 0.395cm measured by a BJH method3The peak value of the mesoporous pore size distribution is at 4.1nm and 9.8 nm.
Thirdly, preparing a hydrocracking catalyst:
7. the carrier A-1 is immersed in mixed metal nitrate solution containing Zn, Zr, Ni and W for 2 hours at room temperature, dried for 4 hours at 120 ℃, and calcined for 4 hours at the programmed temperature of 500 ℃ to obtain the catalyst which is marked as CAT-1.
The catalyst CAT-1 was found to have a support mass fraction of 61%, a NiO mass fraction of 7%, and WO3Is 22%, ZnO is 5%, and ZrO is 5%.
Example 2
This example provides a method for preparing a hydrocracking catalyst, comprising:
firstly, preparing an ammonium fluosilicate modified Y-type zeolite/alumina composite material:
1. 500.15g of industrial pseudo-boehmite is put into a muffle furnace, the temperature is raised to 700 ℃ at the speed of 4 ℃/min, and the activated alumina is obtained after roasting for 4 hours.
2. 140.84g of water glass is placed in a beaker, the temperature in the beaker is controlled at 60 ℃, 130.25g of directing agent and 150g of deionized water are added, 200.7g of activated alumina is added, the mixture is stirred for 3 hours, and the raw materials are fully and uniformly mixed to obtain a raw material mixture, wherein the preparation method of the directing agent is the same as that of the example 1.
3. And (3) putting the raw material mixture into a stainless steel reaction kettle, crystallizing for 72 hours at 100 ℃, and then filtering, washing and drying to obtain the Y-type zeolite/alumina composite material.
4-5, modifying the Y-type zeolite/alumina composite material sample by ammonium fluosilicate according to the method of the step 4-5 in the example 1, except that the ammonium nitrate solution is changed into the ammonium chloride solution, the modification is carried out in the same way, and the Y-type zeolite/alumina composite material modified by the ammonium fluosilicate is obtained.
Secondly, preparing a carrier:
6. the ammonium fluorosilicate modified Y-type zeolite/alumina composite described above was prepared as a support, designated a-2, according to the method of step 6 of example 1.
And (3) carrying out XRD characterization on the sample A-2, wherein the obtained XRD diffraction spectrum is similar to that obtained in example 1, and the sample A-2 has a characteristic peak of the Y-type molecular sieve.
According to the result of XRD scanning, the crystallinity of sample A-2 was found to be 49%, SiO2/Al2O3The molar ratio is 6.58; the specific surface area of sample A-2 measured by the BET method was 509m2(ii)/g, total pore volume 0.568cm3The mesoporous pore volume of the sample A-2 is 0.405cm measured by a BJH method3The peak value of the mesoporous pore size distribution is at 4.0nm and 9.8 nm.
Thirdly, preparing a hydrocracking catalyst:
7. soaking the carrier A-2 in mixed metal chloride solution containing Zn, Zr, Ni and Mo at room temperature for 2 hr, drying at 120 deg.c for 4 hr, and roasting at programmed temperature of 540 deg.c for 4 hr to obtain catalyst CAT-2.
The catalyst CAT-2 was found to have a support mass fraction of 60.9%, a NiO mass fraction of 7.0%, and MoO3The mass fraction of (A) was 22.1%, the mass fraction of ZnO was 5.0%, and the mass fraction of ZrO was 5.0%.
Example 3
This example provides a method for preparing a hydrocracking catalyst, comprising:
firstly, preparing an ammonium fluosilicate modified Y-type zeolite/alumina composite material:
1. 200.11g of alumina trihydrate is placed in a muffle furnace, the temperature is raised to 600 ℃ according to the temperature rise rate of 4 ℃/min, and the activated alumina is obtained after roasting for 2 hours.
2. 149.66g of water glass is placed in a beaker, 100.02g of directing agent and 150g of deionized water are added, 80.51g of activated alumina is added, and the raw materials are stirred and mixed uniformly to obtain a raw material mixture, wherein the preparation method of the directing agent is the same as that of example 1.
3. And (3) putting the raw material mixture into a stainless steel reaction kettle, crystallizing for 5 hours at 110 ℃, and then filtering, washing and drying to obtain the Y-type zeolite/alumina composite material.
4-5, carrying out ammonium fluosilicate modification on a Y-type zeolite/alumina composite material sample according to the method of the step 4-5 in the example 1 to obtain the ammonium fluosilicate modified Y-type zeolite/alumina composite material.
Secondly, preparing a carrier:
6. a sample of the prepared ammonium fluorosilicate-modified Y-type zeolite/alumina composite was prepared as a support, denoted as a-3, according to the method of step 6 in example 1.
XRD characterization was performed on sample A-3, and the XRD diffraction pattern obtained was similar to that obtained in example 1. Sample A-3 has a characteristic peak of type Y molecular sieve.
According to the result of XRD scanning, the crystallinity of sample A-3 was measured to be 15%, SiO2/Al2O3The molar ratio is 8.36; sample A-3 having a specific surface area of 419m as measured by the BET method2Per g, total pore volume of 0.468cm3The mesoporous pore volume of the sample A-3 is 0.325cm determined by the BJH method3The peak value of the mesoporous pore size distribution is at 3.8nm and 9.2 nm.
Thirdly, preparing a hydrocracking catalyst:
7. and (3) soaking the carrier A-3 in a co-impregnation solution of mixed metal nitrates containing Zn, Ga, Ni and W at room temperature for 2 hours, drying at 120 ℃ for 4 hours, and roasting at the programmed temperature of 500 ℃ for 4 hours to obtain the catalyst, which is marked as CAT-3.
The catalyst CAT-3 was measured to have a support mass fraction of 70%, a NiO mass fraction of 5%, and WO320% by mass of (A), 2% by mass of ZnO and 3% by mass of GaO.
Example 4
This example provides a method for preparing a hydrocracking catalyst, comprising:
firstly, preparing an ammonium fluosilicate modified Y-type zeolite/alumina composite material:
1-5, the preparation process of the ammonium fluorosilicate modified Y-type zeolite/alumina composite material was substantially the same as the preparation method provided in example 1, except that the crystallization time in step 3 was 32 hours.
Secondly, preparing a carrier:
6. the ammonium fluorosilicate-modified Y-type zeolite/alumina composite material obtained above was prepared into a support, which was denoted as a-4, by the method of step 6 in example 1.
XRD characterization was performed on sample A-4, and the XRD diffraction pattern obtained was similar to that obtained in example 1. Sample A-4 has a characteristic peak of type Y molecular sieve.
According to the result of XRD scanning, the crystallinity of sample A-4 was measured to be 16%, SiO2/Al2O3The molar ratio is 6.16; the specific surface area of sample A-4 measured by the BET method was 319m2(ii)/g, total pore volume 0.361cm3The mesoporous pore volume of the sample A-4 is 0.225cm measured by BJH method3The peak value of the mesoporous aperture distribution is at 3.8nm and 4.2 nm.
Thirdly, preparing a hydrocracking catalyst:
and (3) soaking the carrier A-4 in a co-impregnation solution of mixed metal nitrates containing Zn, Ti, Ni and Mo at room temperature for 2 hours, drying at 120 ℃ for 4 hours, and roasting at the programmed temperature of 500 ℃ for 4 hours to obtain a catalyst, which is marked as CAT-4.
The catalyst CAT-4 is measured to have the mass fraction of the carrier of 55 percent, the mass fraction of NiO of 6 percent and MoO3The mass fraction of (A) is 24%, the mass fraction of ZnO is 6%, and the mass fraction of TiO is 9%.
Test example 1
The CAT-1 catalyst sample prepared in example 1 was evaluated on a fixed bed hydrogenation test apparatus under the following conditions: the total reaction pressure is 15MPa, and the volume ratio of hydrogen to oil is 1500: 1, liquid hourly space velocity of 1.5h-1Adopts a one-stage series one-pass process flow, uses vacuum distillate oil (VGO) as raw oil, and the property of the raw oilThe results are shown in Table 1 and the results are shown in Table 2.
Comparative example 1
The comparative example provides a preparation method for preparing a hydrocracking catalyst by taking active alumina as a carrier, which specifically comprises the following steps:
300.16g of industrial pseudo-boehmite is put in a muffle furnace, heated to 600 ℃ at the speed of 4 ℃/min and roasted for 4 hours, so that the pseudo-boehmite is fully thermally converted to obtain the activated alumina.
According to the preparation method and the proportion of the catalyst provided in example 1, the activated alumina is used to replace the carrier A-1 in example 1 to prepare a catalyst CD-1, so as to compare the performance of the catalyst in the test example 1.
The CD-1 catalyst samples were evaluated on a fixed bed hydrogenation test apparatus under the same conditions as in test example 1. Vacuum distillate oil (VGO) was used as the feed oil, and the properties of the feed oil used are shown in Table 1 and the evaluation results are shown in Table 2.
Comparative example 2
This comparative example provides a preparation method for preparing a hydrocracking catalyst, which is similar to test example 1 except that:
a hydrocracking catalyst was prepared by replacing the carrier a-1 of example 1 with the activated alumina prepared in comparative example 1 and the process USY molecular sieve (ex. landlocked petrochemical catalyst) according to the crystallinity of the Y-type zeolite in sample a-1 obtained in example 1, to obtain a sample having the same Y molecular sieve content, in the same manner as in example 1, and the obtained catalyst was designated as CD-2.
The CD-2 catalyst samples were evaluated on a fixed bed hydrogenation test apparatus under the same conditions as in test example 1. Vacuum distillate oil (VGO) was used as the feed oil, and the properties of the feed oil used are shown in Table 1 and the evaluation results are shown in Table 2.
TABLE 1
Raw oil Vacuum distillate
Density (20 ℃ C.)/(g/cm)3) 0.8672
Distillation range, deg.C
IBP,m％ 304/362
30％/50％ 394/418
70％/90％ 443/482
95％/EBP 507/550
Freezing point, deg.C 35
Sulfur, wt.% 1.99
Nitrogen, wt% 1227
Carbon, wt.% 85.27
Hydrogen, wt.% 12.47
BMCI value 45.0
TABLE 2 comparison of hydrocracking Performance of the catalysts
Figure BDA0002532123840000121
Figure BDA0002532123840000131
It can be seen from the evaluation results in table 2 that the selectivity, yield and product quality of the middle distillate oil obtained by the hydrocracking experiment using the hydrocracking catalyst provided by the present invention are superior to those of the comparative catalyst under the same process conditions.

Claims (10)

1. A hydrocracking catalyst, comprising: the catalyst comprises a carrier, a hydrogenation metal component and an auxiliary agent, wherein the hydrogenation metal component and the auxiliary agent exist in the form of metal oxides, and the hydrogenation metal component comprises oxides of VIB group metals and oxides of VIII group metals;
the catalyst comprises the following components in percentage by weight based on 100 percent of the total weight of the catalyst: 55-88% of carrier, 10-25% of VIB group metal oxide, 1-10% of VIII group metal oxide and 1-10% of assistant;
wherein the carrier is prepared from an ammonium fluosilicate modified Y-type zeolite/alumina composite material;
the ammonium fluosilicate modified Y-type zeolite/alumina composite material is prepared by mixing active alumina, a guiding agent, a silicon source and water, performing hydrothermal crystallization and modifying ammonium fluosilicate, wherein the dosage ratio of the active alumina, the guiding agent, the silicon source and the water is Na2O：Al2O3：SiO2：H2O ═ 0.1 to 1.5: 1: (0.1-5): (2-100), the activated alumina is obtained by roasting one of kaolin, expanded perlite and gamma-alumina.
2. The hydrocracking catalyst of claim 1, wherein the metal element in the promoter comprises one or a combination of two or more of Zn, Ga, B, Ti and Zr.
3. The hydrocracking catalyst of claim 1, wherein the group VIB metal comprises W and/or Mo;
the group VIII metal includes Ni and/or Co.
4. Hydrocracking catalyst according to claim 1, wherein the SiO of the support2/Al2O3The molar ratio is 4-50;
preferably, the specific surface area of the carrier is less than or equal to 650m2A/g, more preferably 500m or less2/g。
5. Hydrocracking catalyst according to claim 1 or 4, wherein the silicon source comprises water glass and/or silica sol;
the gamma-alumina comprises pseudoboehmite and/or alumina trihydrate.
6. The hydrocracking catalyst of claim 1 or 4, wherein in the preparation process of the activated alumina, the roasting time is 4-10h, and the roasting temperature is 450-1000 ℃, preferably 450-900 ℃;
preferably, in the preparation process of the ammonium fluosilicate modified Y-type zeolite/alumina composite material, the crystallization temperature is 70-120 ℃, and the crystallization time is 0.5-72h, more preferably 2-16 h;
preferably, the carrier is prepared by mixing an ammonium fluosilicate modified Y-type zeolite/alumina composite material, a binder and sesbania powder.
7. The hydrocracking catalyst of claim 1 or 4, wherein the ammonium fluorosilicate modification process comprises: adding an ammonium fluosilicate solution into slurry formed by the Y-type zeolite/alumina composite material and water, stirring, carrying out suction filtration, washing and drying to obtain the ammonium fluosilicate modified Y-type zeolite/alumina composite material;
preferably, the dosage ratio of the ammonium fluosilicate to the Y-type zeolite/alumina composite material is 0.05-0.4 mol: 100g of the total weight of the mixture;
preferably, the concentration of the ammonium fluosilicate solution is 0.1-1.0 mol/L;
preferably, the ammonium fluorosilicate modification is carried out at a temperature of 90 ℃;
preferably, the stirring time is 1-2 h.
8. The hydrocracking catalyst of claim 1 or 4, wherein the preparation process of the ammonium fluorosilicate modified Y-type zeolite/alumina composite further comprises: carrying out post-treatment on the crystallized product before modification of ammonium fluosilicate, wherein the post-treatment comprises ion exchange and roasting on the crystallized product;
preferably, in the post-treatment process, the roasting temperature is 300-900 ℃, and the roasting time is 1-6 h;
preferably, the ion exchange is ammonium ion exchange, or a combination of ammonium ion exchange and rare earth ion exchange;
more preferably, the rare earth ions are from a single rare earth element or a combination of two or more rare earth elements.
9. A process for preparing a hydrocracking catalyst as set forth in any one of claims 1 to 8, which comprises:
preparing a metal salt co-impregnation solution containing a metal element in an auxiliary agent and a metal element in a hydrogenation metal component;
soaking the carrier into the metal salt co-soaking solution, drying and roasting to obtain the hydrocracking catalyst;
preferably, the metal salt co-impregnation solution comprises one or more than two of nitrate, sulfate and chloride of metal;
preferably, the concentration of the metal salt co-impregnation solution is 1-100g/100 mL;
preferably, in the second step, the roasting temperature is 450-1000 ℃, and the roasting time is 2-10 h; more preferably, the roasting temperature is 500-600 ℃, and the roasting time is 4-6 hours.
10. Use of the hydrocracking catalyst as set forth in any one of claims 1 to 8 for hydrocracking heavy oil.
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