CN100497541C - Heavy distillate oil hydrogenation catalyst and its preparation method - Google Patents

Abstract

The invention discloses a heavy distillate oil hydrotreating catalyst and a preparation method thereof. With Group VIB metals and Group VIII metals as hydrogenation components and refractory oxides as carriers, the catalyst also contains a modified zeolite beta with a multi-level pore structure, with a content of 1% to 20%, zeolite beta The molar ratio of SiO ₂ /Al ₂ O ₃ is 80-120, the average particle size is 0.1-0.5 μm, and the pore structures are 0.1-1.7 nm, 1.7-6.0 nm and 10.0-90.0 nm. The catalyst of the present invention has the characteristics of high desulfurization and denitrification activity through selection of beta zeolite with suitable properties, and is especially suitable for the hydrogenation process of low-quality heavy distillate oil (such as low-quality wax oil, etc.) for the purpose of producing FCC raw materials.

Description

A kind of heavy distillate oil hydrogenation treatment catalyst and preparation method thereof

technical field

The invention relates to a hydrogenation treatment catalyst for oil refining industry, in particular to a hydrogenation treatment catalyst for low-quality heavy distillate oil for the purpose of producing FCC raw materials and a preparation method thereof.

Background technique

Crude oil and various distillates obtained from crude oil contain impurities such as sulfur, nitrogen, oxygen and metals. The existence of these impurities not only affects the stability of oil products, but also emits SO _x , NO _x and other harmful gases to pollute the environment during use. During the secondary processing of oil products, the presence of impurities such as sulfur, nitrogen, oxygen and metals can poison catalysts.

Hydrotreating refers to the process of contacting raw oil and hydrogen with a catalyst at a certain temperature and pressure to remove impurities and saturate aromatics. Due to the characteristics of strong adaptability to raw oil and flexible operation scheme, hydrogenation technology can not only provide high-quality feed for other secondary processing units (such as catalytic cracking, etc.), but also directly produce high-quality products.

Hydrotreating catalysts with excellent performance must have excellent hydrogenation activity and certain cracking activity. Typical hydrogenation catalysts generally use VIII and VIB metal oxides or sulfides as hydrogenation components, and the carrier is generally alumina/or silicon-containing alumina. Generally, these catalysts are prepared by impregnating the support one or more times with an aqueous solution of metal compounds, followed by one or more drying and calcining processes, such catalyst preparation methods are described in eg EP0469675. A small amount of molecular sieve is added to the catalyst carrier, the strong acid center of the molecular sieve can change the electrical properties of the hydrogenation component, and significantly improve the denitrification and desulfurization activity of the catalyst. Chinese patent CN00110710 describes a preparation method of a catalyst for hydrogenation of petroleum hydrocarbons. It is characterized in that it uses pseudo-alumina alumina, Y zeolite and compounds containing fluorine as raw materials, together with hydrogenation active metal solution, through mixing, kneading, extruding, and then drying and roasting to make hydrogenation catalyst .

Hydrocracking catalysts generally use oxides or sulfides of Group VIII and VIB metals as hydrogenation components, and amorphous silica-alumina containing molecular sieves as carriers. For the hydrotreating that simply provides FCC feedstock, it is not for the purpose of cracking. Therefore, the use of hydrocracking catalysts in hydrotreating has its limitations. The unique "supercage" of Y zeolite can accommodate aromatic hydrocarbons, especially polycyclic aromatic hydrocarbons. For processing untreated inferior heavy distillate oil (such as wax oil, etc.), Y zeolite deactivates quickly.

Beta zeolites can also be used as components of hydrotreating catalysts. For example, US4,419,220 uses a catalyst containing noble metal and zeolite beta to perform isomerization dewaxing treatment on waxy hydrocarbon materials. US 5,011,593 describes a desulfurization process for feedstocks high in sulfur and aromatics, using a beta zeolite-containing catalyst. For the β zeolite with larger particles, the diffusion force in the particles is greater, the utilization rate of zeolite is low, and secondary reactions are prone to occur in the zeolite particles, which has a significant impact on the selectivity of the reaction. For zeolite beta with smaller particles, such as nano-beta zeolite, its main characteristics are small particle size, large external area, high reactivity and selectivity. However, in hydrotreating catalysts, since the content of beta zeolite is generally small, a small amount of zeolite is "coated" in a large amount of other carrier materials, and the result must be that a large amount of the outer surface of the zeolite is bonded to the carrier material, making the small particle zeolite It is difficult to give full play to the advantages.

Contents of the invention

Aiming at the deficiencies of the prior art, the present invention provides a heavy distillate oil hydrotreating catalyst and its preparation method. The hydrotreating catalyst prepared by the method has the characteristics of high desulfurization and denitrogenation activities, and is especially suitable for the purpose of producing FCC raw materials. Hydrotreating process of inferior heavy distillate oil (such as inferior wax oil, etc.).

The catalyst of the present invention includes: based on the weight percentage of the catalyst, 1% to 20% of modified zeolite beta with a multi-level pore structure, 30% to 70% of inorganic refractory oxides, and 10% to 40% of VIB group metal oxides %, Group VIII metal oxide 1%-10%, the pore volume of the catalyst is 0.2mL/g-0.5mL/g, and the specific surface area is 100m ² /g-300m ² /g. The modified β zeolite has the following characteristics: SiO ₂ /Al ₂ O ₃ is 80-120 (molar ratio), the average particle size is 0.1-0.5 μm, the pore volume is 0.35-0.50ml/g, and the pore diameter is 0.1-1.7 The pores with a diameter of 10.0 to 90.0nm account for 30% to 30% of the total pore volume 60%.

The preparation process of the catalyst of the present invention adopts a conventional impregnation method, a kneading method or a combination of an impregnation method and a kneading method.

The specific conditions in the catalyst preparation process can be determined according to common knowledge in the art.

The beta zeolite used in the invention has suitable particle size and multi-level pore structure. Among them, the micropores are the pores of zeolite beta itself, which is the main reaction site of substances. The main function of mesopores and macropores is to reduce diffusion resistance and reduce secondary reactions. More importantly, this zeolite particle structure protects the outer surface of primary particles from being fully exposed and not affected by other catalyst components. The invention overcomes the influence of the diffusion control of the large particle zeolite, and also overcomes the problem that the outer surface of the small particle or nanometer zeolite cannot be fully utilized when it is used as a catalyst component. It can give full play to the promotion effect of the acid center of zeolite beta on the hydrogenation active center of the catalyst, improve the hydrogenation activity of the catalyst, and improve the denitrification and desulfurization performance of the catalyst. Compared with Y zeolite, the pore channel of β zeolite is channel type without "cavity", and the hydrocarbon molecules with suitable structure enter and exit the zeolite smoothly, so the secondary cracking of hydrocarbon molecules is low, and the catalyst cracking rate is low.

Detailed ways

The catalyst of the present invention is preferably prepared by an impregnation method, that is, according to the composition requirements of the catalyst, a certain amount of modified β zeolite and inorganic refractory oxides with a multi-level pore structure are mixed, kneaded, formed, dried, and roasted to form a carrier. The catalyst is prepared by impregnating with active metal solution, drying and roasting. The mixing and kneading process includes adding the above materials into active metal components, mixing, kneading, molding, drying and roasting to make a catalyst.

The preparation process of the beta zeolite with a multi-level pore structure involved in the catalyst of the present invention includes: the silicon source and the aluminum source are crystallized in two stages by a hydrothermal method in the presence of a tetraethylammonium hydroxide template agent, first low-temperature nucleation, and then high-temperature crystallization One-step crystallization can also be adopted, and ammonium salt is added for treatment for a certain period of time. The above-mentioned crystallization and treatment are carried out under continuous stirring, and then filtered, dried, roasted in three stages to remove organic ammonium, and acid treatment under mild conditions And high temperature and high pressure hydrothermal treatment to produce multi-level channel β zeolite products.

The specific preparation process of the beta zeolite involved in the catalyst of the present invention is as follows: the silicon source is made of porous solid silica gel particles, the aluminum source is made of sodium aluminate, the template is made of tetraethylammonium hydroxide mixed evenly with sodium hydroxide and water, and two-stage crystallization is adopted. Method, first low-temperature nucleation, then high-temperature crystallization, crystallization in a crystallization kettle at 90-130°C for 10-40 hours, at 110-170°C for 20-50 hours, or at 100°C-170°C Crystallize for 10-60 hours. Then directly add ammonium salt and treat at 80-20° C. for 0.2-3.0 hours. Ammonium salt treatment can be carried out 1-3 times, and the concentration of ammonium salt in the mixture is 0.5-3 mol/L. After ammonium salt treatment, filter, wash, and dry, remove organic ammonium by three-stage temperature-controlled roasting, dehydrate at low temperature (150-250°C) for 1.0-6.0 hours, and decompose organic ammonium at medium temperature (250-450°C) for 1.0-4.0 hours. High temperature (450-650°C) removes free carbon for 6.0-20.0 hours. Acid treatment of inorganic acid at 0.1-5.0mol/L (preferably 0.5-1.5mol/L), treatment temperature 20-100°C, treatment time 1.0-3.0 hours, high temperature and high pressure hydrothermal treatment at temperature 500-700°C, pressure 0.05 -0.5MPa, treatment for 0.5-5.0 hours, to obtain multi-stage zeolite beta granular products. Ratio (mole) of each raw material: Na ₂ O/Al ₂ O ₃ is 0.5-5.0, preferably 1.0-2.0; (TEA) ₂ O/Al ₂ O ₃ is 0.5-5.0, preferably 1.0-3.0 ; SiO ₂ /Al ₂ O ₃ is 10-100, preferably 10-50; H ₂ O/Al ₂ O ₃ is 100-500; best is 100-300. The above-mentioned Na ₂ O is obtained by converting sodium hydroxide and sodium aluminate in the raw materials, Al ₂ O ₃ is obtained by converting sodium aluminate in the raw materials, and SiO ₂ is obtained by converting solid silica gel in the raw materials.

Said porous solid silica gel in the preparation process of the beta zeolite involved in the catalyst of the present invention can be coarse-pored, medium-pored, fine-pored silica gel, said aluminum source can be solid sodium aluminate and liquid sodium aluminate, and the sodium source can be It is sodium aluminate or a mixture of sodium aluminate and sodium hydroxide. Said templating agent tetraethylammonium hydroxide comes from tetraethylammonium chloride or tetraethylammonium bromide. Ammonium salt can be ammonium chloride, ammonium nitrate or ammonium sulfate, also can be mixed ammonium salt. The inorganic acid used in acid treatment is generally hydrochloric acid, nitric acid or sulfuric acid.

The process of preparing catalyst by impregnation method of the present invention is as follows:

(1) Forming, drying and calcining the modified β zeolite and inorganic refractory oxides involved in the present invention to obtain the catalyst carrier.

(2) Add active metal components.

(3) One or more drying and roasting processes.

Based on the weight percentage of the catalyst, the hydroprocessing catalyst of the present invention contains 1% to 20%, preferably 3% to 15%, of the modified β zeolite component involved in the present invention.

The inorganic refractory oxide described in step 1 preferably includes macroporous alumina, small pore alumina, silicon-containing alumina or mixtures thereof.

The active metal in step 1 is selected from at least one group VIII and at least one VIB non-noble metal. Group VIB metals are selected from Mo or W, containing 10% to 40% (calculated as metal oxides) in the catalyst, group VIII metals are selected from Co or Ni, preferably Co or a mixture of Co and Ni, and contain 1% to 40% in the catalyst 10% (calculated as metal oxides).

The molding process described in step 1 can include one or more mixing and kneading processes. During the molding process, an appropriate amount of deionized water and acid can be added as needed. The amount of water added and the type and quantity of acid are well known to those skilled in the art .

The molding method of the catalyst described in step 1 can be drop ball molding, extrusion molding, tablet molding, extrusion molding is the best. The shape of the catalyst can be spherical, strip (including special-shaped strips such as cylinder or clover), sheet, and strip is the best.

The method of adding the active metal described in step 2 is preferably the impregnation method.

In the process of step 1 and step 2, additives, such as F, B, P, Zr, Ti, etc., can be added as required, and the method and quantity of addition are well known to those skilled in the art.

The drying and calcination conditions described in steps 1 and 3 can adopt conventional conditions in the art, drying is generally at 60-200°C for 1-20 hours, and calcination is generally at 300-650°C for 1-10 hours.

The features of the present invention are further described below through examples, but these examples cannot limit the present invention.

Example 1

The modified beta zeolite with multi-level pore structure described in the invention is prepared. Mix 78g of sodium aluminate (contains 19.9m% of Al ₂ O ₃ and 21.44m% of Na ₂ O in laboratory preparation), 435g of tetraethylammonium hydroxide aqueous solution (industrial production, concentration 1.4N), coarse-pored silica gel particles 288g (manufactured by Qingdao Haiyang Chemical Factory, containing 95% SiO ₂ ) and 120g of purified water are mixed evenly, and reacted in a 2-liter stainless steel reactor at 100°C for 20 hours under sufficient and continuous stirring conditions, and then raised to 150°C for crystallization for 40 hours After the crystallization is completed, the pressure is relieved, the temperature is lowered, ammonium nitrate solution is added, and the concentration of ammonium nitrate in the system is 2mol/L, and the mixture is stirred at a constant temperature of 95°C for 1 hour, then filtered, and ammonium salt treatment is carried out again according to the above conditions. Then filter, wash with water, dry, remove organic ammonium by three-stage temperature-controlled roasting, dehydrate at a constant temperature of 200°C for 2 hours, decompose organic ammonium at 400°C for 3 hours, decompose free carbon at 550°C for 12 hours, and the concentration of hydrochloric acid for acid treatment is 0.5mol/L , treated at 80°C for 1 hour under fully stirred conditions, then filtered, washed with water, dried, and subjected to high-temperature and high-pressure hydrothermal treatment at a temperature of 650°C and a pressure of 0.1 MPa for 2 hours to obtain zeolite beta B-1 of the present invention. The physical and chemical properties of the zeolite beta are: SiO ₂ /Al ₂ O ₃ is 102 (molar ratio), the average particle size is 0.25 μm, the pore volume is 0.407ml/g, and the pores with a pore diameter of 0.1-1.7nm account for 10% of the total pore volume. 32.2%, pores with a diameter of >1.7-6.0nm accounted for 8.2% of the total pore volume, and pores with a diameter of 10.0-90.0nm accounted for 54.5% of the total pore volume.

Example 2

80g of sodium aluminate (prepared in the laboratory containing Al ₂ O ₃ 18.90m%, containing Na ₂ O 24.11m%), 382g of tetraethylammonium hydroxide aqueous solution (industrial product, concentration 1.55N), 280g of coarse-pore silica gel particles ( The product produced by Qingdao Ocean Chemical Factory contains SiO ₂ (95.2m%) and 158g of purified water, mixed evenly. Other conditions were the same as in Example 1 to obtain zeolite beta B-2. The physical and chemical properties of the zeolite beta are: SiO ₂ /Al ₂ O ₃ is 98 (molar ratio), the average particle size is 0.20 μm, the pore volume is 0.412ml/g, and the pores with a pore diameter of 0.1-1.7nm account for the total pore volume 28.9%, pores with a diameter of >1.7-6.0nm accounted for 12.3% of the total pore volume, and pores with a diameter of 10.0-90.0nm accounted for 54.4% of the total pore volume.

Example 3

According to the method of Example 2, ammonium chloride is used for ammonium salt treatment, the concentration in the system is 0.8mol/L, the temperature is 105°C, the time is 2 hours, and the number of times is 3 times. The acid treatment uses nitric acid, the concentration is at 1.2mol/L, the treatment temperature is 50°C, and the treatment time is 1.5 hours. The high-temperature and high-pressure hydrothermal treatment is at a temperature of 550°C, and a pressure of 0.2MPa, and is processed for 3.0 hours. Others are the same as in Example 1, and the product obtained is B-3. The physical and chemical properties of the zeolite beta are: SiO ₂ /Al ₂ O ₃ is 104 (molar ratio), the average particle size is 0.35 μm, the pore volume is 0.409ml/g, and the pores with a pore diameter of 0.1-1.7nm account for 10% of the total pore volume. 28.4%, pores with a diameter of >1.7-6.0nm accounted for 14.3% of the total pore volume, and pores with a diameter of 10.0-90.0nm accounted for 43.4% of the total pore volume.

Example 4

Catalyst preparation of the present invention. Get zeolite B-18g (dry basis) prepared by Example 1, a kind of macroporous alumina (specific surface area 400m ² /g, pore volume 1.1mL/g) 20g (dry basis) and small pore alumina (specific surface area 240m ² /g, pore volume 1.1mL/g) and 12g (dry basis) were mixed evenly, and 80ml of 3% dilute nitric acid solution was added to peptize 30g (dry basis) of small-pore alumina (specific surface area 240m ² /g, Pore volume 0.5mL/g) obtained adhesive, continue kneading until it becomes a paste, extruded into strips, the obtained shaped strips were dried at 110°C for 8 hours, activated at 500°C for 4 hours to obtain the activated carrier. Then 24g of molybdenum oxide, 6.8g of basic nickel carbonate, 3.57g of 85% phosphoric acid were dissolved and calibrated to 55mL to obtain a Mo—Co—P co-impregnation solution, which was used to impregnate the carrier prepared above, and then dried at 110°C for 8 hours, and after activation at 500°C for 4 hours, catalyst A was obtained. The final composition of the catalyst is: 8wt% of beta zeolite, 20wt% of macroporous alumina, 42wt% of small pore alumina, 3.8wt% of cobalt oxide, 24wt% of molybdenum oxide and 2.2wt% of phosphorus pentoxide.

Example 5

Catalyst preparation of the present invention. Get zeolite B-212g (dry basis) prepared by example 2, a kind of macroporous alumina (specific surface area 400m ² /g, pore volume 1.1mL/g) 18g (dry basis) and small pore alumina (specific surface area 240m ² /g, pore volume 1.1mL/g) and 10g (dry basis) were mixed evenly, and 30g (dry basis) of small-pore alumina (specific surface area 240m 2 /g, specific surface area 240m ² /g, Pore volume 0.5mL/g) obtained adhesive, continue kneading until it becomes a paste, extruded into strips, the obtained shaped strips were dried at 110°C for 8 hours, activated at 500°C for 4 hours to obtain the activated carrier. Then 24g of molybdenum oxide, 3.2g of basic cobalt carbonate, 4.3g of basic nickel carbonate, 3.57g of 85% phosphoric acid were dissolved and calibrated to 55mL to obtain a Mo-Co-P co-impregnation solution, which was used to impregnate the carrier prepared above , and then dried at 110°C for 8 hours and activated at 500°C for 4 hours to obtain catalyst B. The final composition of the catalyst is: 12wt% of beta zeolite, 20wt% of macroporous alumina, 42wt% of small pore alumina, 1.8wt% of cobalt oxide, 2wt% of nickel oxide, 24wt% of molybdenum oxide and 2.2wt% of phosphorus pentoxide.

Example 6

Catalyst preparation of the present invention. Get zeolite B-36g (dry basis) prepared by example 3, a kind of macroporous alumina (specific surface area 400m ² /g, pore volume 1.1mL/g) 20g (dry basis) and small pore alumina (specific surface area 240m ² /g, pore volume 1.1mL/g) 16.2g (dry basis), 24g molybdenum oxide, 8g nickel nitrate, 7.2g cobalt nitrate mix uniformly, add the dilute nitric acid solution peptization that is 3% by the concentration of 80ml 30g (dry base) small-pore alumina (specific surface area 240m ² /g, pore volume 0.5mL/g), continue kneading until it becomes a paste, extrusion molding, and the obtained molding strips are dried at 110°C for 8 hours , Catalyst C was obtained by activation at 500°C for 4 hours. The final composition of the catalyst is: 6wt% of zeolite beta, 20wt% of macroporous alumina, 44.2wt% of small pore alumina, 1.8wt% of cobalt oxide, 2wt% of nickel oxide and 24wt% of molybdenum oxide.

Comparative example 1

Comparative catalyst preparation. Catalyst D was obtained by taking 8 g (dry basis) of USY zeolite (developed by Fushun Petrochemical Research Institute, with a silicon-aluminum ratio of 5.2, a pore volume of 0.51 mL/g, and a specific surface area of 680 m ² /g). Other conditions were the same as in Example 1. The final catalyst composition is: USY zeolite 8wt%, macroporous alumina 20wt%, small pore alumina 42wt%, cobalt oxide 3.8wt%, molybdenum oxide 24wt%, phosphorus pentoxide 2.2wt%.

Comparative example 2

Comparative catalyst preparation. Take 8 g (dry basis) of zeolite beta (manufactured by Fushun Petrochemical Company Catalyst Factory with a silicon-aluminum ratio of 80, a pore volume of 0.54 mL/g, and a specific surface area of 630 m ² /g) (dry basis). Other conditions are the same as in Example 1 to obtain catalyst E. The final composition of the catalyst is: 8wt% of beta zeolite, 20wt% of macroporous alumina, 42wt% of small pore alumina, 3.8wt% of cobalt oxide, 24wt% of molybdenum oxide and 2.2wt% of phosphorus pentoxide.

Example 7

This embodiment is an activity evaluation test of the catalyst of the present invention, and is compared with other catalysts. The evaluation was carried out on a 200ml small hydrogenation device. The properties of the raw oil used are shown in Table 1. See Table 2 for the evaluation results. As can be seen from Table 2, under the same process conditions, when the sulfur content is controlled to be similar, the activity of the catalyst of the present invention is obviously higher than that of the reference catalysts D and E.

The beta zeolite used in the invention has suitable particle size and multi-level pore structure. The structure not only overcomes the influence of the diffusion control of the large-grain zeolite, but also overcomes the problem that the outer surface of the small-grain or nano-scale zeolite cannot be fully utilized when it is used as a catalyst component. It can give full play to the promotion effect of the acid center of zeolite beta on the hydrogenation active center of the catalyst, improve the hydrogenation activity of the catalyst, and improve the denitrification and desulfurization performance of the catalyst. Compared with Y zeolite, the channel of β zeolite is channel type without "cavity", and the hydrocarbon molecules enter and exit the zeolite smoothly, so the secondary cracking of hydrocarbon molecules is low, and the catalyst cracking rate is low.

Table 1 Properties of raw oil

Table 2 Catalyst evaluation results

Claims (7)

1, a kind of heavy distillate hydrotreating catalyst, weight percent with catalyzer is that benchmark comprises: the modified beta zeolite 1%～20% with multi-stage artery structure, inorganic refractory oxide 30%～70%, group vib metal oxide 10%～40%, group VIII metal oxide 1%～10%; Wherein modified beta zeolite has following characteristics: SiO ₂/ Al ₂O ₃Mol ratio is 80～120, mean particle size is 0.1～0.5 μ m, pore volume is 0.35-0.50ml/g, the aperture be the hole of 0.1～1.7nm account for total pore volume 20%～50%, the aperture for the hole of 1.7～6.0nm accounts for 5%～20% of total pore volume, the aperture be the hole of 10.0～90.0nm account for total pore volume 30%～60%.

2,, it is characterized in that pore volume 0.2mL/g～0.5mL/g, the specific surface area 100m of described catalyzer according to the described catalyzer of claim 1 ²/ g～300m ²/ g, modified beta zeolite content are 3%～15%.

3, the described Preparation of catalysts method of a kind of claim 1 is characterized in that adopting conventional pickling process, kneading method or pickling process to combine with kneading method;

Described pickling process process comprises: the composition requirement of pressing catalyzer, to have the multi-stage artery structure modified beta zeolite, inorganic refractory oxide is made carrier through mixing, kneading, moulding, drying, roasting, carrier is made catalyzer through reactive metal solution impregnation, drying, roasting; Described kneading method process comprises above-mentioned material adding active metal component, makes catalyzer through mixing, kneading, moulding, drying, roasting;

The β zeolite preparing process with multi-stage artery structure that relates to comprises: silicon source and aluminium source are in the presence of the tetraethyl ammonium hydroxide template, two sections crystallization of hydrothermal method, elder generation's low temperature nucleation, back high temperature crystallization, or adopt a step crystallization, adding ammonium salt handles, above-mentioned crystallization and handle and to carry out under continuously stirring is filtered, drying then, divides three sections temperature control roastings to remove organic ammonium, acid treatment and High Temperature High Pressure hydrothermal treatment consists make the β zeolite product of multistage pore canal;

In the above-mentioned β zeolite preparing process with multi-stage artery structure: the porosu solid silica gel particle is adopted in the silicon source, sodium aluminate is adopted in the aluminium source, template adopts tetraethyl ammonium hydroxide, above-mentioned raw materials and sodium hydroxide and water mix, and adopt two sections crystallization methods, first low temperature nucleation, back high temperature crystallization, in crystallizing kettle in 90～130 ℃ of following crystallization 10～40 hours, at 110-170 ℃ of following crystallization 20-50 hour, or 100 ℃-170 ℃ crystallization 10-60 hour; Directly add ammonium salt then and handled 0.2～3.0 hour down at 80～120 ℃, ammonium salt is handled and is carried out 1～3 time, and the concentration of ammonium salt in mixture is 0.5～3mol/L; Filter after ammonium salt is handled, wash, drying, remove organic ammonium by three sections temperature control roastings, low temperature 150-250 ℃ was dewatered 1.0～6.0 hours, and middle temperature 250-450 ℃ of organic ammonium decomposed 1.0～4.0 hours, removed uncombined carbon 6.0～20.0 hours for high temperature 450-650 ℃; The mineral acid of 0.1-5.0mol/L, treatment temp 20-100 ℃, treatment time 1.0-3.0 hour are used in acid treatment, the High Temperature High Pressure hydrothermal treatment consists is at temperature 500-700 ℃, pressure 0.05-0.5MPa handled 0.5-5.0 hour, obtained the beta zeolite with multilevel pore canals particulate product; Molar ratio is: Na ₂O/Al ₂O ₃Be 0.5-5.0, (TEA) ₂O/Al ₂O ₃Be 0.5-5.0, SiO ₂/ Al ₂O ₃Be 10-100, H ₂O/Al ₂O ₃Be 100-500.

4, in accordance with the method for claim 3, it is characterized in that described each raw material molar ratio is: Na ₂O/Al ₂O ₃Be 1.0-2.0, (TEA) ₂O/Al ₂O ₃Be 1.0-3.0, SiO ₂/ Al ₂O ₃Be 10-50, H ₂O/Al ₂O ₃Be 100-300.

5, in accordance with the method for claim 3, it is characterized in that described porosu solid silica gel is gross porosity, mesopore or Kiselgel A, said aluminium source is solid sodium aluminate or liquid sodium aluminate, the sodium source is the mixture of sodium aluminate or sodium aluminate and sodium hydroxide, said template tetraethyl ammonium hydroxide is from etamon chloride or tetraethyl-amine bromide, ammonium salt is ammonium chloride, ammonium nitrate or ammonium sulfate, or mixed-ammonium salt.

6, in accordance with the method for claim 3, it is characterized in that described inorganic refractory oxide comprises macroporous aluminium oxide, little porous aluminum oxide, siliceous aluminum oxide or their mixture.

7, in accordance with the method for claim 3, it is characterized in that described drying and roasting condition adopt the condition of capable territory routine, dry 60～200 ℃ dry 1～20 hour down, roasting was 300～650 ℃ of following roastings 1～10 hour.