CN105435836B - A kind of hydrocracking catalyst and its preparation and application - Google Patents

Abstract

A hydrocracking catalyst and its preparation and application, the catalyst contains a carrier containing a molecular sieve solid acid component, the molecular sieve solid acid component is a mixture comprising ZSM‑5 molecular sieve and MoBeta molecular sieve, ZSM‑5 in the molecular sieve mixture 5 The weight ratio of molecular sieve to MoBeta molecular sieve is 9:1～1:9, wherein, the n value of MoBeta molecular sieve is 0<n<1, n=I/αI ₀ , characterized by FT-IR method, I is MoBeta type 3610cm ^-1 absorption peak intensity in the FT-IR spectrogram of zeolite molecular sieve, _I Be the 3610cm ^-1 absorption peak intensity in the FT-IR spectrogram of the parent Beta type zeolite molecular sieve of MoBeta type zeolite molecular sieve, α is MoBeta type zeolite molecular sieve The ratio of the 3740cm ^-1 absorption peak intensity in the FT-IR spectrum to the 3740cm ^-1 absorption peak intensity in the FT-IR spectrum of the parent Beta zeolite molecular sieve. Compared with the prior art, the catalyst provided by the invention significantly improves the conversion of bicyclic and above polycyclic aromatic hydrocarbons and the selectivity of ideal products in the hydrocracking reaction.

Description

A kind of hydrocracking catalyst and its preparation and application

technical field

The invention relates to a hydrogenation treatment catalyst and its preparation and application.

Background technique

The world's crude oil is becoming heavier and inferior, and the content of sulfur and aromatics is gradually increasing, while the demand for clean fuel oil and high-quality chemical raw materials is gradually increasing. As one of the main processes for lightening heavy oil, hydrocracking is also the only important technical means that can directly produce clean fuels and high-quality chemical raw materials while lightening raw materials. At present, how to maximize the conversion of aromatics into ideal components of fuel oil or high-quality chemical raw materials has become one of the difficulties that must be overcome in hydrocracking. E.g:

20120352307.9 discloses a hydrocracking catalyst containing hierarchically porous Beta molecular sieves. The carrier of the catalyst is composed of hierarchically porous Beta molecular sieves, modified Y molecular sieves, alumina and amorphous silica-alumina, and the hydrogenation active component is metal Oxides of Ni and W, additives are P or F. The catalyst is characterized by rich mesoporous structure and homogeneous and moderately strong acid distribution.

201110350783.2 discloses a hydrocracking catalyst, the catalyst is composed of modified Beta molecular sieve, modified Y-type molecular sieve, aluminum oxide carrier and hydrogenation metal component, modified Beta molecular sieve is directly crystallized Beta molecular sieve slurry After ammonium exchange and release agent treatment, hydrothermal treatment first, and then aluminum salt solution treatment, the purpose is to uniformly remove part of the non-skeleton aluminum under the condition of maintaining the high crystallinity of Beta molecular sieve, and optimize the acid distribution and pores of the molecular sieve distributed.

201110369112.0 discloses a catalyst for converting polycyclic aromatic hydrocarbons into monocyclic aromatic hydrocarbons, the catalyst comprising 34.5-60% by weight of FAU type zeolite and a mixture of at least one molecular sieve selected from MOR, BEA, MFI or MCM-22, 39.5- 65% by weight of at least one selected from γ-alumina, η-alumina or pseudo-boehmite is the binder and 0.05-0.9% of at least one metal selected from Pt, Pd or Ir.

The difficulty in achieving high-efficiency conversion of aromatics in the hydrocracking process lies in improving the selectivity of ideal products, suppressing coke formation, and prolonging the service life of catalysts. The ideal products for the conversion of bicyclic and above aromatics are high value-added components such as benzene, toluene, xylene (BTX) and high cetane number components such as long side chain alkylbenzenes. The key to improving the selectivity of ideal products is to achieve a high level of synergy and matching between the hydrogenation function and the cracking function.

Contents of the invention

The technical problem to be solved by the present invention is to provide a hydrocracking catalyst with improved performance, a preparation method and application of the catalyst.

The content of the invention that the present invention relates to comprises:

1. A hydrocracking catalyst containing a carrier containing a molecular sieve solid acid component, the molecular sieve solid acid component being a mixture comprising ZSM-5 molecular sieve and MoBeta molecular sieve, ZSM-5 molecular sieve and Beta molecular sieve in the molecular sieve mixture The weight ratio is 9:1～1:9, wherein, the n value of MoBeta molecular sieve is 0<n<1, n=I/αI ₀ , characterized by FT-IR method, I is the FT- 3610cm ^-1 absorption peak intensity in the IR spectrum, I ₀ is the 3610cm ^-1 absorption peak intensity in the FT-IR spectrum of the parent Beta zeolite molecular sieve of MoBeta type zeolite molecular sieve, α is the FT-IR spectrum of MoBeta type zeolite molecular sieve The ratio of the 3740cm ^-1 absorption peak intensity in the medium to the 3740cm ^-1 absorption peak intensity in the FT-IR spectrum of the parent Beta zeolite molecular sieve.

2. The catalyst according to 1, characterized in that the weight ratio of ZSM-5 molecular sieve and Beta molecular sieve in the molecular sieve mixture is 4:1-1:1.

3. The catalyst according to 1, wherein the n value of the MoBeta molecular sieve is 0.3≤n≤0.8.

4. The catalyst according to 1, characterized in that, based on the MoBeta zeolite molecular sieve, the molybdenum content in the MoBeta zeolite molecular sieve is 0.5-10% by weight.

5. The catalyst according to 4, characterized in that, based on the MoBeta zeolite molecular sieve, the molybdenum content in the MoBeta zeolite molecular sieve is 1-9% by weight.

6. The catalyst according to 1, characterized in that the hydrogenation active metal component in the catalyst is selected from at least one Group VIII metal component and at least one VIB metal component, calculated as oxides and based on the Based on the catalyst mentioned above, the content of the Group VIII metal component is 1-10% by weight, and the content of the Group VIB metal component is 5-50% by weight.

7. The catalyst according to 6, characterized in that the Group VIII metal component is selected from cobalt and/or nickel, and the VIB metal component is selected from molybdenum and/or tungsten, in terms of oxides and the catalyst is Based on this, the content of the Group VIII metal component is 1.5-6% by weight, and the content of the Group VIB metal component is 10-40% by weight.

8. The catalyst according to 1, characterized in that the carrier contains a heat-resistant inorganic oxide matrix, based on the carrier, the content of the heat-resistant inorganic oxide matrix is greater than 0 to less than or equal to 99% by weight %.

9. The catalyst according to 8, characterized in that the heat-resistant inorganic oxide substrate is selected from one or more of alumina, silica and silica-alumina, based on the carrier, the The content of the heat-resistant inorganic oxide matrix is 10-90% by weight.

10. The catalyst according to 1 or 8, characterized in that, based on the catalyst, the content of the carrier in the catalyst is 45-90% by weight, and the content of the Group VIII metal component in terms of oxides is 1-10% by weight, and the content of the Group VIB metal component in terms of oxide is 5-50% by weight.

11. The catalyst according to 10, characterized in that, based on the catalyst, the content of the carrier in the catalyst is 55-85% by weight, and the content of the Group VIII metal component in terms of oxides is 1.5 -6% by weight, the content of the Group VIB metal component in terms of oxide is 10-40% by weight.

12. A method for preparing a hydrocracking catalyst, comprising preparing a carrier containing a molecular sieve solid acid component, and the molecular sieve solid acid component is a mixture comprising ZSM-5 molecular sieve and MoBeta molecular sieve, and in the molecular sieve mixture, ZSM- 5 The weight ratio of molecular sieve to Beta molecular sieve is 9:1~1:9, wherein, the n value of MoBeta molecular sieve is 0<n<1, n=I/αI ₀ , characterized by FT-IR method, I is MoBeta type 3610cm ^-1 absorption peak intensity in the FT-IR spectrum of zeolite molecular sieve, I ₀ is the 3610cm ^-1 absorption peak intensity in the FT-IR spectrum of the parent Beta type zeolite molecular sieve of MoBeta type zeolite molecular sieve, α is MoBeta type zeolite molecular sieve The ratio of the 3740cm ^-1 absorption peak intensity in the FT-IR spectrum to the 3740cm ^-1 absorption peak intensity in the FT-IR spectrum of the parent Beta zeolite molecular sieve.

13. The method according to 12, characterized in that the weight ratio of ZSM-5 molecular sieve and Beta molecular sieve in the molecular sieve mixture is 4:1-1:1; the n value of the MoBeta molecular sieve is 0.3≤n≤ 0.8.

14. The method according to 12, characterized in that, based on the MoBeta zeolite molecular sieve, the molybdenum content in the MoBeta zeolite molecular sieve is 0.5-10% by weight.

15. The method according to 14, characterized in that, based on the MoBeta zeolite molecular sieve, the molybdenum content in the MoBeta zeolite molecular sieve is 1-9% by weight.

16. The method according to 12, characterized in that the preparation method of the MoBeta-type zeolite molecular sieve comprises: (1) mixing the Beta-type zeolite molecular sieve with the Mo-containing compound to obtain a mixture of the Beta-type zeolite molecular sieve and the Mo-containing compound The mixture is based on the MoBeta-type zeolite molecular sieve, and the consumption of each component is such that in the final MoBeta-type zeolite molecular sieve, the molybdenum content in terms of oxide is 0.5-10% by weight; (2) the mixture obtained in step (1) High-temperature treatment in an atmosphere containing water vapor, the conditions of the high-temperature treatment include a calcination temperature of 200-700°C, a calcination time of 1-24 hours, and a gas flow rate of 0.3-2 standard cubic meters/kg·hour containing water vapor, Obtain MoBeta type zeolite molecular sieve.

17. The method according to 16, characterized in that, taking the MoBeta-type zeolite molecular sieve as a benchmark, the amount of each component in the step (1) is such that the molybdenum content calculated as oxide in the final MoBeta-type zeolite molecular sieve is 1-9% by weight; the conditions of the high temperature treatment in the step (2) include that the calcination temperature is 400-650° C., the calcination time is 2-12 hours, and the gas flow rate containing water vapor is 0.6-1.5 standard cubic meters/kg ·Hour.

18. The method according to 17, characterized in that the atmosphere containing water vapor contains diluent gas, wherein the volume mixing ratio of water vapor and diluent gas is 1:10-100.

19. The method according to 18, characterized in that the diluent gas is selected from hydrogen, nitrogen and a mixture thereof, preferably hydrogen, or a mixture of air and air and nitrogen; the water vapor and the diluent gas The volume mixing ratio is 1:20-80.

20. The method according to 12, characterized in that the method includes the step of introducing a hydrogenation active metal component into the carrier, and the hydrogenation active metal component in the hydrocracking catalyst is selected from at least A metal component of Group VIII and at least one metal component of VIB, calculated as oxides and based on the catalyst, the introduction amount of metal component of Group VIII makes the content of metal component of Group VIII in the final catalyst be 1-10% by weight, the introduction amount of the Group VIB metal component makes the content of the Group VIB metal component in the final catalyst 5-50% by weight.

21. The method according to 20, characterized in that the Group VIII metal component is selected from cobalt and/or nickel, and the VIB metal component is selected from molybdenum and/or tungsten, calculated as oxides and based on the catalyst Standard, the introduction amount of the Group VIII metal component makes the content of the Group VIII metal component in the final catalyst be 1.5-6% by weight, and the introduction amount of the VIB Group metal component makes the content of the VIB Group metal component in the final catalyst The content is 10-40% by weight.

22. The method according to 12, characterized in that the method includes the step of introducing a heat-resistant inorganic oxide matrix into the carrier, based on the carrier, the introduction of the heat-resistant inorganic oxide matrix The amount is such that the content of the refractory inorganic oxide matrix in the final support is greater than 0 to less than or equal to 99% by weight.

23. The method according to 22, characterized in that, based on the carrier, the amount of the heat-resistant inorganic oxide matrix introduced is such that the content of the heat-resistant inorganic oxide matrix in the final carrier is 10-90% by weight.

24. A hydrocracking method, comprising contacting hydrocarbon oil with a catalyst under hydrocracking conditions, wherein the catalyst is the catalyst provided in 1-11 above.

In the present invention's description about molecular sieves, the Beta (or MoBeta, ZSM-5, etc.) type zeolite molecular sieve, Beta (or MoBeta, ZSM-5, etc.) zeolite or Beta (or MoBeta, ZSM-5, etc.) molecular sieve have the same meaning .

In the present invention, the 3610cm ^-1 absorption peak in the FT-IR spectrum of the Beta zeolite refers to the absorption peak at 3610 ± 10cm ^-1 in the FT-IR spectrum, which belongs to the Beta-type zeolite acidic hydroxyl group vibration absorption peak. The 3740cm ^-1 absorption peak in the FT-IR spectrum of the Beta zeolite refers to the absorption peak at 3740cm ^-1 ±10cm ^-1 in the FT-IR spectrum, which belongs to the Beta-type zeolite Si-OH Vibration absorption peak.

The inventors found that when n=I/αI ₀ represents the change of the 3610cm ^-1 absorption peak intensity in the FT-IR spectrogram before and after the introduction of the Mo metal component into the Beta zeolite molecular sieve, the Mo-Beta prepared by the method provided by the invention The intensity of the vibration characteristic absorption peak of this acidic hydroxyl group of the type zeolite molecular sieve is reduced. However, the catalyst prepared by using the Mo-Beta zeolite molecular sieve has significantly improved hydrogenation aromatics saturation ring opening and cracking performance.

In the present invention, the Mo-Beta zeolite is a Beta type zeolite with 0<n<1, preferably 0.3≤n≤0.8. Preferably, the Mo-Beta type zeolite molecular sieve is used as a benchmark (in the present invention, the content (mass fraction) of molybdenum oxide in the Mo-Beta type zeolite molecular sieve=the measured value/ (the amount of the Mo-Beta type zeolite molecular sieve to be tested × dry basis). The dry basis is the ratio of the weight of the sample to be tested after roasting at 600 ° C for 4 hours in an air atmosphere to the weight before roasting), and the Mo in the Mo-Beta zeolite The content is 0.5-10% by weight, more preferably 1-9% by weight.

The method of introducing Mo to Beta type zeolite molecular sieve of the present invention comprises:

(1) Beta-type zeolite molecular sieves are mixed with Mo-containing compounds to obtain a mixture of Beta-type zeolite molecular sieves and Mo-containing compounds;

(2) Roasting the mixture obtained in step (1) in an atmosphere containing water vapor to obtain Mo-Beta type zeolite molecular sieve;

Wherein, the Mo-Beta type zeolite molecular sieve is based on the dry basis, and the consumption of each component in the step (1) is such that in the final Mo-Beta type zeolite molecular sieve, the molybdenum content in terms of oxides is preferably 0.5 -10% by weight, further preferably the molybdenum content in terms of oxides is 1-6% by weight; the molybdenum-containing compound is preferably selected from molybdenum oxides, chlorides or molybdates; the roasting in the step (2) The conditions include: the temperature is 200-700°C, preferably 400-650°C, the time is 1-24 hours, preferably 3-12 hours, the gas flow rate containing water vapor is 0.3-2 standard cubic meters/kg·hour, preferably 0.6-1.5 Nm3/kg·h.

In the aforementioned method, it is preferable that the atmosphere containing water vapor contains a diluent gas, and the diluent gas can be selected from examples such as: selected from hydrogen, nitrogen and a mixture thereof, or selected from air and a mixture of air and nitrogen, wherein preferably It is hydrogen, wherein the volume mixing ratio of the water vapor and the diluent gas is preferably 1:10-100, more preferably 1:20-80.

In the present invention, the ZSM-5 is not particularly limited, and may be a commercially available product or prepared by any prior art.

According to the catalyst provided by the present invention, the carrier can be made into various easy-to-handle moldings, such as microspheres, spheres, tablets or strips, etc. depending on different requirements. The molding can be carried out by conventional methods, for example, the compound molecular sieve containing ZSM-5 zeolite molecular sieve and MoBeta type zeolite molecular sieve, with or without heat-resistant inorganic oxide is extruded and calcined. During extrusion molding, an appropriate amount of extrusion aid and/or adhesive can be added to the material to be formed, and then extruded. The type and amount of the extrusion aid and the peptizing agent are well known to those skilled in the art, for example, the common extrusion aid can be selected from one of squash powder, methyl cellulose, starch, polyvinyl alcohol, polyethanol or several, and the peptizer can be selected from one or more of inorganic acids and organic acids.

Catalysts according to the present invention are provided in which the hydrogenation-active metal component is selected conventionally for such catalysts, for example, comprising at least one metal component selected from Group VIII and at least one metal component selected from Group VIB. Preferred Group VIII metal components are cobalt and/or nickel and Group VIB metal components are molybdenum and/or tungsten. In terms of oxides and based on the catalyst, the content of the Group VIII metal component is preferably 1-10% by weight, more preferably 1.5-6% by weight, and the content of the Group VIB metal component is preferably 5% by weight. -50% by weight, more preferably 10-40% by weight. The present invention includes Mo in the MoBeta molecular sieve when calculating the content of the VIB group metal component.

On the premise that it is sufficient to load the hydrogenation active metal component on the carrier, the present invention has no special limitation on the loading method, and the preferred method is the impregnation method, including the impregnation of preparing the compound containing the metal solution, which is then used to impregnate the carrier. The impregnation method is a conventional method, for example, it may be impregnation with excess liquid or pore saturation method. Wherein, a specified content of the catalyst can be prepared by adjusting and controlling the concentration and amount of the solution containing the metal component or the amount of the carrier, which is easily understood and realized by those skilled in the art.

According to the present invention, after the metal impregnation step is completed, steps such as drying, calcination or non-calcination may be carried out as required. The conditions of the drying and calcination are conventional, for example, the drying temperature is 100-300°C, preferably 100-280°C, and the drying time is 1-12 hours, preferably 2-8 hours; the calcination temperature is 350-550°C. °C, preferably 400-500 °C, and the firing time is 1-10 hours, preferably 2-8 hours.

The metal component compound selected from group VIB is selected from one or more of the soluble compounds in them, such as one or more of molybdenum oxide, molybdate, paramolybdate, preferably among them Molybdenum oxide, ammonium molybdate, ammonium paramolybdate; one or more of tungstate, metatungstate, ethyl metatungstate, preferably ammonium metatungstate, ethyl ammonium metatungstate . The compound containing metal components selected from Group VIII is selected from one or more of their soluble compounds, such as cobalt nitrate, cobalt acetate, basic cobalt carbonate, cobalt chloride and cobalt soluble complexes One or more, preferably cobalt nitrate, basic cobalt carbonate; one or more of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel soluble complexes, preferably nickel nitrate , Basic nickel carbonate.

The catalyst provided by the present invention may also contain any material that does not affect the catalytic performance of the catalyst provided by the present invention or that can improve the catalytic performance of the catalyst provided by the present invention. For example, one or two of the components such as phosphorus and titanium can be introduced, calculated as elements and based on the catalyst, the introduction amount of the above additives is 0-10% by weight, preferably 0.5-5% by weight.

When the catalyst also contains one or two components selected from components such as phosphorus, titanium or silicon, the introduction method of the components selected from phosphorus, titanium and the like is a conventional method, such as including The compound of the auxiliary agent is directly mixed with the solid acid component and pseudo-boehmite, shaped and roasted; it can be mixed with the compound containing the auxiliary agent and the compound containing the hydrogenation active metal component after preparing a mixed solution The carrier is contacted; it can also be that the compound containing the auxiliary agent is separately prepared into a solution, then contacted with the carrier and calcined. When the auxiliary agent and the hydrogenation active metal are respectively introduced into the carrier, it is preferable to first contact the carrier with a solution containing the auxiliary agent compound and roast it, and then contact it with the solution containing the compound of the hydrogenation active metal component, for example, by impregnating method, the calcination temperature is 250-600°C, preferably 350-500°C, and the calcination time is 2-8 hours, preferably 3-6 hours.

The catalyst provided by the invention can also contain one or more organic compounds selected from oxygen-containing or nitrogen-containing organic compounds, and preferred oxygen-containing organic compounds are selected from one or more of organic alcohols and organic acids; preferably The nitrogen-containing organic compound is selected from one or more of organic amines. For example, the oxygen-containing organic compound can include ethylene glycol, glycerol, polyethylene glycol (molecular weight is 200-1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, One or more of 1,2-cyclohexanediaminetetraacetic acid, citric acid, tartaric acid and malic acid, and the nitrogen-containing organic compound can be ethylenediamine, EDTA and its ammonium salts. The molar ratio of the organic compound to the sum of Group VIII and Group VIB metal components calculated as oxides is 0.03-2, preferably 0.08-1.5.

According to conventional methods in this field, before use, the hydrotreating catalyst can be presulfurized with sulfur, hydrogen sulfide or sulfur-containing raw materials at a temperature of 140-370° C. in the presence of hydrogen, such presulfurization It can be vulcanized outside or in-situ, and the active metal components supported by it can be converted into metal sulfide components.

In the hydrocracking method provided by the present invention, there are no special restrictions on the conditions of the hydrocracking reaction, and common reaction conditions can be used, for example, the reaction temperature is 200-420°C, more preferably 220- 400°C, the pressure is 2-18 MPa, more preferably 2-15 MPa, the liquid hourly space velocity is 0.3-10 hours ^-1 , more preferably 0.3-5 hours ^-1 , the hydrogen-oil volume ratio is 50-5000, further Preferably 50-4000.

The device for the hydroprocessing reaction can be carried out in any reaction device sufficient to allow the feed oil to contact the catalyst under the hydroprocessing reaction conditions, for example, in the fixed bed reactor, moving bed reaction in reactors or ebullating bed reactors.

Compared with the prior art, when the catalyst provided by the invention is used in the hydrocracking reaction process, the conversion of bicyclic and above polycyclic aromatic hydrocarbons in raw materials and the selectivity of ideal products are obviously improved. It can be directly used to process various hydrocarbon oil raw materials for hydrogenation upgrading. The hydrocarbon oil raw materials include various heavy mineral oils or synthetic oils or their mixed distillates, for example, selected from crude oil, distillate oil, solvent refined oil, wax paste, wax bottom oil, Fischer-Tropsch synthetic oil, coal liquefied oil One or more of light deasphalted oil and heavy deasphalted oil. It is especially suitable for hydrocracking of oil rich in aromatics or hydro-upgrading of inferior diesel oil.

Detailed ways

The following examples will further illustrate the present invention.

The hydroxyl group of the molecular sieve skeleton was measured by Fourier transform infrared (FT-IR). Firstly, the sample was calcined at 350°C for 2 hours, and the vacuum degree was kept at 10 ^-6 Pa. Then, the hydroxyl group infrared spectrum of the molecular sieve was measured at room temperature. The Mo content in the MoY molecular sieve is measured by X-ray fluorescence spectrometry (XRF). The experimental method is that the molecular sieve sample is pressed into tablets, rhodium target, laser voltage 50kV, laser current 50mA, and an external standard method is used for semi-quantitative analysis.

Example 1

Take 200.0 grams of Beta molecular sieve (product of Changling Catalyst Branch Company, silicon/aluminum 30, dry basis 0.81) and 0.8 grams of molybdenum trioxide, grind them in a mortar, and mix them evenly. Then put it in the constant temperature zone of the tube furnace, and bake it at 420°C for 24 hours under the atmosphere of hydrogen and water vapor, the gas flow rate is 0.5m ³ /(kg·h), and the mixing ratio of water vapor and hydrogen is 1:40. The Mo-modified Beta-type molecular sieve MoBeta1 was obtained, and the content of MoO ₃ in Mo-Beta1 and its n value are listed in Table 1.

200.0 gram of pseudo-boehmite (product of Changling Catalyst Branch Company, dry basis 0.71) is mixed with 19.1 gram of ZSM-5 (product of Changling Catalyst Branch Company, silicon/aluminum 60, dry basis 0.94), 159.1 gram of MoBeta1 samples, Extruded into a clover-shaped strip with a circumscribed circle diameter of 1.6 mm, dried the wet strip at 150°C for 3 hours, and calcined at 550°C for 3 hours to obtain carrier Z1.

Take 100.2 grams of carrier Z1, impregnate with 95 ml of a mixed solution containing MoO ₃ 182.1 g/L, NiO 78.9 g/L ammonium heptamolybdate and nickel nitrate for 4 hours, dry at 150°C for 3 hours, and bake at 400°C for 3 hours to obtain the catalyst C1. Based on the catalyst, the composition of the C1 catalyst after calcination is shown in Table 2 (the active metal component is measured by X-ray fluorescence spectrometry (XRF), the same below).

Example 2

Take 200.0 grams of Beta molecular sieve (product of Changling Catalyst Branch Company, silicon/aluminum 30, dry basis 0.81) and 8.5 grams of molybdenum trioxide, grind them in a mortar, and mix them evenly. Then put it in the constant temperature zone of the tube furnace, and bake it at 450°C for 4 hours under the atmosphere of hydrogen and water vapor. The gas flow rate is 0.8m ³ /(kg·h), and the mixing ratio of water vapor and hydrogen is 1:30. Obtained MoBeta2 modified Beta molecular sieve, the content of _MoO3 in MoBeta2 and its n value are listed in Table 1. .

200.0 gram of pseudo-boehmite (product of Changling Catalyst Branch Company, dry base 0.71) is mixed with 9.8 gram of BZSM-5 (same as embodiment 1), 36.6 gram of MoBeta2 samples, extruded into a clover shape with a circumscribed circle diameter of 1.6 mm Strips, wet strips were dried at 150°C for 3 hours and calcined at 550°C for 3 hours to obtain carrier Z2.

Take 101.0 grams of carrier Z2, impregnate with 78 milliliters of nickel and molybdenum complex solution containing MoO ₃ 648.9 g/L, NiO 128.2 g/L, P ₂ O ₅ 64.1 g/L, and 138.5 g/L citric acid for 4 hours. Dry at 150°C for 3 hours to obtain catalyst C2. Based on the catalyst, the composition of the C2 catalyst after calcination is shown in Table 2.

Example 3

200.0 gram of pseudo-boehmite (product of Changling Catalyst Branch Company, dry base 0.71) is mixed with 52.6 gram of ZSM-5 (same as embodiment 1), 49.2 gram of MoBeta Samples are mixed, extruded into a clover shape whose circumscribed circle diameter is 1.6 mm Strips, wet strips were dried at 150°C for 3 hours and calcined at 550°C for 3 hours to obtain carrier Z3.

Take 101.7 grams of carrier Z3, impregnate with 90 milliliters of nickel and molybdenum complex solution containing MoO ₃ 277.4 g/L, NiO 44.4 g/L, P ₂ O ₅ 29.7 g/L, and 48.0 g/L citric acid for 4 hours. Dry at 150°C for 3 hours to obtain catalyst C3. Based on the catalyst, the composition of the C3 catalyst after calcination is shown in Table 2.

Example 4

Take 200.0 grams of Beta molecular sieve (product of Changling Catalyst Branch Company, silicon/aluminum 30, dry basis 0.81) and 14.1 grams of molybdenum trioxide, grind them in a mortar and mix them evenly. Then put it in the constant temperature zone of the tube furnace, and bake it at 450°C for 8 hours under the atmosphere of hydrogen and water vapor. The gas flow rate is 0.8m ³ /(kg·h), and the mixing ratio of water vapor and hydrogen is 1:30. The MoBeta3 molecular sieve modified by MoBeta3 was obtained. The content of _MoO3 in MoBeta3 and its n value are listed in Table 1.

200.0 gram of pseudo-boehmite (product of Changling Catalyst Branch Company, dry basis 0.71) is mixed with 54.8 gram of ZSM-5 (same as Example 1), 50.5 gram of MoBeta3 samples, extruded into a clover shape with circumscribed circle diameter of 1.6 mm Strips, wet strips were dried at 150°C for 3 hours and calcined at 550°C for 3 hours to obtain carrier Z3.

Take 103.3 grams of carrier Z4, impregnate with 88 milliliters of nickel and molybdenum complex solution containing MoO _265.5 g/L, NiO 45.5 g/L, P ₂ O ₅ 30.3 g/L, and 49.1 g/L citric acid for 4 hours, Dry at 150°C for 3 hours to obtain catalyst C4. Based on the catalyst, the composition of the C4 catalyst after calcination is shown in Table 2.

Example 5

200.0 grams of pseudo-boehmite (product of Changling Catalyst Branch Company, dry basis 0.71) and 69.7 grams of Beta (product of Changling Catalyst Branch Company, silicon/aluminum 30, dry basis 0.81), 16.1 gram of MoBeta3 samples are mixed, extruded A clover-shaped strip with a circumscribed circle diameter of 1.6 mm was dried at 150° C. for 3 hours and then calcined at 550° C. for 3 hours to obtain the carrier Z5.

Take 102.9 grams of carrier Z5, impregnate with 90 milliliters of nickel and molybdenum complex solutions containing MoO ₃ 541.9 g/L, NiO 101.0 g/L, P ₂ O ₅ 55.6 g/L, and 109.2 g/L citric acid for 4 hours. Dry at 150°C for 3 hours to obtain catalyst C5. Based on the catalyst, the composition of the C5 catalyst after calcination is shown in Table 2.

Example 6

Take 200.0 grams of Beta molecular sieve (product of Changling Catalyst Branch Company, silicon/aluminum 30, dry basis 0.81) and 14.1 grams of molybdenum trioxide, grind them in a mortar and mix them evenly. Then put it in the constant temperature zone of the tube furnace, and bake it at 450°C for 12 hours under the atmosphere of air and water vapor. The gas flow rate is 1.2m ³ /(kg·h), and the mixing ratio of water vapor and air is 1:15. The MoBeta4 modified Beta molecular sieve was obtained. The content of _MoO3 in MoBeta4 and its n value are listed in Table 1.

200.0 gram of pseudo-boehmite (product of Changling Catalyst Branch Company, dry base 0.71) is mixed with 73.0 gram of ZSM-5 (same as embodiment 1), 33.7 gram of MoBeta4 samples, extruded into a clover shape with circumscribed circle diameter of 1.6 mm Strips, wet strips were dried at 150°C for 3h and calcined at 550°C for 3h to obtain carrier Z6.

Take 103.3 grams of carrier Z4, impregnate with 88 milliliters of nickel and molybdenum complex solution containing MoO _265.5 g/L, NiO 45.5 g/L, P ₂ O ₅ 30.3 g/L, and 49.1 g/L citric acid for 4 hours, Dry at 150°C for 3 hours to obtain catalyst C6. Based on the catalyst, the composition of the C6 catalyst after calcination is shown in Table 2.

Example 7

Take 200.0 grams of Beta molecular sieve (product of Changling Catalyst Branch Company, silicon/aluminum 30, dry basis 0.81) and 26.8 grams of molybdenum pentachloride, grind them in a mortar and mix them evenly. Then put it in the constant temperature zone of the tube furnace, and bake it at 300°C for 24 hours under the atmosphere of nitrogen and water vapor. The gas flow rate is 1.2m ³ /(kg·h), and the mixing ratio of water vapor and nitrogen is 1:15. The Mo-modified Beta-type molecular sieve MoBeta5 was obtained, and the content of MoO ₃ in MoBeta5 and its n value are listed in Table 1.

With 200.0 grams of pseudo-boehmite (product of Changling Catalyst Branch Company, dry basis 0.71), 46.7 grams of silica-alumina (product of Changling Catalyst Branch Company, dry basis 76%) and 28.2 grams of ZSM-5 (same implementation Example 1), 52.2 grams of MoBeta samples were mixed, extruded into a clover-shaped bar with a circumscribed circle diameter of 1.6 mm, the wet bar was dried at 150°C for 3 hours, and then calcined at 550°C for 3 hours to obtain carrier Z7.

Take 102.3 grams of carrier Z7, impregnate with 95 ml of a mixed solution containing MoO ₃ 160.0 g/L, NiO 78.9 g/L ammonium heptamolybdate and nickel nitrate for 4 hours, dry at 150°C for 3 hours, and bake at 400°C for 3 hours to obtain the catalyst C7. Based on the catalyst, the composition of the C7 catalyst after calcination is shown in Table 2.

Example 8

Take 200.0 grams of Beta molecular sieve (product of Changling Catalyst Branch Company, silicon/aluminum 30, dry basis 0.81) and 14.1 grams of molybdenum trioxide, grind them in a mortar and mix them evenly. Then put it in the constant temperature zone of the tube furnace, and bake it at 300°C for 8 hours under the water vapor atmosphere, and the gas flow rate in it is 0.4m ³ /(kg·h). The MoBeta6 molecular sieve modified by MoBeta was obtained. The content of _MoO3 in MoBeta6 and its n value are listed in Table 1.

200.0 gram of pseudo-boehmite (product of Changling Catalyst Branch Company, dry base 0.71), 122.0 gram of ZSM-5 (same as Example 1) and 12.6 gram of MoBeta6 samples are mixed, extruded into a diameter cylindrical bar of 1.6 mm , the wet strip was dried at 150°C for 3h, and then calcined at 550°C for 3h to obtain carrier Z8.

Take 103.9 grams of carrier Z8, impregnate with 90 ml of a mixed solution containing MoO ₃ 151.1 g/L, NiO 83.3 g/L ammonium heptamolybdate and nickel nitrate for 4 hours, dry at 150°C for 3 hours, and bake at 400°C for 3 hours to obtain the catalyst C8. Based on the catalyst, the composition of the C8 catalyst after calcination is shown in Table 2.

Example 9

Take 150.0 g of ZSM-5 (same as in Example 1) molecular sieve and 93.0 g of MoBeta 1 molecular sieve and mix evenly, press on a DY-20 powder tablet press, press at 10 MPa, and dry at 150° C. for 3 hours to prepare carrier Z9.

Take 105.2 grams of Z9, impregnate with 75 milliliters of nickel and molybdenum complex solution containing MoO ₃ 286.2 g/L, NiO 53.3 g/L, P ₂ O ₅ 35.6 g/L, 57.6 g/L citric acid for 4 hours, at 150 °C for 3 hours to obtain catalyst C9. Based on the catalyst, the composition of the C9 catalyst after calcination is shown in Table 2.

Comparative example 1

Get 180.0 grams of Beta molecular sieves (products of Changling Catalyst Branch Company, dry basis 0.75) and impregnate 11.7 grams of ammonium heptamolybdate solution isometrically for 4 hours, dry at 150°C for 3 hours, and roast at 450°C for 3 hours to obtain Prepared Mo-modified Beta molecular sieve DMoBeta. The Mo-modified Beta-type molecular sieve DMoBeta was obtained, and the content of MoO ₃ in DMoBeta and its n value are listed in Table 1.

200.0 gram of pseudo-boehmite (product of Changling Catalyst Branch Company, dry base 0.71), 78.9 gram of ZSM-5 (same as Example 1) and 94.6 gram of DMoBeta molecular sieves are mixed, extruded into a clover shape with circumscribed circle diameter of 1.6 mm Strips, wet strips were dried at 150°C for 3 hours and calcined at 550°C for 3 hours to obtain carrier DZ1.

Take 100.0 grams of carrier DZ1, impregnate with 90 milliliters of nickel and molybdenum complex solution containing MoO ₃ 287.3 g/L, NiO 44.4 g/L, P ₂ O ₅ 29.7 g/L, and 48.0 g/L citric acid for 4 hours. Dry at 150°C for 3 hours to obtain catalyst DC1. Based on the catalyst, the composition of the DC1 catalyst after calcination is shown in Table 2.

Table 1 Composition information of Mo modified Beta molecular sieves

Table 2 Carrier and catalyst composition information

Examples 10-12

The following examples illustrate the performance of the catalysts provided by the present invention.

With the tetrahydronaphthalene of purity 99% as raw material (analysis pure), evaluate the tetrahydronaphthalene reaction performance of catalyst C3, C4, C6 that the present invention provides on micro-fixed bed, catalyst loading is 1.2 grams, and reaction condition is 330 ℃～ 390°C, pressure 4.0MPa. For better comparison, the following two performance indicators (conversion rate, BTX selectivity) are given and defined. Taking the reaction result of the reference catalyst DC1 as 100%, calculate the relative conversion rate of different catalysts at the same reaction temperature, and the relative S _BTX value of different catalysts at the same conversion rate, the results are listed in Table 3.

Comparative example 2

DC1 was evaluated by the same method as in Examples 10-12, and the results are listed in Table 3.

Table 3 Catalyst tetralin hydrocracking evaluation results

The results in Table 3 show that, compared with the comparison catalyst DC1: the relative conversion rate of the patented tetralin provided by the present invention is increased by 12% to 23%; under the same conversion rate, the relative BTX selectivity is increased by 37% to 48%.

Claims (20)

1. a kind of hydrocracking catalyst contains the carrier and hydrogenation active metal component of the acid constituents containing molecular sieve solid, described Hydrogenation active metal component is selected from least one VIII race's metal component and at least one VI B metal components, in terms of oxide and with On the basis of the catalyst, the content of VIII race metal component is 1-10 weight %, and the content of VI B races metal component is 5-50 Weight %；The molecular sieve solid acid constituents is the mixture for including ZSM-5 molecular sieve and MoBeta type zeolite molecular sieves, described The weight ratio of ZSM-5 molecular sieve and MoBeta type zeolite molecular sieves is 9 in molecular sieve mixture:1~1:9, wherein MoBeta Type zeolite molecular sievenValue is 0<n <1,n=I/αI₀, characterized in FT-IR methods, I is MoBeta type zeolite molecular sieves 3610cm in FT-IR spectrograms^-1Absorption peak strength, I₀For the parent Beta type zeolite molecular sieves of MoBeta type zeolite molecular sieves 3610cm in FT-IR spectrograms^-1Absorption peak strength,αFor 3740cm in the FT-IR spectrograms of MoBeta type zeolite molecular sieves^-1Absorption peak Intensity and 3740cm in the FT-IR spectrograms of parent Beta type zeolite molecular sieves^-1The ratio of absorption peak strength；With the MoBeta types On the basis of zeolite molecular sieve, the content of the molybdenum in the MoBeta types zeolite molecular sieve in terms of oxide is 0.5-10 weight %.

2. catalyst according to claim 1, which is characterized in that in the molecular sieve mixture ZSM-5 molecular sieve and The weight ratio of Beta type zeolite molecular sieves is 4:1~1:1.

3. catalyst according to claim 1, which is characterized in that the MoBeta types zeolite molecular sievenValue is 0.3 ≤n≤0.8。

4. catalyst according to claim 1, which is characterized in that on the basis of the MoBeta types zeolite molecular sieve, institute The content for stating the molybdenum in MoBeta type zeolite molecular sieves in terms of oxide is 1-9 weight %.

5. catalyst according to claim 1, which is characterized in that VIII race metal component is selected from cobalt and/or nickel, VI B Race's metal component is selected from molybdenum and/or tungsten, is counted by oxide and on the basis of the catalyst, the content of VIII race metal component Content for 1.5-6 weight %, VI B races metal component is 10-40 weight %.

6. catalyst according to claim 1, which is characterized in that contain heat-resistant inorganic oxide matrix in the carrier, On the basis of the carrier, the content of the heat-resistant inorganic oxide matrix is more than 0 to less than equal to 99 weight %.

7. catalyst according to claim 6, which is characterized in that the heat-resistant inorganic oxide matrix be selected from aluminium oxide, One or more of silica and silica-alumina, on the basis of the carrier, the heat-resistant inorganic oxide matrix Content is 10-90 weight %.

8. catalyst according to claim 1 or 6, which is characterized in that on the basis of the catalyst, in the catalyst The content of carrier is 45-90 weight %.

9. catalyst according to claim 8, which is characterized in that on the basis of the catalyst, carried in the catalyst The content of body is 55-85 weight %, and the content of VIII race metal component in terms of oxide is 1.5-6 weight %, with oxide The content of VI B races metal component of meter is 10-40 weight %.

10. a kind of preparation method of hydrocracking catalyst, including prepare the carrier containing the acid constituents containing molecular sieve solid and to In the carrier the step of introducing hydrogenation active metal component, the hydrogenation active metal component choosing in the hydrocracking catalyst From at least one VIII race's metal component and at least one VI B races metal component, the molecular sieve solid acid constituents be include ZSM-5 The mixture of molecular sieve and MoBeta molecular sieves, ZSM-5 molecular sieve and Beta type zeolite molecular sieves in the molecular sieve mixture Weight ratio be 9:1~1:9, wherein MoBeta type zeolite molecular sievesnValue is 0<n <1,n=I/αI₀, with FT-IR Method characterizes, and I is 3610cm in the FT-IR spectrograms of MoBeta type zeolite molecular sieves^-1Absorption peak strength, I₀For MoBeta type zeolites 3610cm in the FT-IR spectrograms of the parent Beta type zeolite molecular sieves of molecular sieve^-1Absorption peak strength,αFor MoBeta type zeolites point 3740cm in the FT-IR spectrograms of son sieve^-1Absorption peak strength and 3740cm in the FT-IR spectrograms of parent Beta type zeolite molecular sieves^-1 The ratio of absorption peak strength；

The preparation method of the MoBeta types zeolite molecular sieve includes：（1）Beta types zeolite molecular sieve and compound containing Mo are mixed It closes, a kind of mixture of Beta types zeolite molecular sieve and the compound containing Mo is obtained, using the MoBeta types zeolite molecular sieve as base The dosage of standard, each component makes in final MoBeta types zeolite molecular sieve, and the molybdenum content in terms of oxide is 0.5-10 weight %；（2） By step（1）Obtained mixture encloses lower high-temperature process in steam-laden atmosphere, and the condition of the high-temperature process includes roasting Temperature be 200-700 DEG C, roasting time be 1-24 hour, steam-laden gas flow for 0.3-2 standard cubic meters/kilogram Hour, obtain MoBeta type zeolite molecular sieves；

In described the step of being introduced into hydrogenation active metal component into the carrier, counted using oxide and using the catalyst as base The introduction volume of standard, VIII race metal component makes the content of VIII race's metal component in final catalyst for 1-10 weight %, and described VI The introduction volume of B races metal component makes the content of VI B races metal component in final catalyst be 5-50 weight %.

11. according to the method described in claim 10, it is characterized in that, in the molecular sieve mixture ZSM-5 molecular sieve and The weight ratio of Beta molecular sieves is 4:1~1:1；The MoBeta types zeolite molecular sievenValue for 0.3≤n≤0.8。

12. according to the method described in claim 10, it is characterized in that, on the basis of the MoBeta types zeolite molecular sieve, respectively The dosage of component makes in final MoBeta types zeolite molecular sieve, and the molybdenum content in terms of oxide is 1-9 weight %.

13. according to the method described in claim 10, it is characterized in that, on the basis of the MoBeta types zeolite molecular sieve, institute State step（1）The dosage of middle each component makes in final MoBeta types zeolite molecular sieve, and the molybdenum content in terms of oxide is 1-6 weights Measure %；The step（2）In high-temperature process condition include calcination temperature be 400-650 DEG C, roasting time be 2-12 hours, Steam-laden gas flow is 0.6-1.5 standard cubic meters/kilogram hour.

14. according to the method for claim 13, which is characterized in that contain diluent gas in the steam-laden atmosphere, Wherein, the volume mixture ratio of the vapor and diluent gas is 1：10-100.

15. according to the method for claim 14, which is characterized in that the diluent gas is selected from hydrogen, nitrogen and its mixing Gas, or the gaseous mixture selected from air and air and nitrogen；The volume mixture ratio of the vapor and diluent gas is 1： 20-80。

16. according to the method for claim 15, which is characterized in that the diluent gas is hydrogen.

17. according to the method described in claim 10, it is characterized in that, VIII race metal component is selected from cobalt and/or nickel, VI B Race's metal component is selected from molybdenum and/or tungsten, is counted by oxide and on the basis of the catalyst, the introducing of VIII race metal component Amount, which makes the content of VIII race's metal component in final catalyst be the introduction volume of 1.5-6 weight %, VI B races metal component, to be made most The content of VI B races metal component is 10-40 weight % in whole catalyst.

18. according to the method described in claim 10, it is characterized in that, the method include introduced into the carrier it is heat-resisting The step of inorganic oxide matrix, on the basis of the carrier, the introduction volume of the heat-resistant inorganic oxide matrix makes finally to carry The content of heat-resistant inorganic oxide matrix is more than 0 to less than equal to 99 weight % in body.

19. according to the method for claim 18, which is characterized in that on the basis of the carrier, the heat resistant inorganic oxidation The introduction volume of object matrix makes the content of heat-resistant inorganic oxide matrix in final carrier be 10-90 weight %.

20. a kind of method for hydrogen cracking is included under hydrocracking condition and contacts hydrocarbon ils with catalyst, wherein the catalysis Agent is the catalyst that preceding claims 1-9 any one provides.