CN109718834B - Modified molecular sieve and preparation method and application thereof - Google Patents

Abstract

The invention belongs to the field of hydrocracking, and discloses a modified molecular sieve and a preparation method and application thereof. The method for modifying the molecular sieve disclosed by the invention comprises the following steps of a) dropwise adding ammonia water into a mixed solution containing a nickel source and a molybdenum source until the pH value of the system is within a range of 9-11; b) impregnating the Y-type molecular sieve with the system obtained in the step a), and then drying and roasting. Also discloses the modified molecular sieve prepared by the method and the application of the modified molecular sieve as a carrier of a supported catalyst. In addition, the catalyst with hydrocracking function and the application thereof as the catalyst for hydrocracking reaction are disclosed, the catalyst contains a carrier, and a VIII group metal element and a VIB group metal element which are loaded on the carrier, and the carrier is the modified molecular sieve. The invention also discloses a hydrocracking method using the catalyst. The modified molecular sieve has higher hydrogenation activity when being used for hydrocracking of aromatic hydrocarbon.

Description

Modified molecular sieve and preparation method and application thereof

Technical Field

The invention relates to the technical field of hydrocracking, in particular to a modified molecular sieve and a preparation method and application thereof, and especially relates to an application of the modified molecular sieve as a hydrocracking catalyst.

Background

In recent years, the tendency toward crude oil heaviness and deterioration has been increasingly apparent worldwide, and at the same time, there has been an increasing demand for middle distillate and reforming, steam cracking feedstocks. This has prompted the rapid development of heavy distillate processing techniques, of which catalysts are the most important and critical.

The hydrocracking technology can produce high-quality middle distillate oil, the product variety and yield can be adjusted according to market demands, naphtha with high aromatic hydrocarbon potential content is produced to be used as a reforming raw material to produce aromatic hydrocarbon, tail oil with low aromatic hydrocarbon index (BMCI) is produced to be used as a steam cracking raw material to produce ethylene or is used as an isomeric pour point depressing raw material to produce high-viscosity index lubricating oil base oil and the like through the combination and gradation of various catalysts according to the actual condition of a refinery, and the economic benefit is further improved.

Hydrocracking catalysts are typically bifunctional catalysts consisting of components having a hydrogenation function (metal component) and a cracking function (acidic support). The metal components generally consist of VIII group and VIB group elements and can be divided into two types of noble metals (Pt and Pd) and non-noble metals (Ni, Co, Mo and W); the acidic support is typically SiO₂-Al₂O₃、SiO₂Amorphous refractory inorganic oxides such as MgO and molecular sieves, and in addition to these, some auxiliary components such as binders and auxiliaries may be included in the catalyst. The hydrogenation and cracking functions of a high performance hydrocracking catalyst should be matched and have high activity in addition to high middle distillate selectivity when used in the production of middle distillate. To meet these requirements, there is a need for an acidic material and a hydrogenated material having excellent properties, and for synergy and compatibility with the materials used.

The acidic component can be classified into amorphous oxides (e.g., SiO) according to the crystallization state₂-Al₂O₃，SiO₂MgO, etc.) and molecular sieves, each of which has characteristics. It is well known that crystalline aluminosilicates (otherwise known as molecular sieves or zeolites), such as Y, ZSM-5 or mordenite, are widely used in the hydrocarbon processing field either directly as catalysts or as an integral part of catalysts, and that Y-type molecular sieves used in hydrocracking catalysts are generally modified.

Molecular sieves are generally crystalline materials consisting of silicon-oxygen tetrahedra and aluminum-oxygen tetrahedra (some molecular sieves also contain other framework atoms, such as phosphorus, titanium, etc.) with a regular pore structure. The siloxatetrahedra and aluminoxatetrahedra are linked together by sharing an oxygen atom, by means of which chain-like or ring-like structural units are formed, which in turn form cage-like structures, which often have openings with unequal pore sizesThe ports are connected together and the interiors are communicated with each other, and finally a pore channel is formed. The pore size and the pore connection mode inside the molecular sieve are different with the type and preparation method of the molecular sieve, and the pore diameter of the common molecular sieve is below 1 nm. Since the aluminum atom in the alundum tetrahedron is +3 to 4 coordinated, each alundum tetrahedron has a positive charge for charge balance, the common compensation cations are sodium ion and potassium ion, and the metal cations for charge compensation can be exchanged for other ions by ion exchange, such as: NH (NH)₄ ⁺、H⁺Or rare earth metal ions, etc.

The molecular sieve used by the hydrocracking catalyst is generally a macroporous silicon-aluminum molecular sieve and mainly comprises a Y-type molecular sieve and a beta molecular sieve, wherein the Y-type molecular sieve has the characteristics of low cost, large adjustment range and the like, and is widely applied to the current hydrocracking catalyst.

US4925820 proposes a process for the preparation of a middle distillate type catalyst using a unit cell constant of less than

And the water adsorption capacity is not less than 8%, amorphous silica-alumina and alumina adhesive. JP2007313409 proposes a similar catalyst using a unit cell constant of

The comparison result shows that the unit cell constant is less than

The middle distillate oil of the molecular sieve has high selectivity. US20020160906 proposes a preparation method of acidic amorphous silica-alumina, and it is considered that a hydrocracking catalyst prepared by using the material together with a modified Y-type molecular sieve has high middle distillate selectivity. Wherein the unit cell constant of the modified Y-type molecular sieve is less than

In order to improve the activity and selectivity of petroleum processing catalysts, the zeolites used therein are generally modified, known modification methods including: the cation of the zeolite is changed through ion exchange and the silicon-aluminum ratio of the zeolite is improved through framework modification of the zeolite, wherein the zeolite obtained by the latter modification method has low aluminum content, reduced unit cell constant and improved silicon-aluminum ratio of the zeolite framework, thereby reducing acid density, improving acid strength and improving thermal stability and hydrothermal stability of the catalyst.

The prior art processes for achieving this goal include: hydrothermal dealuminization and chemical dealuminization; the former is a high-temperature calcination of NH in the presence of steam₄Preparing high-silicon Y zeolite from NaY zeolite, and named as ultrastable Y zeolite (USY); the latter is obtained by removing NH from a fluorine-containing compound, such as ammonium fluorosilicate or other fluorine-containing salts, such as ammonium fluoride, ammonium fluoroborate, ammonium fluorotitanate, as a dealuminating agent₃Aluminum in the framework of Y or NaY zeolites, and also silicon which migrates into the vacancies in the framework after dealumination, are referred to as framework silicon-rich Y zeolites (FSEY); or high silicon Y zeolite (DAY) prepared by using EDTA (ethylene diamine tetraacetic acid) as dealuminizing agent; chemical dealumination was combined with hydrothermal treatment and used alternately to make a new high-silicon Y zeolite (NHSY).

When the chemical dealuminization framework silicon-rich Y zeolite is adopted, EDTA is adopted, when the dealuminization degree exceeds 30 percent of the framework aluminum content, the crystallinity of the zeolite begins to reduce, more than 50 percent, and the reduction is more serious, and simultaneously, because the EDTA has stronger acidity and small solubility in water and is combined with Al³⁺The complexing power of (A) is weak, so that in order to maintain the crystallinity of the zeolite during the dealumination reaction, it is necessary to add very dilute solution to the reaction system at an extremely slow rate. By using SiCl₄The isomorphous substitution process has the disadvantages of strong corrosivity, difficult uniform reaction, difficult elution of the produced non-framework aluminum, reduced pore patency of zeolite, and SiCl₄Isomorphous substitution produces little to no secondary pores. By using (NH)₄)₂SiF₆Isomorphous substitution is carried out, although the reaction condition is mild, the prepared dealuminized zeolite has low non-framework aluminum content and few defect parts in the crystal structure, when the aluminum of the zeolite framework is removed by more than 50-60 percent, the zeolite crystal structure is still seriously damagedOn the other hand, the insoluble fluoride mixed in the zeolite is not easily washed out, and the residual fluoride may destroy the crystal structure of the zeolite at a high temperature.

In review, based on the existing methods, even if the Y-type molecular sieve is modified with the metal component, the catalytic activity thereof cannot be effectively improved.

Disclosure of Invention

The invention aims to provide a modified molecular sieve, a preparation method and application thereof, wherein the modified molecular sieve is used as a carrier of a hydrocracking catalyst, so that the hydrocracking catalyst has higher catalytic activity.

According to a first aspect of the present invention there is provided a method of modifying a molecular sieve, the method comprising the steps of:

(a) dropwise adding ammonia water into the mixed solution containing the nickel source and the molybdenum source until the pH value of the system is within the range of 9-11;

(b) impregnating the Y-type molecular sieve with the system obtained in the step (a), and then drying and roasting.

According to a second aspect of the present invention there is provided a modified molecular sieve produced by the process of the first aspect of the present invention.

According to a third aspect of the present invention there is provided the use of a modified molecular sieve according to the second aspect of the present invention as a support for a supported catalyst.

According to a fourth aspect of the present invention, the present invention provides a catalyst with hydrocracking effect, which comprises a carrier and a group VIII metal element and a group VIB metal element loaded on the carrier, wherein the carrier is the modified molecular sieve of the second aspect of the present invention.

According to a fifth aspect of the invention there is provided the use of a catalyst according to the fourth aspect of the invention as a catalyst for hydrocracking reactions.

According to a sixth aspect of the present invention there is provided a hydrocracking process comprising contacting a feedstock under hydrocracking conditions with a catalyst, said catalyst being as described in the fourth aspect of the present invention.

The (metallic nickel and molybdenum) modified molecular sieve has higher catalytic activity and higher hydrogenation activity when being used for hydrocracking aromatic hydrocarbon.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

According to a first aspect of the present invention there is provided a method of modifying a molecular sieve, characterised in that the method comprises the steps of:

(a) dropwise adding ammonia water into the mixed solution containing the nickel source and the molybdenum source until the pH value of the system is within 9-11 (such as 9, 9.5, 10, 10.5 and 11 or any value between the above values);

(b) impregnating the Y-type molecular sieve with the system obtained in the step (a), and then drying and roasting.

In the step (a), ammonia water is dripped into the solution, blue precipitate appears at first, ammonia water is dripped continuously, the precipitate is slowly dissolved, and when the pH value reaches 9-11, blue transparent solution is obtained, wherein the solution may contain nickel and molybdenum complexes. The inventors of the present invention have found that the catalytic activity of the Y-type molecular sieve can be further improved by modifying the Y-type molecular sieve with the nickel element and the molybdenum element blended in a specific ratio, and therefore, it is preferable that the molar ratio of nickel to molybdenum in terms of elements in a mixed solution containing a nickel source and a molybdenum source is 1 (1-10), more preferably 1 (2-8) (most preferably 1 (2-5)).

The concentration of the mixed solution containing the nickel source and the molybdenum source used in step (a) is preferably 0.1 to 1.5mol/L (or 0.8 to 1.5mol/L) in terms of the metal element.

In the step (a), the nickel source and the molybdenum source can be various water-soluble nickel-containing compounds and molybdenum-containing compounds, and specifically, the molybdenum source can be selected from ammonium molybdate and/or ammonium paramolybdate; the nickel source may be selected from at least one of nickel nitrate, nickel sulfate, nickel acetate, basic nickel carbonate, and nickel chloride.

In step (a), the ammonia water may be ammonia water with a high concentration, preferably, the concentration of ammonia water (as NH)₃Calculated) is 15-25 wt%.

In the step (a), the aqueous ammonia may be added dropwise at a conventional rate, but preferably, the aqueous ammonia is added dropwise at a rate of 1 to 10mL/min based on 100mL of the solution of the metal element-containing compound. The temperature in the dropping is not particularly required, and the dropping may be carried out at normal temperature.

According to a particular embodiment of the invention, step (a) does not involve the use of a transition metal element-containing starting material other than a nickel source and a molybdenum source.

In the step (b), there is no particular requirement for the amount of the system obtained in the step (a), as long as impregnation is convenient. The amount of the system obtained in step (a) is preferably 1 to 5mL, more preferably 1.3 to 2mL, per gram of the Y-type molecular sieve.

In step (b), the impregnation, drying and calcination may be carried out under conventional conditions.

Preferably, the impregnation conditions include: the temperature is 10-50 ℃. More preferably, the impregnation conditions further comprise: the time is 1.5-5 h.

Preferably, the drying conditions include: the temperature is 90-120 ℃. More preferably, the drying conditions further comprise: the time is 1.5-5 h. The impregnated sieve may also be washed, e.g., with water, before drying.

Preferably, the conditions of the calcination include: the temperature is 280-350 ℃. More preferably, the firing conditions further include: the time is 0.5-5 h.

The Y-type molecular sieve may be any common Y-type molecular sieve, and according to a preferred embodiment of the present invention, the Y-type molecular sieve is a molecular sieve having a specific unit cell constant, relative crystallinity, secondary pore volume, and non-framework aluminum number, i.e., a pre-modified molecular sieve. Thus, in this preferred embodiment, the Y-type molecular sieve used in step (b) is prepared by a process comprising specific steps. The inventors of the present invention have found that the modification method of the present invention is particularly suitable for modifying the Y-type molecular sieve obtained in the preferred embodiment, thereby improving the catalytic activity, especially the hydrogenation activity for aromatic hydrocarbons. The method of the present invention for obtaining the preferred embodiment of the Y-type molecular sieve comprises the step (1): and carrying out ion exchange on the ion exchange solution containing the ion exchanger and the raw material Y-type molecular sieve with at least part of compensation cations being alkali metal ions to obtain the exchanged molecular sieve.

At least part of the compensating cations of the raw material Y-type molecular sieve are alkali metal ions, and the alkali metal ions can be sodium ions and/or potassium ions, and are preferably sodium ions (namely, the raw material Y-type molecular sieve is a NaY molecular sieve). The content of alkali metal ions in the raw material Y-type molecular sieve is not particularly limited, depending on the source of the Y-type molecular sieve. Generally, the alkali metal ion as a compensating cation is contained in the raw material Y-type molecular sieve in an amount of 10 to 20% by weight, for example 12 to 16% by weight, in terms of oxide.

The silicon to aluminum ratio of the starting Y-type molecular sieve in the process according to the invention is not particularly limited and may be selected conventionally. Typically, the silica to alumina ratio of the starting Y-type molecular sieve is 4 or less, such as 3.5 or less, typically 2.5 to 3.5.

The crystallinity of the starting Y-type molecular sieve is not particularly limited by the process according to the invention. The crystallinity of the starting Y-type molecular sieve may be selected according to the use of the finally prepared Y-type molecular sieve. Typically, the relative crystallinity of the starting Y-type molecular sieve is above 85% (e.g., 85-120%). For Y-type molecular sieves used in hydrocracking catalysts, the relative crystallinity of the feedstock Y-type molecular sieve is preferably above 90%, such as from 90 to 95%.

The method of the present invention is not particularly limited with respect to the specific surface area and pore volume of the raw material Y-type molecular sieve, and may be selected according to the use situation of the finally produced Y-type molecular sieve. Specifically, when the finally prepared Y-type molecular sieve is used in a hydrocracking catalyst, the specific surface area of the raw material Y-type molecular sieve can be 650-850m²Per g, preferably 680-800m²Per g, more preferably700-750m²(ii)/g; the pore volume of the raw material Y-type molecular sieve can be 0.3-0.45mL/g, and preferably 0.32-0.4 mL/g.

In the step (1), the ion exchanger and the raw material Y-type molecular sieve are subjected to ion exchange, so that part of compensation cations in the raw material Y-type molecular sieve are replaced by ion exchange groups of the ion exchanger. Ion exchange can be achieved by contacting the starting Y-type molecular sieve with an ion exchange liquid containing the ion exchanger. The solvent for the ion-exchange liquid is not particularly limited, and may be selected according to the solubility of the ion exchanger, and is generally water.

According to the process of the present invention, from the viewpoint of further improving the crystallinity retention of the finally prepared Y-type molecular sieve, in step (1), the conditions of ion exchange are such that the alkali metal ion content in the exchanged molecular sieve is 20 to 40%, preferably 25 to 35%, more preferably 28 to 35%, such as 30 to 33%, of the alkali metal ion content in the starting Y-type molecular sieve.

The conditions of ion exchange can be adjusted to achieve a desired degree of ion exchange to control the alkali metal ion content of the exchanged molecular sieve within the above range. In a preferred embodiment of the invention, the ion exchange is carried out at a temperature not higher than 60 ℃. More preferably, the ion exchange is carried out at a temperature of 20-55 ℃.

In the preferred embodiment, the ion exchanger may be used in an amount of 20 to 60 parts by weight, preferably 30 to 55 parts by weight, and more preferably 35 to 50 parts by weight, relative to 100 parts by weight of the raw material Y-type molecular sieve.

In this preferred embodiment, the concentration of the ion exchanger in the ion exchange liquid may be conventionally selected, and is preferably 0.05 to 10mol/L, more preferably 0.1 to 8mol/L, still more preferably 1 to 7mol/L, such as 1.5 to 6 mol/L. In this preferred embodiment, the duration of the ion exchange can be selected based on the temperature at which the ion exchange is carried out and the concentration of the ion exchange liquid, so that the desired degree of ion exchange is achieved. Generally, the duration of the ion exchange may be 1 to 500min, preferably 5 to 300min, more preferably 10 to 150min, and still more preferably 20 to 60 min. In the present invention, the "duration of ion exchange" refers to the duration from the start of contact of the starting Y-type molecular sieve with the ion exchanger to the completion of the contact. In the actual operation process, the ion exchange liquid containing the ion exchanger can be dripped into the slurry containing the raw material Y-type molecular sieve, and the ion exchange is carried out in the dripping process, wherein the dripping time is the duration time of the ion exchange.

In the step (1), after ion exchange is completed, solid-liquid separation can be carried out, so that the exchanged molecular sieve is obtained. The exchanged molecular sieve may be dried under conventional conditions to remove residual ion exchange liquid. Generally, drying can be carried out at a temperature of 50-200 ℃, preferably 80-180 ℃, more preferably 100-150 ℃, and still more preferably 105-130 ℃. The drying may be performed in an air atmosphere, or may be performed in an inert atmosphere (e.g., a group zero gas, which may be argon and/or helium) without particular limitation. The drying may be carried out at ambient pressure (typically 1 atm) or reduced pressure (below ambient pressure). The duration of the drying can be selected according to the drying temperature and the specific drying mode, so that the ion exchange liquid in the exchanged molecular sieve can be removed, and generally the duration can be 1 to 10 hours, preferably 1.5 to 6 hours, and more preferably 2 to 4 hours.

The method comprises the following steps (2): and carrying out hydrothermal treatment on the exchanged molecular sieve to obtain the first hydrothermally treated molecular sieve.

In the present invention, the hydrothermal treatment may be carried out by subjecting the molecular sieve to a heat treatment in an atmosphere containing water vapor, for example, by continuously introducing an atmosphere containing water vapor into a vessel filled with the molecular sieve during the hydrothermal treatment; or by heat treating an aqueous molecular sieve slurry in a closed vessel; a combination of the two approaches may also be used. In the present invention, the hydrothermal treatment may be carried out at a temperature of 500 ℃ to 700 ℃. The atmosphere containing water vapor may be entirely water vapor. The water vapor-containing atmosphere may also contain a carrier gas, such as one or a combination of two or more of air, a group zero gas (e.g., argon and/or helium), and nitrogen. The extent of the reaction and the reaction rate can be adjusted by adjusting the content of the carrier gas in the atmosphere.

According to the method, the hydrothermal treatment in the step (2) is carried out under the condition that the structure-sensitive antisymmetric vibration frequency sigma in the infrared spectrogram of the molecular sieve after the first hydrothermal treatment₁The following conditions are satisfied:

35≤0.766×(1086－σ₁)≤42。

therefore, the finally prepared Y-type molecular sieve has rich secondary pores, and can obtain higher crystallinity retention rate and lower sodium oxide content.

Preferably, the hydrothermal treatment in step (2) is carried out under conditions such that the structure-sensitive antisymmetric vibration frequency σ in the infrared spectrogram of the molecular sieve after the first hydrothermal treatment₁The following conditions are satisfied:

38≤0.766×(1086－σ₁)≤41.8。

more preferably, the hydrothermal treatment in step (2) is carried out under conditions such that the structure-sensitive antisymmetric vibration frequency σ in the infrared spectrogram of the molecular sieve after the first hydrothermal treatment₁The following conditions are satisfied:

38≤0.766×(1086－σ₁)≤40。

the structure-sensitive antisymmetric vibration frequency sigma₁Refers to a vibration peak which is positioned in the range of 1050-.

In one embodiment of step (2), the hydrothermal treatment is carried out in an atmosphere containing water vapor. The atmosphere containing water vapor may contain no carrier gas or a carrier gas. When the water vapor-containing atmosphere contains a carrier gas, the content of the carrier gas may be 10 to 99% by volume, preferably 30 to 98.5% by volume, preferably 50% by volume or more, more preferably 80% by volume or more, further preferably 90% by volume or more, such as 95% by volume or more. In this embodiment, the amount of steam introduced may be 0.1 to 1mL/min, preferably 0.2 to 0.5mL/min, relative to 1g of the molecular sieve after the first hydrothermal treatment. In this embodiment, the hydrothermal treatment may be carried out at a temperature of 500-700 ℃, preferably at a temperature of 550-680 ℃, and the duration of the hydrothermal treatment may be selected according to the desired degree of hydrothermal treatment, and may be generally 0.5-5 hours, preferably 1-4 hours, more preferably 2-4 hours.

In another embodiment of step (2), the aqueous molecular sieve slurry is subjected to a heat treatment in a closed vessel. The water content of the aqueous molecular sieve slurry may be in the range of from 30 to 85 wt%, preferably from 45 to 70 wt%, more preferably from 50 to 65 wt%, and even more preferably from 52 to 58 wt%. In this embodiment, the temperature of the heat treatment may be 480-. The duration of the heat treatment may be selected according to the desired degree of heat treatment, and may be generally 0.5 to 5 hours, preferably 1 to 4 hours, and more preferably 1.5 to 3 hours. In this embodiment, the heat treatment may be performed without additionally applying pressure, i.e., under self pressure; additional pressure may also be applied. When the pressure is additionally applied, the pressure in the closed vessel in which the heat treatment is performed may be 0.05 to 0.3 MPa.

The method comprises the following steps (3): and under the dealuminization reaction condition, contacting the molecular sieve subjected to the first hydrothermal treatment with a dealuminization solution containing a dealuminization agent and an ion exchanger to obtain a dealuminization molecular sieve.

The dealuminating agent is selected from acids. The acid may be an organic acid and/or an inorganic acid. Specifically, the dealuminizing agent may be one or more of ethylenediaminetetraacetic acid, oxalic acid, sulfosalicylic acid, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, and fluorosilicic acid. Preferably, the dealuminating agent is an oxygen-containing inorganic acid and/or hydrochloric acid. More preferably, the dealuminating agent is one or more of hydrochloric acid, sulfuric acid, nitric acid, perchloric acid and phosphoric acid. Further preferably, the dealuminating agent is hydrochloric acid, sulfuric acid and nitric acid.

The solvent of the dealumination solution can be selected according to the solubility of the dealumination agent and the ion exchanger, so that the dealumination agent and the ion exchanger can be dissolved to form the solution. Preferably, the solvent of the dealumination solution is water.

In step (3), the ratio of the dealuminating agent (in moles) to the molecular sieve (in grams) after the first hydrothermal treatment is 0.0005 to 0.005, preferably 0.0008 to 0.004, more preferably 0.001 to 0.0035. The molar ratio of the dealuminating agent to the ion exchanger is 0.2 to 0.8, preferably 0.6 or less, more preferably 0.5 or less, still more preferably 0.45 or less, even more preferably 0.4 or less, particularly preferably 0.35 or less, such as 0.25 or less.

As a preferred example of the present invention, the ratio of the dealuminating agent (in moles) to the molecular sieve after the first hydrothermal treatment (in grams) is 0.001 to 0.0035, and the molar ratio of the dealuminating agent to the ion exchanger is 0.2 to 0.45. According to this preferred embodiment, the finally prepared Y-type molecular sieve is still able to maintain a higher relative crystallinity.

In the dealumination solution, the concentration of the dealumination agent may be 0.1 to 5mol/L, preferably 0.2 to 4mol/L, more preferably 0.4 to 3mol/L, still more preferably 0.5 to 2.5mol/L, and still more preferably 0.6 to 2 mol/L.

The contacting in step (3) may be carried out at a temperature of 10 to 100 deg.C, preferably 15 to 50 deg.C, more preferably 20 to 40 deg.C. In step (3), the duration of the contact can be selected according to the temperature and the amounts of the dealuminating agent and the ion exchanger, so that the desired degree of contact can be obtained. Generally, the duration of the contact may be from 0.25 to 5 hours, preferably from 0.5 to 3 hours, more preferably from 0.8 to 2.5 hours. The "duration of contact" refers to the time from the start of contact of the molecular sieve with the liquid phase containing the dealuminating agent and the ion exchanger to the completion of the contact after the first hydrothermal treatment. In practical operation, the dealuminizing agent and the ion exchanger are prepared into a solution, the solution is dripped into the slurry containing the molecular sieve after the first hydrothermal treatment, and then the stirring is continued for a period of time, wherein the contact duration is the total duration of the dripping and the stirring. The time of the dropwise addition generally represents 30 to 80% of the duration of the contact, preferably 40 to 60% of the duration of the contact.

The method comprises the following steps (4): and carrying out hydrothermal treatment on the dealuminized molecular sieve to obtain a molecular sieve after second hydrothermal treatment.

In the step (4), the hydrothermal treatment may be performed under a conventional condition, and is not particularly limited.

In one embodiment of step (4), the hydrothermal treatment is carried out in an atmosphere containing water vapor. The atmosphere containing water vapor may contain no carrier gas or a carrier gas. When the water vapor-containing atmosphere contains a carrier gas, the carrier gas may be introduced at a rate of 20 to 80L/min, preferably 40 to 70L/min, relative to the water vapor introduced at a rate of 1 mL/min. In this embodiment, the steam may be introduced at a rate of 0.1 to 1mL/min, preferably 0.2 to 0.5mL/min, relative to 1g of the dealuminated molecular sieve. In this embodiment, the hydrothermal treatment may be carried out at a temperature of 500-700 ℃, preferably 600-680 ℃. The duration of the hydrothermal treatment may be selected depending on the temperature at which the heat treatment is carried out, and may be generally 1 to 5 hours, preferably 2 to 3 hours.

In another embodiment of step (4), the aqueous molecular sieve slurry is subjected to a heat treatment in a closed vessel. The water content of the aqueous molecular sieve slurry may be in the range of from 30 to 85 wt.%, preferably from 45 to 70 wt.%, more preferably from 60 to 68 wt.%. In this embodiment, the temperature of the heat treatment may be 480-. The duration of the heat treatment may be selected depending on the temperature at which the heat treatment is carried out, and may be generally 0.5 to 5 hours, preferably 1 to 4 hours, and more preferably 2 to 4 hours. In this embodiment, the heat treatment may be performed without additionally applying pressure, i.e., under self pressure; additional pressure may also be applied. When the pressure is additionally applied, the pressure in the closed vessel for heat treatment may be 0.05 to 0.3 MPa.

Preferably, the second hydrothermal treatment is carried out in an atmosphere containing water vapor.

The method comprises the following steps (5): and under the condition of dealumination reaction, contacting the molecular sieve subjected to the second hydrothermal treatment with a dealumination solution containing an ion exchanger and fluosilicic acid to obtain the Y-type molecular sieve.

The solvent of the dealumination solution in the step (5) is not particularly limited, and may be selected according to the solubility of the ion exchanger and the fluorosilicic acid so as to dissolve the ion exchanger and the fluorosilicic acid. Generally, the solvent of the dealumination solution of step (5) is water.

In step (5), the molar ratio of the ion exchanger to the fluorosilicic acid may be from 0.1 to 8, preferably from 0.2 to 7, more preferably from 0.4 to 6. In step (5), the ratio of ion exchanger (in moles) to dealuminated molecular sieve (in grams) may be from 0.0005 to 0.01, preferably from 0.001 to 0.008.

In the dealuminizing solution in the step (5), the concentration of the fluosilicic acid can be selected conventionally. Preferably, in the dealumination solution in the step (5), the content of the fluosilicic acid can be 0.1-5mol/L, preferably 0.5-2.5mol/L, and more preferably 0.6-1.5 mol/L.

Step (5) may be carried out under conventional dealumination reaction conditions. Generally, the molecular sieve after the second hydrothermal treatment may be contacted with an ion exchanger and fluorosilicic acid at a temperature of 40 to 100 ℃, preferably 50 to 95 ℃, more preferably 55 to 80 ℃, further preferably 60 to 70 ℃. The duration of the contacting may be selected based on the temperature of the contacting and the amounts of fluorosilicic acid and ion exchanger used. In general, the duration of the contact may be from 0.5 to 5 hours, preferably from 0.8 to 3.5 hours. The "duration of contact" refers to the time from the start of contact of the molecular sieve with the liquid phase containing fluorosilicic acid and ion exchanger to the completion of contact after the second hydrothermal treatment. In the actual operation process, the fluosilicic acid and the ion exchanger are prepared into a solution and are dripped into the slurry containing the molecular sieve after the second hydrothermal treatment, and then the stirring is continued for a period of time, wherein the contact duration is the total duration of the dripping and the stirring. The time of the dropwise addition generally represents 30 to 60% of the duration of the contact, preferably 40 to 50% of the duration of the contact.

According to the method of the present invention, the kinds of the ion exchanger in the step (1), the ion exchanger in the step (3) and the ion exchanger in the step (5) may be the same or different, and the specific kinds are not particularly limited, and may be selected according to the kind of the compensating cation to be introduced into the Y-type molecular sieve. Specifically, when the finally prepared Y-type molecular sieve is used in a hydrocracking catalyst, the ion exchanger of step (1), the ion exchanger of step (3), and the ion exchanger of step (5) may each be an ammonium salt (i.e., ammonium ions are introduced as compensation cations by ion exchange). The ammonium salt may be an organic ammonium salt and/or an inorganic ammonium salt, and specific examples thereof may include, but are not limited to, one or more of ammonium oxalate, ammonium citrate, ammonium acetate, ammonium tartrate, ammonium sulfate, ammonium chloride, and ammonium nitrate. Preferably, the ammonium salt is an inorganic ammonium salt, such as one or more of ammonium sulfate, ammonium chloride and ammonium nitrate.

The ion exchanger in the step (3) and the dealuminating agent in the step (3) may have the same anion or different anions, and are not particularly limited.

According to a second aspect of the invention, there is also provided a modified molecular sieve prepared by the process of the invention. The modified molecular sieves according to the invention are particularly suitable for use in catalyst cracking catalysts.

According to a third aspect of the invention, there is provided the use of the modified molecular sieve of the invention as a support for a supported catalyst.

The supported catalyst may be a conventional catalyst in which an active ingredient is supported on a carrier. Preferably, the supported catalyst is a catalyst having a hydrogenation effect. More preferably, the supported catalyst is a catalyst having hydrocracking action.

According to a fourth aspect of the present invention, the present invention provides a catalyst with hydrocracking effect, which comprises a carrier and a group VIII metal element and a group VIB metal element loaded on the carrier, wherein the carrier is the modified molecular sieve of the present invention.

According to the catalyst of the present invention, the types of the group VIII metal element and the group VIB metal element are not particularly limited, and may be metal elements having a hydrocracking function, which are generally used in the hydrocracking technical field. Generally, the group VIII metal element is preferably nickel and/or cobalt; the group VIB metal element is preferably molybdenum and/or tungsten.

The loading amounts of the group VIII metal element and the group VIB metal element on the carrier in the present invention are not particularly limited, and may be conventionally selected. In general, the group VIB metal content, calculated as oxide, may be from 10 to 40% by weight, preferably from 20 to 30% by weight, based on the total amount of the catalyst; the content of the group VIII metal, calculated as oxide, may be from 2 to 10% by weight, preferably from 2.5 to 8% by weight; the carrier may be present in an amount of 50 to 88 wt%, preferably 62 to 77.5 wt%.

The group VIII metal element and the group VIB metal element may be supported on the carrier by a conventional method. In a preferred embodiment of the present invention, the group VIII metal element and the group VIB metal element are supported on the carrier by impregnation.

In this preferred embodiment, the impregnation may be a saturated impregnation or an excess impregnation, and is not particularly limited.

In this preferred embodiment, the group VIII metal element and the group VIB metal element may be simultaneously supported on the carrier, or the group VIII metal element and the group VIB metal element may be separately supported on the carrier. When the group VIII metal elements and the group VIB metal elements are respectively loaded on the carrier, the loading order of the group VIII metal elements and the group VIB metal elements is not particularly limited, and the group VIII metal elements may be loaded first and then the group VIB metal elements may be loaded, the group VIB metal elements may be loaded first and then the group VIII metal elements may be loaded, or the group VIII metal elements and the group VIB metal elements may be loaded at intervals. The interval loading of the VIII group metal element and the VIB group metal element is suitable for the situation that the VIII group metal element and the VIB group metal element are loaded on the carrier in multiple times. Preferably, the VIII group metal element and the VIB group metal element are simultaneously loaded on the carrier, so that the simplicity of the process can be improved, and the efficiency can be improved.

In this preferred embodiment, the impregnation solution may be formulated using a compound containing a group VIII metal element and a compound containing a group VIB metal element. The specific types of the group VIII metal element-containing compound and the group VIB metal element-containing compound may be selected according to the solvent of the impregnation solution, so that the impregnation solution can be dispersed in the solvent to form a stable impregnation solution. Preferably, the solvent of the impregnation liquid is water, in this case, the compound containing the group VIII metal element is preferably a water-soluble compound containing the group VIII metal element, and the compound containing the group VIB metal element is preferably a water-soluble compound containing the group VIB metal element.

Specifically, the group VIB metal element-containing compound may be selected from ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, molybdenum oxide, and tungsten oxide.

The group VIII metal element-containing compound may be selected from the group consisting of a nitrate of a group VIII metal element, a chloride of a group VIII metal element, a sulfate of a group VIII metal element, a formate of a group VIII metal element, an acetate of a group VIII metal element, a phosphate of a group VIII metal element, a citrate of a group VIII metal element, an oxalate of a group VIII metal element, a carbonate of a group VIII metal element, a basic carbonate of a group VIII metal element, a hydroxide of a group VIII metal element, a phosphate of a group VIII metal element, a phosphide of a group VIII metal element, a sulfide of a group VIII metal element, an aluminate of a group VIII metal element, a molybdate of a group VIII metal element, a tungstate of a group VIII metal element, and a water-soluble oxide of a group VIII metal element.

Preferably, the group VIII metal element-containing compound is selected from the group consisting of an oxalate of a group VIII metal element, a nitrate of a group VIII metal element, a sulfate of a group VIII metal element, an acetate of a group VIII metal element, a chloride of a group VIII metal element, a carbonate of a group VIII metal element, a basic carbonate of a group VIII metal element, a hydroxide of a group VIII metal element, a phosphate of a group VIII metal element, a molybdate of a group VIII metal element, a tungstate of a group VIII metal element, and a water-soluble oxide of a group VIII metal element.

Specifically, the group VIII metal element-containing compound may be selected from, but is not limited to: nickel nitrate, nickel sulfate, nickel acetate, basic nickel carbonate, cobalt nitrate, cobalt sulfate, cobalt acetate, basic cobalt carbonate, cobalt chloride and nickel chloride.

The content of the compound containing the VIII group metal element and the content of the compound containing the VIB group metal element in the impregnation liquid can be selected according to the times of impregnation so as to meet the requirement of the load capacity of the VIII group metal element and the VIB group metal element on the carrier.

The impregnation liquid can also contain at least one organic additive, so that the prepared catalyst has more excellent catalytic performance. The organic additive is selected from organic acid and organic amine. The organic acid is an organic compound containing at least one carboxyl (-COOH) group in a molecular structure, and the organic amine is an organic compound containing at least one amino (-NH) group in the molecular structure₂) The organic compound of (1). Preferably, the organic acid has a molecular structure containing at least two carboxyl groups, and the organic amine has a molecular structure containing at least two amine groups. The organic additive is preferably selected from citric acid, nitrilotriacetic acid, ethylenediamine and ethylenediamine tetraacetic acid. More preferably, the organic additive is selected from organic carboxylic acids, such as citric acid.

The content of the organic additive may be selected according to the content of the group VIII metal element-containing compound. Generally, the molar ratio of the organic additive to the group VIII metal element, calculated as the element, may be from 0.1 to 10, preferably from 0.4 to 8, more preferably from 0.5 to 4, even more preferably from 0.8 to 2, even more preferably from 0.9 to 1.5, such as from 0.95 to 1.2.

In the preferred embodiment, when the impregnation is carried out by excess impregnation, filtration may be carried out after the completion of the impregnation to remove an excess liquid phase.

In this preferred embodiment, after impregnation and optional filtration, the solid mass can be dried and optionally calcined to obtain the catalyst with hydrocracking according to the invention.

In the method for preparing the catalyst, calcination may or may not be carried out. In the present invention, the conditions for the drying and firing are not particularly limited and may be selected conventionally. Generally, the drying may be carried out at a temperature of 50 to 300 ℃, preferably 80 to 280 ℃, more preferably 100 ℃ to 250 ℃, further preferably 110 ℃ to 180 ℃. The duration of the drying may be selected according to the temperature of drying, subject to the removal of volatile substances. Generally, the drying time may be 1 to 12 hours, preferably 2 to 8 hours. The drying may be carried out in stages at different temperatures. For example: the first drying may be performed at a temperature not higher than 150c, followed by the second drying at a temperature higher than 150 c. The first drying may be performed at a temperature of 50 to 150 ℃, preferably 80 to 130 ℃, and further preferably 90 to 120 ℃, and the duration of the first drying may be 1 to 3 hours. The second drying may be performed at a temperature of more than 150 ℃ to 250 ℃, preferably at a temperature of 160 ℃. — -200 ℃, more preferably at a temperature of 165 — -180 ℃, and the duration of the second drying may be 1-5 hours, preferably 2-4 hours. The calcination may be carried out at a temperature of 350-550 deg.C, preferably 400-500 deg.C. The duration of the calcination may be 1 to 8 hours, preferably 2 to 6 hours.

According to a fifth aspect of the present invention, there is provided the use of a catalyst according to the present invention as a catalyst for hydrocracking reactions.

According to a sixth aspect of the present invention there is provided a hydrocracking process comprising contacting a feedstock under hydrocracking conditions with a catalyst, which catalyst is a catalyst of the present invention.

According to the hydrocracking process of the present invention, the feedstock may be various hydrocarbon oils such as heavy mineral oil, synthetic oil or mixtures thereof. Specifically, examples of the hydrocarbon oil may be, but are not limited to: vacuum gas oils, demetallized oils, atmospheric residues, deasphalted vacuum residues, coker distillates, shale oils, tar sand oils, and coal liquefaction oils.

The present invention is directed to the purpose of improving the conversion of a raw material in hydrocracking and the like by using the catalyst according to the present invention, and the remaining conditions for hydrocracking are not particularly limited and may be conventional conditions in the art.Preferably, the hydrocracking conditions include: the temperature is 200-650 ℃, preferably 300-510 ℃; the hydrogen partial pressure can be 3-24MPa, preferably 4-10 MPa; the liquid hourly space velocity of the raw material can be 0.1-50h^-1Preferably 1-40h^-1。

According to the hydrocracking process of the present invention, the catalyst is preferably presulfided prior to use. The conditions of the prevulcanisation may be conventional in the art. For example, the conditions of the prevulcanisation may include: presulfiding with sulfur, hydrogen sulfide or a sulfur-containing feedstock in the presence of hydrogen at a temperature of 140 ℃ and 370 ℃. According to the hydrocracking process of the present invention, the presulfiding can be carried out either outside the reactor or in situ within the reactor.

The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.

In the following examples, the IR spectroscopy was carried out on an IR spectrometer, model NICOLET 6700, from Thermo Scientific, scanning at 400-4000cm^-1The number of scans was 20, and the absorption mode was used.

In the following examples and comparative examples, the dry basis was determined by baking the sample at 600 ℃ for 4 hours.

TABLE 1

Example 1

(1) 100g (dry basis) NaY molecular sieve (produced by Zhongpetrochemical catalyst ChangLing division, whose physicochemical property parameters are listed in Table 1) was dispersed in 1500mL of water, and 200mL of an aqueous solution containing 50g of ammonium sulfate (purchased from Yili chemical reagent works, Beijing) was uniformly dropped at ambient temperature (25 ℃ C., the same applies hereinafter) with stirring (the dropping time was controlled at 30 min). After the ammonium sulfate aqueous solution was added dropwise, stirring was stopped and the mixture was filtered, and the solid phase was washed with deionized water 3 times and then dried at atmospheric pressure (1 atm, the same applies hereinafter) in an air atmosphere at 105 ℃ for 3 hours to obtain an exchanged molecular sieve having sodium ion contents as listed in table 2.

(2) Placing the exchanged molecular sieve prepared in the step (1) in a tubular furnace, continuously introducing steam (the introduction speed of the steam is 0.35 mL/(min. g molecular sieve)) into the tubular furnace, maintaining the temperature in the tubular furnace at 650 ℃, and carrying out hydrothermal treatment for 2 hours. Naturally cooling to ambient temperature, and taking out to obtain a first hydrothermally treated molecular sieve with a structure-sensitive antisymmetric vibration frequency sigma in an infrared spectrogram₁Listed in table 2.

(3) 80g (dry basis) of the first hydrothermally treated molecular sieve was dispersed in 800mL of distilled water, and 150mL of an aqueous solution containing 60g of ammonium chloride (purchased from Yili chemical Co., Ltd., Beijing) and 10g of HCl (the dropping time was controlled at 30min) was added dropwise at a constant rate at ambient temperature with stirring. After the addition was complete, stirring was continued for 30 min. Then, filtering is carried out, the solid phase is washed by deionized water for 3 times, and then is dried for 2 hours under normal pressure in the air atmosphere at the temperature of 105 ℃, so as to obtain the dealuminized molecular sieve.

(4) And (3) placing the dealuminized molecular sieve obtained in the step (3) in a tube furnace, continuously introducing steam into the tube furnace (the introduction speed of the steam is 0.20 mL/(min. g molecular sieve)), maintaining the temperature in the tube furnace at 650 ℃, and carrying out hydrothermal treatment for 2 hours. And after the hydrothermal treatment is finished, naturally cooling to the ambient temperature (25 ℃, the same below), and then taking out to obtain the molecular sieve after the second hydrothermal treatment.

(5) And (3) dispersing 60g (dry basis) of the molecular sieve prepared in the step (4) after the second hydrothermal treatment in 600mL of distilled water, heating the mixed solution to 60 ℃, and dropwise adding 150mL of aqueous solution containing 10g of ammonium sulfate and 27g of fluosilicic acid at a constant speed while stirring (the dropwise adding time is controlled to be 30 min). After the addition was complete, stirring was continued for 30 min. And after the temperature is naturally reduced to the ambient temperature, filtering the mixture, washing the solid phase with deionized water for 3 times, and drying the solid phase for 2.5 hours at the atmospheric pressure in the air atmosphere of 105 ℃ to obtain the dealuminized Y-type molecular sieve SDa.

(6) 5g of nickel nitrate and 10g of ammonium heptamolybdate are dissolved in 100mL of water, 21 wt% of concentrated ammonia water is dripped at the speed of 10mL/min to start to generate blue precipitate, the dripping is continued until the precipitate is dissolved, and the dripping is continued until the pH value reaches 9.6, so that 135mL of blue transparent solution is obtained.

(7) And (3) adding 100g of the dealuminized Y-type molecular sieve prepared in the step (5) into the blue transparent solution obtained in the step (6), continuously stirring for 2 hours, filtering, washing with clear water, drying at 105 ℃ for 2 hours, and roasting at 300 ℃ for 1 hour to obtain the modified molecular sieve S1.

Comparative example 1

The modified molecular sieve was prepared in the same manner as in example 1, except that in step (6), 5g of nickel nitrate and 10g of ammonium heptamolybdate were directly dissolved in 100mL of water (without the step of dropwise addition of concentrated aqueous ammonia) to obtain a nickel nitrate solution, which was used in the subsequent step to obtain modified molecular sieve SD 1.

Comparative example 2

A modified molecular sieve was prepared in the same manner as in example 1, except that in step (6), nickel nitrate was replaced with equimolar cobalt nitrate to give a modified molecular sieve SD 2.

Comparative example 3

A modified molecular sieve was prepared in the same manner as in example 1, except that in step (6), nickel nitrate was replaced with equimolar ammonium heptamolybdate to give a modified molecular sieve SD 3.

Example 2

(1) 100g (dry basis) of NaY molecular sieve (same as in example 1) was dispersed in 1500mL of water, and 300mL of an aqueous solution containing 50g of ammonium nitrate (purchased from Yili chemical Co., Ltd., Beijing) was added dropwise at a constant rate at ambient temperature (25 ℃ C., the same applies hereinafter) with stirring (the addition time was controlled at 50 min). After the ammonium nitrate aqueous solution was added dropwise, stirring was stopped and the mixed solution was filtered, and the solid phase was washed with deionized water 3 times and dried at 120 ℃ under atmospheric pressure for 3 hours to obtain an exchanged molecular sieve whose sodium ion content is shown in table 2.

(2) The exchanged molecular sieve prepared in step (1) was mixed with water to obtain a slurry containing the molecular sieve (55 wt% on a dry basis). The slurry containing the molecular sieve was filled in a crucible (specification of crucible: inner diameter 40mm, height 40mm, the same applies hereinafter), sealed and placed in a muffle furnace, heated to 550 ℃ and held at that temperature for 2 hours. Naturally cooling to ambient temperature to obtain a first hydrothermally treated molecular sieve with a structure-sensitive antisymmetric vibration frequency sigma in an infrared spectrogram₁Are listed in Table 2。

(3) Dispersing 85g (dry basis) of the molecular sieve subjected to the first hydrothermal treatment in 900mL of distilled water, and dropwise adding 100mL of solution containing 30g of ammonium sulfate and 6g of HNO at constant speed at ambient temperature while stirring₃The dropping time was controlled to be 30 min. After the addition was complete, stirring was continued for 20 min. Then, filtering is carried out, the solid phase is washed by deionized water for 3 times, and then is dried for 3 hours under normal pressure in the air atmosphere at 120 ℃, so as to obtain the dealuminized molecular sieve.

(4) Mixing the dealuminized molecular sieve prepared in step (3) with water to obtain a slurry containing the molecular sieve (the water content is 65 weight percent). The slurry containing the molecular sieve was filled in a crucible, which was sealed and placed in a muffle furnace, and the temperature was raised to 550 ℃ and held at that temperature for 2 hours. And after the hydrothermal treatment is finished, naturally cooling to the ambient temperature to obtain the molecular sieve after the second hydrothermal treatment.

(5) And (3) dispersing 80g (dry basis) of the molecular sieve prepared in the step (4) after the second hydrothermal treatment in 800mL of distilled water, heating the mixed solution to 70 ℃, and dropwise adding 100mL of aqueous solution containing 20g of ammonium chloride and 10g of fluosilicic acid at a constant speed while stirring (the dropwise adding time is controlled to be 30 min). After the addition was complete, stirring was continued for 40 min. And after the temperature is naturally reduced to the ambient temperature, filtering the mixture, washing the solid phase with deionized water for 3 times, and drying the solid phase for 4 hours at the normal pressure in the air atmosphere of 120 ℃ to obtain the dealuminized Y-type molecular sieve.

(6) 5g of nickel nitrate and 15g of ammonium heptamolybdate are dissolved in 100mL of water, 15 wt% of concentrated ammonia water is dripped at the speed of 1mL/min, blue precipitate begins to appear, the dripping is continued until the precipitate is dissolved, and the dripping is continued until the pH value reaches 9, so that 140mL of blue transparent solution is obtained.

(7) And (3) adding 100g of the dealuminized Y-shaped molecular sieve prepared in the step (5) into the blue transparent solution obtained in the step (6), continuously stirring for 2 hours, filtering, washing with clear water, drying at 100 ℃ for 2.5 hours, and roasting at 350 ℃ for 0.5 hour to obtain the modified molecular sieve S2.

Example 3

(1) 100g (dry basis) NaY molecular sieve (manufactured by Zhongjingshi catalyst Zhongyucun division, whose physicochemical property parameters are listed in Table 1) was dispersed in 1300mL of water, and 100mL of an aqueous solution containing 45g of ammonium nitrate (purchased from Beijing Yili chemical reagent factory) was uniformly dropped at 35 ℃ with stirring (dropping time was controlled at 40 min). After the aqueous solution was added dropwise, stirring was stopped and the mixture was filtered, and the solid phase was washed with deionized water 3 times and dried at atmospheric pressure in an air atmosphere at 110 ℃ for 3.5 hours to obtain an exchanged molecular sieve whose sodium ion content is shown in table 2.

(2) 85g (dry basis) of the exchanged molecular sieve prepared in the step (1) was placed in a tube furnace, and water vapor was continuously introduced into the tube furnace at a rate of 0.30 mL/(min. g molecular sieve) while maintaining the temperature in the tube furnace at 600 ℃ for 2.5 hours of hydrothermal treatment. Naturally cooling to the ambient temperature, and taking out to obtain the molecular sieve after the first hydrothermal treatment.

(3) 80g (dry basis) of the molecular sieve after the first hydrothermal treatment was dispersed in 1000mL of distilled water, and 150mL of an aqueous solution containing 60g of ammonium sulfate and 10g of sulfuric acid was uniformly dropped at 35 ℃ with stirring (dropping time was controlled at 45 min). After the addition was complete, stirring was continued for 60 min. Then, filtering is carried out, the solid phase is washed for 2 times by deionized water, and then is dried for 3 hours under the atmospheric pressure in the air atmosphere at the temperature of 110 ℃, so as to obtain the dealuminized molecular sieve.

(4) 60g (dry basis) of the molecular sieve obtained in the step (3) was placed in a tube furnace, and a mixed gas of water vapor and air (the water vapor was introduced at a rate of 0.3 mL/(min. g molecular sieve) and the air was introduced at a rate of 15L/(min. g molecular sieve)) was continuously introduced into the tube furnace, and the hydrothermal treatment was carried out for 3 hours while maintaining the temperature in the tube furnace at 620 ℃. And after the hydrothermal treatment is finished, naturally cooling to the ambient temperature to obtain the molecular sieve after the second hydrothermal treatment.

(5) And (3) dispersing 60g (dry basis) of the molecular sieve prepared in the step (4) after the second hydrothermal treatment in 650mL of distilled water, heating the mixed solution to 60 ℃, and dropwise adding 100mL of an aqueous solution containing 25g of ammonium chloride and 15g of fluosilicic acid at a constant speed while stirring (the dropwise adding time is controlled to be 25 min). After the addition was complete, stirring was continued for 30 min. And after the temperature is naturally reduced to the ambient temperature, filtering the mixture, washing the solid phase with deionized water for 2 times, and drying the solid phase for 3 hours at the normal pressure in the air atmosphere of 110 ℃ to obtain the dealuminized Y-type molecular sieve.

(6) 5g of nickel nitrate and 20g of ammonium heptamolybdate are dissolved in 100mL of water, 25 wt% concentrated ammonia water is dripped at the speed of 5mL/min, blue precipitate begins to appear, the dripping is continued until the precipitate is dissolved, and the dripping is continued until the pH value reaches 11, so that 145mL of blue transparent solution is obtained.

(7) And (3) adding 100g of the dealuminized Y-shaped molecular sieve prepared in the step (5) into the blue transparent solution obtained in the step (6), continuously stirring for 2 hours, filtering, washing with clear water, drying at 115 ℃ for 1.5 hours, and roasting at 280 ℃ for 2 hours to obtain the modified molecular sieve S3.

Example 4

(1) 100g (dry basis) of NaY molecular sieve (same as in example 3) was dispersed in 1100mL of water, and 150mL of an aqueous solution containing 40g of ammonium chloride (purchased from Yili chemical reagent works, Beijing, the same below) was added dropwise at a constant rate at 45 ℃ while stirring (the addition time was controlled at 30 min). After the aqueous solution was added dropwise, stirring was stopped and the mixture was filtered, and the solid phase was washed with deionized water 2 times and dried at atmospheric pressure in an air atmosphere at 115 ℃ for 3 hours to obtain the exchanged molecular sieve, the sodium ion content of which is shown in table 2.

(2) 85g (dry basis) of the exchanged molecular sieve prepared in the step (1) was placed in a tube furnace, and water vapor was continuously introduced into the tube furnace at a rate of 0.4 mL/(min. g molecular sieve) while maintaining the temperature in the tube furnace at 580 ℃ for 3 hours. Naturally cooling to the ambient temperature, and taking out to obtain the molecular sieve after the first hydrothermal treatment.

(3) 80g (dry basis) of the molecular sieve after the first hydrothermal treatment was dispersed in 900mL of distilled water, and 150mL of an aqueous solution containing 40g of ammonium nitrate and 8g of nitric acid was uniformly dropped at ambient temperature with stirring (dropping time was controlled at 40 min). After the addition was complete, stirring was continued for 45 min. Then, filtering is carried out, the solid phase is washed by deionized water for 3 times, and then is dried for 2 hours under normal pressure in the air atmosphere at the temperature of 130 ℃, so as to obtain the dealuminized molecular sieve.

(4) 60g of the molecular sieve (dry basis) obtained in the step (3) was placed in a tube furnace, and water vapor was continuously introduced into the tube furnace (the introduction rate of water vapor was 0.4 mL/(min. g of molecular sieve)) while maintaining the temperature in the tube furnace at 670 ℃ for 2 hours of hydrothermal treatment. And after the hydrothermal treatment is finished, naturally cooling to the ambient temperature to obtain the molecular sieve after the second hydrothermal treatment.

(5) And (3) dispersing 60g (dry basis) of the second hydrothermally treated molecular sieve prepared in the step (4) in 700mL of distilled water, heating the mixed solution to 60 ℃, and dropwise adding 120mL of an aqueous solution containing 15g of ammonium oxalate and 23g of fluosilicic acid at a constant speed while stirring (the dropwise adding time is controlled to be 35 min). After the addition was complete, stirring was continued for 45 min. And after the temperature is naturally reduced to the ambient temperature, filtering the mixture, washing the solid phase with deionized water for 3 times, and drying at 120 ℃ in the air atmosphere for 3.5 hours under normal pressure to obtain the dealuminized Y-type molecular sieve.

(6) The same as in example 2.

(7) In the same manner as in example 2, modified molecular sieve S4 was obtained.

Example 5

(1) 100g (dry basis) of NaY molecular sieve (same as in example 1) was dispersed in 1000mL of water, and 120mL of an aqueous solution containing 35g of ammonium chloride (purchased from Yili chemical Co., Ltd. of Beijing) was uniformly dropped at 55 ℃ while stirring (the dropping time was controlled at 45 min). After the aqueous solution was added dropwise, stirring was stopped and the mixture was filtered, and the solid phase was washed with deionized water 2 times and dried at 120 ℃ under atmospheric pressure for 2 hours to obtain the exchanged molecular sieve, the sodium ion content of which is shown in table 2.

(2) 85g (dry basis) of the exchanged molecular sieve prepared in the step (1) was placed in a tube furnace, and hydrothermal treatment was carried out for 3 hours while continuously feeding steam (the feeding rate of steam was 0.25 mL/(min. g molecular sieve)) into the tube furnace and maintaining the temperature in the tube furnace at 620 ℃. Naturally cooling to the ambient temperature, and taking out to obtain the molecular sieve after the first hydrothermal treatment.

(3) 80g (dry basis) of the molecular sieve after the first hydrothermal treatment was dispersed in 850mL of distilled water, and 150mL of an aqueous solution containing 60g of ammonium sulfate and 17g of fluorosilicic acid was uniformly dropped at 40 ℃ with stirring (dropping time was controlled at 60 min). After the addition was complete, stirring was continued for 75 min. Then, filtering is carried out, the solid phase is washed by deionized water for 3 times, and then is dried for 3 hours under normal pressure in the air atmosphere at 120 ℃, so as to obtain the dealuminized molecular sieve.

(4) 60g (dry basis) of the dealuminized molecular sieve obtained in the step (3) is placed in a tube furnace, a mixed gas of water vapor and air is continuously introduced into the tube furnace (the introduction speed of the water vapor is 0.25 mL/(min. g molecular sieve), the introduction amount of the air is 10L/(min. g molecular sieve)), the temperature in the tube furnace is maintained at 600 ℃, and hydrothermal treatment is carried out for 3.5 h. And after the hydrothermal treatment is finished, naturally cooling to the ambient temperature, and taking out to obtain the molecular sieve subjected to the second hydrothermal treatment.

(5) And (3) dispersing 60g (dry basis) of the molecular sieve prepared in the step (4) after the second hydrothermal treatment in 750mL of distilled water, heating the mixed solution to 60 ℃, and dropwise adding 130mL of aqueous solution containing 20g of ammonium chloride and 20g of fluosilicic acid at a constant speed while stirring (the dropwise adding time is controlled to be 30 min). After the addition was complete, stirring was continued for 40 min. And after the temperature is naturally reduced to the ambient temperature, filtering the mixture, washing the solid phase with deionized water for 2 times, and drying the solid phase for 3 hours at normal pressure in the air atmosphere of 115 ℃ to obtain the dealuminized Y-type molecular sieve.

(6) The same as in example 2.

(7) In the same manner as in example 2, modified molecular sieve S5 was obtained.

Example 6

(1) 100g (dry basis) of NaY molecular sieve (same as in example 3) was dispersed in 1200mL of water, and 200mL of an aqueous solution containing 50g of ammonium sulfate (purchased from Yili chemical Co., Ltd. of Beijing) was uniformly added dropwise at 20 ℃ with stirring (the addition time was controlled at 25 min). After the aqueous solution was added dropwise, stirring was stopped and the mixture was filtered, and the solid phase was washed 4 times with deionized water and dried at atmospheric pressure in an air atmosphere at 130 ℃ for 2 hours to obtain the exchanged molecular sieve, the sodium ion content of which is shown in table 2.

(2) 85g (dry basis) of the exchanged molecular sieve prepared in the step (1) was placed in a tube furnace, and water vapor was continuously introduced into the tube furnace at a rate of 0.45 mL/(min. g molecular sieve) while maintaining the temperature in the tube furnace at 670 ℃ for 2 hours. Naturally cooling to the ambient temperature, and taking out to obtain the molecular sieve after the first hydrothermal treatment.

(3) 80g (dry basis) of the molecular sieve after the first hydrothermal treatment was dispersed in 950mL of distilled water, and 150mL of an aqueous solution containing 60g of ammonium nitrate and 15g of oxalic acid was uniformly dropped at ambient temperature with stirring (dropping time was controlled at 45 min). After the addition was complete, stirring was continued for 60 min. Then, filtering is carried out, the solid phase is washed for 2 times by deionized water and then dried for 3 hours under normal pressure in the air atmosphere at 120 ℃, thereby obtaining the dealuminized molecular sieve.

(4) 60g (dry basis) of the dealuminized molecular sieve obtained in the step (3) was placed in a tube furnace, and a mixed gas of steam and air (the steam introduction rate was 0.3 mL/(min. g molecular sieve) and the air introduction rate was 20L/(min. g molecular sieve)) was continuously introduced into the tube furnace, and the hydrothermal treatment was carried out for 2.5 hours while maintaining the temperature in the tube furnace at 645 ℃. And after the hydrothermal treatment is finished, naturally cooling to the ambient temperature, and taking out to obtain the molecular sieve subjected to the second hydrothermal treatment.

(5) And (3) dispersing 60g (dry basis) of the molecular sieve prepared in the step (4) after the second hydrothermal treatment in 650mL of distilled water, heating the mixed solution to 60 ℃, and dropwise adding 110mL of aqueous solution containing 15g of ammonium nitrate and 10g of fluosilicic acid at a constant speed while stirring (the dropwise adding time is controlled to be 25 min). After the addition was complete, stirring was continued for 35 min. And after the temperature is naturally reduced to the ambient temperature, filtering the mixture, washing the solid phase with deionized water for 3 times, and drying the solid phase for 3 hours at the normal pressure in the air atmosphere of 120 ℃ to obtain the dealuminized Y-type molecular sieve.

(6) The same as in example 3.

(7) In the same manner as in example 3, modified molecular sieve S6 was obtained.

Example 7

A modified molecular sieve was prepared in the same manner as in example 1, except that the following process flow was used to prepare the dealuminated Y-type molecular sieve.

(1) 100g (dry basis) of NaY molecular sieve (same as in example 1) was dispersed in 950mL of distilled water, and the mixture was heated to 60 ℃ and 60mL of an aqueous solution containing 30g of ammonium sulfate and 25g of fluorosilicic acid was added dropwise at a constant rate while stirring (the addition time was controlled at 30 min). After the addition was complete, stirring was continued for 30 min. And after the temperature is naturally reduced to the ambient temperature, filtering the mixture, washing the solid phase for 3 times by using deionized water, and drying the solid phase for 2.5 hours at the atmospheric pressure in the air atmosphere of 105 ℃.

(2) Placing the exchanged molecular sieve prepared in the step (1) in a tubular furnace, continuously introducing steam (the introduction speed of the steam is 0.35 mL/(min. g molecular sieve)) into the tubular furnace, maintaining the temperature in the tubular furnace at 650 ℃, and carrying out hydrothermal treatment for 2 hours. Naturally cooling to the ambient temperature and then taking out.

(3) 80g (dry basis) of the molecular sieve obtained in step (2) was dispersed in 800mL of distilled water, and 70mL of an aqueous solution containing 10g of ammonium chloride and 10g of HCl was uniformly dropped at ambient temperature while stirring (dropping time was controlled at 30 min). After the addition was complete, stirring was continued for 30 min. Then, filtration was carried out, and the solid phase was washed 3 times with deionized water and then dried under atmospheric pressure at 105 ℃ for 2 hours in an air atmosphere.

(4) And (3) putting the molecular sieve obtained in the step (3) into a tubular furnace, continuously introducing steam into the tubular furnace (the introduction speed of the steam is 0.20 mL/(min. g molecular sieve)), maintaining the temperature in the tubular furnace at 600 ℃, and carrying out hydrothermal treatment for 3 hours. And after the hydrothermal treatment is finished, naturally cooling to the ambient temperature.

(5) 70g (dry basis) of the molecular sieve obtained in step (4) was dispersed in 1500mL of water, and 100mL of an aqueous solution containing 40g of ammonium sulfate was uniformly dropped at ambient temperature with stirring (dropping time was controlled at 30 min). And after the ammonium sulfate aqueous solution is dropwise added, stopping stirring, filtering the mixed solution, washing the solid phase with deionized water for 3 times, and drying the solid phase for 3 hours at the atmospheric pressure in the air atmosphere at the temperature of 105 ℃ to obtain the dealuminized Y-type molecular sieve.

(6) The same as in example 1.

(7) In the same manner as in example 1, modified molecular sieve S7 was obtained.

Example 8

A modified molecular sieve was prepared in the same manner as in example 1, except that the dealuminized Y-type molecular sieve was prepared in the same manner as in example 1 disclosed in the specification of CN1388064A, and the specific operating conditions were as follows:

(1) dissolving 50g ammonium sulfate in 1500mL water, adding 100g (dry basis) NaY molecular sieve (same as example 1) into the prepared solution, stirring at 20 deg.C for 30min, filtering, pulping with deionized water, washing, and filtering to obtain the selective ammonium exchange Y-type molecular sieve.

(2) The molecular sieve obtained was placed in a tube furnace at 650 ℃ and hydrothermal calcined for 2h in a steam atmosphere of 50 wt% (balance nitrogen).

(3) Adding the above calcined zeolite 20g and ammonium sulfate 20g into 300mL distilled water, stirring, adding 0.1mol/L hydrochloric acid 30mL within 60min under stirring, filtering, pulping with water, filtering, and drying at 105 deg.C for 3 hr.

And carrying out hydrothermal roasting (namely, the step (2)) and hydrochloric acid treatment (the step (3)) once more according to the steps to obtain the dealuminized Y-type molecular sieve.

(4) Same as in step (6) of example 1.

(5) The same procedure as in step (7) of example 1 gave modified molecular sieve S8.

Example 9

A modified molecular sieve was prepared in the same manner as in example 1, except that in step (6), nickel nitrate was used in an amount of 10g and ammonium heptamolybdate was used in an amount of 5g, to obtain a modified molecular sieve S9.

TABLE 2

Test example 1

This test example was used to characterize the acidity of the modified molecular sieves of the present invention, and the results are shown in table 3.

The acidity of the molecular sieve is measured by two methods respectively, and two probe molecules with different molecular sizes are adopted: pyridine and ammonia. The molecular sieve of ammonia gas has small size and can contact with almost all acid centers of the molecular sieve, the measured acid amount is the total acid amount of the molecular sieve, the molecular size of pyridine is relatively large and can only contact with the acid centers in the molecular sieve pore passages with the pore diameters larger than a certain pore diameter, and the acid centers measured by the two modes reflect the accessibility of the acid centers. Dividing total acid content by NH measured by pyridine absorption infrared spectrometry₃-total acid amount determined by TPD method, multiplied by 100, as index of acid center accessibility for a certain material. The result is an integer and the fractional part is rounded off. For macromolecular transformations, larger values are better.

Wherein the acidity determination method using pyridine as a probe molecule is pyridine infrared spectrometry. The specific determination method is shown in Industrial catalyst analysis and test characterization (China)Petrochemical press, Liu xi Yao et al, Beijing, 1993, 349 + 360). The acidity determination method using ammonia as a probe molecule is NH₃TPD method, see "Industrial catalyst assay characterization" (China petrochemical Press, Yao of Liu xi et al, Beijing, 1993, 349) 360). Where appropriate, use is made of NH₃The TPD method is used for measuring the acidity of the molecular sieve, and a dehydration column is required to be added before a TCD detector.

Test example 2

This test example is presented to illustrate the use of the modified molecular sieve of the present invention in catalyst supports, catalysts and hydrocracking processes.

Preparation of the catalyst: 31.5g of nickel nitrate was added to 300mL of water and completely dissolved, and 60g of the molecular sieve sample obtained in each example and comparative example was added to the solution, and the solution was heated to 96 ℃ with stirring and stirred under reflux for 4 hours. After filtration, the mixture is washed twice with deionized water, dried at 120 ℃ for 3 hours and roasted at 400 ℃ for 2 hours. Crushing the prepared molecular sieve tablets, and sieving to obtain 40-60 mesh granules for later use.

Micro-reverse evaluation: a mixture of n-decane and toluene (weight ratio of the two: 9:1) was used as a reactant. Taking 0.5g of catalyst particles with 40-60 meshes, filling the catalyst particles into a reactor, and keeping the hydrogen partial pressure and the sulfurized oil space velocity at 300 ℃ and 4MPa for 40h^-1Under the condition of 2 hours of vulcanization, at 360 ℃, 4MPa of hydrogen partial pressure and 40 hours of reaction oil airspeed^-1The hydrogenation activity (conversion of toluene to first order reaction rate constant) and hydrocracking activity (conversion of n-decane) of the catalyst were evaluated under the conditions of (1). The results are shown in table 3 below.

Wherein, the material after reaction is analyzed by adopting an online gas chromatography method, and the conditions comprise: an agilent 6850 chromatograph is adopted, an HP-1 chromatographic column is adopted, and the temperature is kept for 2min at 40 ℃ and is increased to 160 ℃ at 10 ℃/min and is kept for 2min by adopting a programmed heating method. The method of chromatography-mass spectrometry is used for the qualitative determination of the cracking hydrocarbon below C10 in advance. The higher the toluene (or n-decane) conversion rate is, the better the hydrogenation activity is, the higher the toluene (or n-decane) conversion rate is, the more the toluene (or n-decane) conversion rate is, the (molar amount of toluene (or n-decane) before the reaction-molar amount of toluene (or n-decane) after the reaction)/the molar amount of toluene (or n-decane) before the reaction is.

TABLE 3

Molecular sieve numbering	Toluene conversion (%)	N-decane conversion (%)	Acid center accessibility index
				S1	17.9	65.3	66
SD1	12.8	56.7	66
				SD2	13.3	63.2	66
SD3	5.6	52.1	66
				S2	18.4	63.6	69
S3	19.1	60.7	70
				S4	19.7	64.8	72
S5	19.3	63.5	71
				S6	20.6	65.5	74
S7	12.3	58.8	66
				S8	15.6	64.2	57
S9	5.8	55.4	57

From the results in table 3, it can be seen that the modified molecular sieve obtained by the method of the present invention has higher hydrogenation activity when used for preparing a hydrocracking catalyst.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (12)

1. A method for modifying a Y-type molecular sieve, comprising the steps of:

(a) dropwise adding ammonia water into the mixed solution containing the nickel source and the molybdenum source until the pH value of the system is within the range of 9-11;

(b) dipping the Y-type molecular sieve by using the system obtained in the step (a), and then drying and roasting;

the Y-type molecular sieve used in the step (b) is prepared by a method comprising the following steps:

(1) carrying out ion exchange on an ion exchange solution containing an ion exchanger and a raw material Y-type molecular sieve with at least part of compensation cations being alkali metal ions to obtain an exchanged molecular sieve;

(2) carrying out hydro-thermal treatment on the exchanged molecular sieve to obtain a first hydro-thermally treated molecular sieve, wherein the hydro-thermal treatment conditions enable the structure-sensitive anti-symmetric vibration frequency sigma in an infrared spectrogram of the first hydro-thermally treated molecular sieve₁The following conditions are satisfied:

35≤0.766×(1086－σ₁)≤42；

(3) contacting the first hydrothermally treated molecular sieve with a dealumination solution containing a dealumination agent and an ion exchanger under dealumination reaction conditions to obtain a dealumination molecular sieve, wherein the dealumination agent is selected from acid, the ratio of the dealumination agent to the first hydrothermally treated molecular sieve is 0.0005-0.005, the dealumination agent is calculated by mole, the first hydrothermally treated molecular sieve is calculated by gram, and the molar ratio of the dealumination agent to the ion exchanger is 0.2-0.8;

(4) carrying out hydrothermal treatment on the dealuminized molecular sieve to obtain a molecular sieve after second hydrothermal treatment;

(5) under the dealumination reaction condition, contacting the molecular sieve subjected to the second hydrothermal treatment with a dealumination solution containing an ion exchanger and fluosilicic acid to obtain a pre-modified molecular sieve;

wherein the roasting conditions comprise: the temperature is 280-350 ℃, and the time is 0.5-5 h.

2. The method according to claim 1, wherein in the mixed solution containing the nickel source and the molybdenum source, the molar ratio of nickel to molybdenum in terms of elements is 1:1-10, and the concentration in terms of metal elements is 0.1-1.5 mol/L; and/or the concentration of the ammonia water is 15-25 wt%;

and/or the dropping speed of the ammonia water is 1-10mL/min based on 100mL of the mixed solution containing the nickel source and the molybdenum source.

3. The process according to claim 1 or 2, wherein the amount of the system obtained in step (a) is 1-5mL per gram of the Y-type molecular sieve.

4. The method of claim 1, wherein the conditions of the impregnation comprise: the temperature is 10-50 ℃ and the time is 1.5-5 h;

and/or, the drying conditions include: the temperature is 90-120 ℃ and the time is 1.5-5 h.

5. A modified molecular sieve prepared by the method of any one of claims 1-4.

6. Use of the modified molecular sieve of claim 5 as a support for a supported catalyst.

7. A catalyst with hydrocracking effect, which comprises a carrier and a VIII group metal element and a VIB group metal element loaded on the carrier, and is characterized in that the carrier is the modified molecular sieve in claim 5.

8. The catalyst according to claim 7, wherein the content of the group VIII metal element in terms of oxide is 2 to 10% by weight based on the total amount of the catalyst; the content of the VIB group metal element calculated by oxide is 10-40 wt%; the content of the carrier is 50-88 wt%.

9. The catalyst according to claim 8, wherein the content of the group VIII metal element in terms of oxide is 2.5 to 8% by weight based on the total amount of the catalyst; the content of the VIB group metal element calculated by oxide is 20-30 wt%; the content of the carrier is 62-77.5 wt%.

10. The catalyst according to claim 7 or 8, wherein the group VIII metal element is nickel and/or cobalt and the group VIB metal element is molybdenum and/or tungsten.

11. Use of a catalyst according to any one of claims 7 to 10 as a catalyst for hydrocracking reactions.

12. A hydrocracking process comprising contacting a feedstock with a catalyst under hydrocracking conditions, the catalyst being as claimed in any one of claims 7 to 10.