JPWO2019104543A5 - - Google Patents

Description

The present invention relates to the field of hydrocracking, specifically, a modified Y-type molecular sieve and a manufacturing method, a hydrocracking catalyst and a manufacturing method, and a method for hydrocracking hydrocarbon oil.

Hydrocracking technology has features such as high adaptability of raw materials, flexible product scheme, high selectivity of target products, high quality of products, high added value, etc. It can directly convert poor quality raw materials into clean fuel oils and high quality chemical industrial raw materials, making it one of the most important heavy oil advanced processing technologies in modern petroleum refining and petroleum chemical industry, and is being used more and more widely in China and abroad. It came to be done. The processing capacity of China's current hydrocracking equipment exceeds 50.0 Mt / a, but the quality of crude oil in China is deteriorating year by year, so the import volume of crude oil with high sulfur content has increased significantly. As a result, environmental protection requirements for the refining process itself and the quality of petroleum products have become stricter, and the market demand for clean fuel oils and raw materials for the chemical industry continues to increase. Therefore, it can be predicted that the hydrocracking technique will be used more widely, and accordingly, higher requirements for the hydrocracking technique itself will be required.

The core of the hydrocracking technology is the hydrocracking catalyst, the hydrocracking catalyst is a dual-function catalyst with cracking and hydroactive activity, and the cracking function is provided by an acidic carrier material such as a molecular sieve. The hydrogenation function is provided by the active metals of Group VI and Group VIII of the element cycle carried on the catalyst, and meets the needs of various reactions by coordinating the two functional sites of decomposition and hydrogenation. The performance of molecular sieves as a decomposition component of a hydrogenation decomposition catalyst plays a decisive role in the reaction performance of the catalyst. Currently, the types of molecular sieves used for hydrocracking catalysts are mainly Y-type and β-type. The Y-type molecular sieve has a three-dimensional supercage, a tetrahedron-like 12-membered ring macropore, and an open pore structure, and has excellent ring-opening selectivity for large molecular cyclic hydrocarbons. Heavy naphtha products have a high potential content of aromatic hydrocarbons and a low BMCI value of hydrogenated tail oil and are currently the most widely used in hydrocracking catalysts.

As a decomposition component of a hydrocracking catalyst, a Y-type molecular sieve usually improves the hydrothermal and chemical stability of the molecular sieve and also improves its acidic properties and pore structure to provide an acidic environment suitable for the hydrocracking reaction. And need to be modified prior to use in order to obtain a favorable pore structure. Usually, the modification technique of the Y-type molecular sieve includes a hydrothermal modification method; a chemical dealumination modification method using an inorganic acid, an organic acid, a salt or a complexing agent; a combination of a hydrothermal modification method and a chemical dealumination modification method. There is. However, in the modified Y-type molecular sieves obtained by the current modification method, acidic centers are distributed in different pores (micropores and secondary pores) of the molecular sieves, and in this case, on the other hand, the acidic centers in the micropores are distributed. The availability is low, on the other hand, excessive secondary decomposition reactions are likely to occur, reducing reaction selectivity and yield of liquid products.

US4503023 discloses a method for modifying molecular sieves, and molecular sieves produced by liquid phase dealuminum and silicon replenishment of NaY zeolite with ammonium fluorosilicate have a high crystallinity and a silica / alumina ratio. Although it has a certain resistance to organic nitrogen poisoning, it has few secondary pores because its structure is too perfect, and the acidic center is mainly located in the micropores, which is a large molecule of inferior raw material. Reactants are difficult to approach.

CN1178193A occupies 45% or more of the volume of pores having a pore diameter of more than 1.7 × 10-10 m, has a surface area of 750 to 900 m ² / g, and has a lattice constant of 24.23 × 10-10 m to ^25.45 × ¹⁰ . A modified Y zeolite having a crystallinity of ^-10 meters, a crystallinity of 95 to 110%, and a SiO ₂ / Al ₂ O3 ratio of ₇ to 20 is disclosed. The method is to use ^NaY zeolite as a raw material, first exchange ammonium until the Na ₂ O content is less than 2 m%, and then perform steam treatment. It is characterized by treatment with a buffer solution containing H ⁺ and other metal cations. The molecular sieve obtained by modifying the Y molecular sieve by a combination of hydrothermal desulfurization and treatment with a buffer solution has abundant secondary pores and good diffusion performance. However, the modified Y molecular sieve obtained by this modification method. Has many acidic sites existing in the micropore structure, the degree of dispersion of the acidic sites on the molecular sieve is large, and the reaction selectivity is low.

CN1178721A is a silica / alumina characterized by a lattice constant of 2.425 to 2.436 nm, a SiO ₂ / Al _{2O 3} molar ratio of 15 to 200, a specific surface area of 700 to 780 m ² / g, and a relative crystallinity of 100 to 125%. We disclose Y-type molecular sieves with high specific surface area and high crystallinity. The manufacturing method is as follows. The NH ₄ NaY molecular sieve raw material is dealuminated and replenished with silicon using ammonium hexafluorosilicate, hydrothermally treated with saturated steam, and finally treated with an aluminum salt solution. However, the obtained modified Y-type molecular sieve has a low secondary pore content and a large number of acidic centers are distributed in the micropores, which causes an excessive decomposition reaction in the reaction process and a decrease in the yield of the liquid. Will end up.

US40367639 discloses a hydrocracking method, which is treated by contacting with steam of at least 0.5 psi for a certain period of time at a temperature of 315 to 899 ° C. to obtain modified Y-type molecular sieves having a lattice constant of 2.440 to 2.464 nm. A method for modifying a Y-type molecular sieve obtained by exchanging ammonium with the treated Y molecular sieve to obtain an intermediate having a sodium content of less than 1%, and then obtaining a modified Y molecular sieve having a lattice constant of less than 2.440 nm. However, due to the strictness of this treatment process, the obtained modified Y molecular sieve has a serious destruction of the degree of crystallization, and the degree of crystallization is lowered, which affects the use performance thereof.

When the Y-type molecular sieve provided in the prior art is used for a hydrocracking reaction, it has a drawback of excessive decomposition and poor reaction selectivity.

An object of the present invention is to solve the problems of the prior art such as excessive decomposition and poor reaction selectivity existing in a hydrocracking reaction, a modified Y-type molecular sieve and a manufacturing method, a hydrocracking catalyst and a manufacturing method, and It is to provide a method for hydrocracking hydrogenated oil. The acidic center sites of this modified Y-type molecular sieve are concentrated and distributed inside the macropores, and the obtained hydrocracking catalyst improves the selectivity of the catalytic reaction process when used in the hydrocracking reaction of wax oil. It is possible to reduce the occurrence of secondary decomposition reactions, improve the quality of tail oil due to hydrocracking, and improve the yield of liquid products in the reaction.

As a result of research by the inventor of the present invention, in the modified Y-type molecular sieve manufactured by the prior art, a large amount of acidic centers are present in the micropore structure, and the total acid amount and n-butyl by pyridine infrared spectroscopy are present. We have found that the ratio to acid by pyridine infrared spectroscopy is generally greater than 1.5. However, an excessive decomposition reaction occurs due to a large amount of acidic centers present in the micropores, and the reaction selectivity deteriorates. On the other hand, the inventor limits the distribution of acidic centers in the modified Y-type molecular sieve and controls the number of acidic centers in the micropores to prevent excessive decomposition and poor reaction selectivity present in the hydrocracking reaction. The present invention is proposed to solve the problem.

For defects existing in the prior art, the first aspect of the present invention provides a modified Y-type molecular sieve, and the modified Y-type molecular sieve is Na ₂ O 0.5 based on the total amount of the modified Y-type molecular sieve. The ratio of the total acid amount of the modified Y-type molecular sieve by pyridine infrared spectroscopy to the total acid amount of the modified Y-type molecular sieve by n-butyl pyridine infrared spectroscopy is 1 to 1. The total acid content of the modified Y-type molecular sieve is 0.1 to 1.2 mmol / g by pyridine infrared spectroscopy.

Preferably, the modified Y-type molecular sieve has a specific surface area of 500 to 900 m ² / g, a pore volume of 0.28 to 0.7 ml / g, a relative crystallinity of 50% to 130%, and a lattice constant of 2.425 to 2. 45 nm, silica / alumina molar ratio (6-80): 1.

A second aspect of the present invention provides a method for producing the modified Y-type molecular sieve of the present invention.
Step (1) of pretreating NaY molecular sieves to obtain desodium-dealuminum-dealuminum Y-type molecular sieves,
In the step (2) of obtaining sodium-containing Y-type molecular sieves by exchanging sodium ions with the desodium-dealuminum Y-type molecular sieves.
The step (3) of immersing the sodium-containing Y-type molecular sieve with a large molecular ammonium salt solution and then drying and roasting to obtain a modified Y-type molecular sieve is included.

Preferably, in step (1), the pretreatment process is one or more of ammonium ion exchange, hydrothermal dealuminum, aluminum salt dealuminum, fluorosilicate dealuminum, and acid dealuminum. Including combinations of.

Preferably, in step (1), the pretreatment process is
The step (a) of obtaining a desodium Y-type molecular sieve by subjecting a NaY molecular sieve and an aqueous ammonium salt solution to an ammonium ion exchange reaction,
The step (b) of obtaining the product of hydrothermally dealuminum by hydrothermally dealuminating the desodium Y-type molecular sieve.
The step (c) of chemically dealuminating the hydrothermally dealuminum product to obtain the desodium-dealuminum-dealuminum Y-type molecular sieve is included.
The chemical dealuminum includes dealuminum with an aluminum salt, dealuminum with a fluorosilicate, or dealuminum with an acid.

A third aspect of the present invention provides a method for producing a hydrocracking catalyst, wherein the method provides.
The modified Y-type molecular sieve, amorphous silica-alumina and / or aluminum oxide of the present invention are mixed in a weight ratio of (5 to 90) :( 0 to 50) :( 0.6 to 80) to prepare a carrier mixing material. Next, the step (I) of adding an aqueous nitrate solution having a mass percentage of 3 to 30% by weight to the carrier mixed material to form a slurry and performing extrusion molding.
The extrusion product obtained in step (I) is dried at 80 to 120 ° C. for 1 to 5 hours and then roasted at 400 to 500 ° C. for 1 to 5 hours to obtain a silica-alumina carrier in step (II).
The silica / alumina carrier is saturated and immersed in a solution containing an active metal hydride, and the obtained product is dried and roasted to obtain a hydrocracking catalyst (III).

A fourth aspect of the present invention provides a hydrocracking catalyst produced by the method of the present invention, wherein the hydrocracking catalyst comprises a silica-alumina carrier and a hydroactive metal, and the hydrocracking catalyst. The content of the silica-alumina carrier is 55 to 85% by weight, the content of the hydride active metal is 15 to 45% by weight of the metal oxide, and the silica-alumina carrier is based on the total amount of the metal oxide. The modified Y-type molecular sieve of the present invention is contained, and the content of the modified Y-type molecular sieve in the silica-alumina carrier is 5 to 90% by weight.

A fifth aspect of the present invention provides a method for hydrocracking a hydrocarbon oil, in which the method is a step of contacting the hydrocarbon oil with the hydrocracking catalyst of the present invention to cause a hydrocracking reaction in the presence of hydrogen gas. The reaction temperature is 340 to 420 ° C., the reaction pressure is 8 to 20 MPa, the volumetric space velocity at the time of supplying the hydrocarbon oil is 0.1 to 2 h ^-1 , hydrogen gas and the hydrocarbon. The volume ratio with oil is (200-2000): 1.

According to the above technical proposal, the present invention provides a modified Y-type molecular sieve in which acidic center sites are concentrated and distributed in macropores (that is, secondary pores). Most of the acidic center sites in the micropores of the modified Y-type molecular sieve are occupied by sodium ions, and only the acidic center inside the macropores remains, so that hydrocarbon molecules enter the micropores and perform a secondary decomposition reaction. Occurrence is reduced. When the acid content of the modified Y-type molecular sieves was measured by the infrared method using alkaline organic substances with different molecular sizes, for example, pyridine and n-butyl pyridine, if the acid contents of both were equal, they were distributed on the modified Y-type molecular sieves. It shows that the acidic centers are concentrated in the macropores.

The present invention provides a method for producing a modified Y-type molecular sieve. First, the acidic center of the modified Y-type molecular sieve is exchanged with sodium ions, and the acidic center sites in various pores of the Y-type molecular sieve are occupied by sodium ions. Then, ammonium ion exchange treatment is performed using a benzyl quaternary ammonium salt having a large molecular size. Since the benzyl quaternary ammonium salt has a large molecular size, the sodium ions distributed in the macropores are selectively benzyl quaternary. After being exchanged for ammonium cations and further dried and roasted, only the benzyl quaternary ammonium cations are removed, the acidic center sites in the macropores of the Y-type molecular sieves are exposed, and the acidic center sites in the micropores are occupied by sodium ions. The molecular sieves according to the present invention are characterized in that the acidic center sites are concentrated and distributed in the macropores, and this feature is that pyridine and n-butyl having different molecular sizes are distributed. It can be determined by performing acidity measurement by the infrared method using pyridine, whereby a modified Y-type molecular sieve having the above characteristics can be obtained.

Furthermore, when a hydrogenation decomposition catalyst is produced using the modified Y-type molecular sieve of the present invention and used in the hydrogenation decomposition reaction process of wax oil, the reaction selectivity of large molecular cyclic hydrocarbon substances in wax oil is improved. It contributes to reducing the occurrence of secondary decomposition reactions, improving the quality of tail oil due to hydrocracking, and increasing the yield of liquid products in the reaction.

The endpoints and arbitrary values of the ranges disclosed herein are not limited to this exact range or value, and it should be understood that these ranges or values include values close to these ranges or values. Is. For numeric ranges, one or more new numeric ranges can be obtained by combining each other between the endpoints of each range, between the endpoint values of each range and the values of individual points, and between the values of individual points. The range of values of is to be considered as specifically disclosed herein.

The first aspect of the present invention provides a modified Y-type molecular sieve, wherein the modified Y-type molecular sieve contains 0.5 to 2% by weight of Na _2O based on the total amount of the modified Y-type molecular sieve, and the modification is performed. The ratio of the total acid amount of the Y-type molecular sieve by pyridine infrared spectroscopy to the total acid amount of the modified Y-type molecular sieve by n-butyl pyridine infrared spectroscopy is 1 to 1.2, and the modified Y-type molecular sieve has a total acid amount of 1 to 1.2. It is characterized in that the total acid amount by pyridine infrared spectroscopy is 0.1 to 1.2 mmol / g.

In the present invention, the modified Y-type molecular sieve is a molecular sieve obtained by chemically treating Y-type molecular sieve raw powder (for example, the method described later described in the present invention).

In the modified Y-type molecular sieve according to the present invention, the acidic centers are mainly distributed in the macropores, and the micropores have a small amount of acidic centers or no acidic centers, whereby the hydrocarbon oil molecule becomes micropores. It is possible to reduce the number of secondary decomposition reactions that enter and carry out secondary decomposition reactions at acidic centers.

The distribution characteristic of the acidic center in the pores of the modified Y-type molecular sieve according to the present invention can be expressed by the results of measuring the acidity of the modified Y-type molecular sieve using pyridine and n-butylpyridine as two types of probe molecules. The molecular diameter of n-butylpyridine is about 0.8 nm and can only enter the macropores of the modified Y-type molecular sieves according to the invention, thereby reflecting the total amount of acidic centers in the macropores. The molecular diameter of pyridine is about 0.6 nm and can enter both the micropores and macropores of the modified Y-type molecular sieves to reflect the total amount of acidic centers in all the pores of the modified Y-type molecular sieves. Specifically, as a test process, a Nicolet 6700 Fourier infrared spectrometer manufactured by NICOLET, USA can be used by pyridine, n-butylpyridine adsorption infrared spectroscopy.
20 mg of a finely ground sample (less than 200 mesh in grain size) is pressed onto a sheet with a diameter of 20 mm, set in the sample holder of the absorption cell, and 200 mg of the sample (sheet) is placed in a cup at the lower end of the quartz spring (before adding the sample). Record the length of the spring, put it in x ₁ , mm), connect the absorption cell and the suction tube, vacuum suction and purify, and when the degree of vacuum becomes 4 x 10 ^-2 Pa, it rises to 500 ° C. It is kept warm for 1 hour to remove adsorbents on the surface of the sample (at this time, the spring length after purification of the sample, x ₂ , mm). Next, the temperature is lowered to room temperature, pyridine (or n-butylpyridine) is adsorbed to saturation, then the temperature is raised to 160 ° C., equilibrium is performed for 1 hour, and the physically adsorbed pyridine is desorbed (at this time). The total amount of acid was determined by the spring length after pyridine adsorption, _x3 , mm), and the pyridine (or n-butylpyridine) weight adsorption method.
The total acid amount is calculated by the pyridine weight adsorption method, and specifically, it is as follows.

Note: 79.1 and 136.1 are molar masses of pyridine and n-butylpyridine, respectively, in units of g / mol.

In the present invention, the reaction of hydrocarbon oil molecules on molecular sieves is controlled by adjusting the concentrated distribution of acidic center sites in the micropores and macropores of Y-type molecular sieves. The distribution of acidic center sites is indicated by total acidity by infrared measurements of pyridine and n-butylpyridine. In a general Y-type molecular sieve in which the acidic center site in the pores is not adjusted, the ratio of the total acid amount by pyridine infrared spectroscopy to the total acid amount by n-butyl pyridine infrared spectroscopy is generally 1. Greater than 2. Thereby, it can be determined whether or not the acidic center site in the micropores of the Y-type molecular sieve is controlled.

When the total acid amount measured with n-butylpyridine and pyridine for the modified Y-type molecular sieve is the same, or the total acid amount with n-butylpyridine is slightly smaller, that is, the pyridine infrared of the modified Y-type molecular sieve. When the ratio of the total acid amount by spectroscopy to the total acid amount of the modified Y-type molecular sieve by n-butylpyridine infrared spectroscopy is limited to 1 to 1.2, the acidic center contained in the modified Y-type molecular sieve. Indicates that is mainly concentrated in the macropores.

According to the present invention, preferably, the modified Y-type molecular sieve contains 0.8 to 1.8% by weight of Na _2O based on the total amount of the modified Y-type molecular sieve, and the pyridine of the modified Y-type molecular sieve. The ratio of the total acid amount by infrared spectroscopy to the total acid amount of the modified Y-type molecular sieve by n-butylpyridine infrared spectroscopy is 1.02 to 1.15.

More preferably, the modified Y-type molecular sieve contains 1 to 1.5% by weight of Na _2O based on the total amount of the modified Y-type molecular sieve, and the total acid of the modified Y-type molecular sieve by pyridine infrared spectroscopy. The ratio of the amount to the total acid amount of the modified Y-type molecular sieve by n-butylpyridine infrared spectroscopy is 1.05 to 1.12.

According to the present invention, the total acid amount of the modified Y-type molecular sieve by pyridine infrared spectroscopy is preferably 0.2 to 1 mmol / g.

More preferably, the total acid content of the modified Y-type molecular sieve by pyridine infrared spectroscopy is 0.3 to 0.8 mmol / g.

According to the present invention, when the modified Y-type molecular sieve is used in the hydrocracking reaction process of wax oil, it contributes to improving the quality of tail oil by hydrocracking and improving the yield of the reaction liquid product. It also has other characteristics such as hydrogenation. When it is preferable, the specific surface area of the modified Y-type molecular sieve is 500 to 900 m ² / g, preferably 550 to 850 m ² / g, and more preferably 600 to 750 m ² / g.

Preferably, the pore volume of the modified Y-type molecular sieve is 0.28 to 0.7 ml / g, preferably 0.3 to 0.65 ml / g, and more preferably 0.35 to 0.6 ml / g. ..

Preferably, the relative crystallinity of the modified Y-type molecular sieve is 50% to 130%, 60% to 110%, and more preferably 70% to 100%.

Preferably, the lattice constant of the modified Y-type molecular sieve is 2.425 to 2.45 nm, preferably 2.428 to 2.448 nm, and more preferably 2.43 to 2.445 nm.

Preferably, the silica / alumina molar ratio of the modified Y-type molecular sieve is (6 to 80): 1, preferably (8 to 60): 1, and more preferably (10 to 50): 1.

A second aspect of the present invention provides a method for producing the modified Y-type molecular sieve of the present invention.
Step (1) of pretreating NaY molecular sieves to obtain desodium-dealuminum-dealuminum Y-type molecular sieves,
In the step (2) of obtaining sodium-containing Y-type molecular sieves by exchanging sodium ions with the desodium-dealuminum Y-type molecular sieves.
The step (3) of immersing the sodium-containing Y-type molecular sieve with a large molecular ammonium salt solution and then drying and roasting to obtain a modified Y-type molecular sieve is included.

According to the present invention, step (1) forms macropores on the NaY molecular sieve, which is advantageous for subsequent modification of the macropores and micropores respectively. If preferred, in step (1), the pretreatment process is one of ammonium ion exchange, hydrothermal dealuminum, dealuminum with an aluminum salt, dealuminum with a fluorosilicate, and dealuminum with an acid. Includes multiple combinations. In the present invention, the pretreatment of the NaY molecular sieve is one or more of ammonium ion exchange, hydrothermal dealuminum, dealuminum with aluminum salt, dealuminum with fluorosilicate, and dealuminum with acid. The desodium-dealuminum Y-type molecular sieve may be provided without limitation in the order between the steps. For example, the desodium-dealuminum Y-type molecular sieve contains Na _2O . The amount is less than 3% by weight, SiO ₂ / Al ₂ O ₃ molar ratio (6 to 80): 1, lattice constant 2.425 to 2.450. In general, first, the NaY molecular sieve is desodiumized by exchanging ammonium ions, and then one of hydrothermal dealuminum, dealuminum with an aluminum salt, dealuminum with a fluorosilicate, and dealuminum with an acid. Alternatively, the desalting product is dealuminated by a combination of two or more.

In a preferred embodiment of the invention, the pretreatment process of step (1) is
The step (a) of obtaining a desodium Y-type molecular sieve by subjecting a NaY molecular sieve and an aqueous ammonium salt solution to an ammonium ion exchange reaction,
The step (b) of obtaining the product of hydrothermally dealuminum by hydrothermally dealuminating the desodium Y-type molecular sieve.
The step (c) of chemically dealuminating the hydrothermally dealuminum product to obtain the desodium-dealuminum-dealuminum Y-type molecular sieve is included.
The chemical dealuminum is dealuminum with an aluminum salt, dealuminum with a fluorosilicate, or dealuminum with an acid.

According to the present invention, step (a) removes Na ions on NaY molecular sieves so that the subsequent dealuminum removal process can be carried out smoothly. If preferable, in step (a), the process of the ion exchange reaction with the ammonium salt involves sieving the NaY molecular sieve and the ammonium salt aqueous solution at 60 to 120 ° C., preferably 60 to 90 ° C., 1 to 4 times, 1 to 3 h. The exchange is to obtain the desodium Y-type molecular sieve.

Preferably, the Na ₂ O content of the desodium Y-type molecular sieve is less than 3% by weight.

Preferably, the SiO ₂ / Al ₂ O ₃ molar ratio of the NaY molecular sieve is (3 to 6): 1 and the Na ₂ O content is 6 to 12% by weight.

Preferably, the ammonium salt is one or more selected from ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate and ammonium oxalate, and the molar concentration of the ammonium salt aqueous solution is 0.3 to 6 mol / L, preferably 1. It is ~ 3 mol / L.

According to the present invention, in step (b), the desodium Y-type molecular sieve is dealuminated to form macropores. Preferably, in step (b), the hydrothermal dealuminum process uses the desodium Y-type molecular sieve and steam under the conditions of a temperature of 520 to 700 ° C. and a pressure of 0.01 to 0.5 MPa for 1 to 6 hours. To make contact.

Preferably, the number of times of the hydrothermal dealuminum is 1 to 3 times.

According to the present invention, step (c) chemically dealuminates the molecular sieve to form macropores. Preferably, in step (c), the chemical dealumination process takes the hydrothermal dealuminum product with an aluminum salt solution, an ammonium fluorosilicate solution or a nitrate solution at a temperature of 50-120 ° C. It is a constant temperature reaction for 0.5 to 3 hours.

Preferably, the aluminum salt solution is an aqueous solution of at least one of aluminum chloride, aluminum sulfate, and aluminum nitrate.

Preferably, the molar concentration of the aluminum salt solution, ammonium fluorosilicate solution or nitric acid solution is 0.05 to 2 mol / L. The constant temperature reaction between the product of the hydrothermal dealuminum and the aluminum salt solution is dealumination by the aluminum salt. The constant temperature reaction between the hydrothermally dealuminum product and the ammonium fluorosilicate solution is dealuminumization with the fluorosilicate. The constant temperature reaction between the product of the hydrothermal dealuminum and the nitric acid solution is dealumination with the acid.

According to the present invention, in step (2), the acidic centers having macropores and micropores in the desodium-dealuminum Y-type molecular sieve are neutralized with sodium ions. In step (2), the sodium ion exchange process uses the desodium / dealuminum Y-type molecular sieve and the NaNO ₃ aqueous solution having a mass percentage of NaNO ₃ of 0.1 to 3% by weight at 40 to 80 ° C. It is a constant temperature reaction for 1 to 4 hours.

According to the present invention, the dipping treatment of step (3) exposes the acidic center in the macropores by exchanging the sodium ion occupying the acidic center in the macropores of the Y-type molecular sieve with a large molecular ammonium salt. Large-molecular-weight ammonium salts cannot enter the micropores of Y-type molecular sieves, and sodium ions still occupy the acidic center in the micropores. The finally obtained modified Y-type molecular sieve of the present invention has an acidic center in the macropores and an extremely small or no acidic center in the micropores, and is used for the hydrocracking reaction. And reduce the occurrence of secondary decomposition reactions of hydrocarbon oils. When it is preferable, the process of the dipping treatment in step (3) is to soak the sodium-containing Y-type molecular sieve in the large molecular ammonium salt solution for 2 to 6 hours at 40 to 80 ° C.

In the present invention, the large molecular weight ammonium salt is preferably a benzyl quaternary ammonium salt.

Preferably, the benzyl quaternary ammonium salt is at least one of benzyltripropylammonium bromide, benzyltributylammonium bromide, benzyltripropylammonium chloride, and benzyltributylammonium chloride.

Preferably, it is the concentration of bromine or element chlorine in the large molecule ammonium salt solution, and the molar concentration of the large molecule ammonium salt solution is 0.2 to 2 mol / L.

In the present invention, the distribution of acidic centers in the produced modified Y-type molecular sieves can be measured by the pyridine infrared adsorption method and the n-butyl pyridine infrared adsorption method. The specific method and test results are the same as described above, and will not be described in detail here.

According to the present invention, if preferred, in step (3), the drying process is drying at 100 to 150 ° C. for 1 to 4 hours, and the roasting process is roasting at 500 to 700 ° C. for 2 to 6 hours. Is to process.

A third aspect of the present invention provides a method for producing a hydrocracking catalyst, wherein the method provides.
The modified Y-type molecular sieve, amorphous silica-alumina and / or aluminum oxide of the present invention are mixed in a weight ratio of (5 to 90) :( 0 to 50) :( 0.6 to 80) to prepare a carrier mixing material. Next, the step (I) of adding an aqueous nitrate solution having a mass percentage of 3 to 30% by weight to the carrier mixed material to form a slurry and performing extrusion molding.
The extrusion product obtained in step (I) is dried at 80 to 120 ° C. for 1 to 5 hours and then roasted at 400 to 500 ° C. for 1 to 5 hours to obtain a silica-alumina carrier in step (II).
The silica / alumina carrier is saturated and immersed in a solution containing an active metal hydride, and the obtained product is dried and roasted to obtain a hydrocracking catalyst (III).

In step (I) of the catalyst production method according to the present invention, the solid content of the slurry may be suitable for extrusion molding of long strand extrusion products. Preferably, the solid content of the slurry is 30-60% by weight.

In the present invention, in step (III), the amount of the solution containing the hydroactive metal added is such that the obtained hydrocracking catalyst contains 15 to 45% by weight of the hydroactive metal as a metal oxide. do. In the solution containing the hydrogenated active metal, the hydrogenated active metal is a metal oxide and may have a concentration of 20 to 70 mol / L.

In the present invention, the solution containing the hydrogenated active metal may be a solution of a compound containing a metal element of Group VIII and / or Group VI. Preferably, it may be a solution of a compound containing Ni and / or Co, or a solution of a compound containing W and / or Mo. More preferably, the solution containing the active metal hydride may be a solution containing nickel nitrate, cobalt nitrate, ammonium metatungstate, ammonium molybdate, and molybdenum oxide.

In the present invention, the drying of step (III) can be carried out at 90 to 150 ° C. for 2 to 20 hours. Roasting can be carried out at 400-600 ° C. for 2-10 hours. Thereby, the hydroactive metal is converted into the form of an oxide and exists in the hydrocracking catalyst.

A fourth aspect of the present invention provides a hydrocracking catalyst produced by the method of the present invention, wherein the hydrocracking catalyst comprises a silica-alumina carrier and a hydroactive metal, and the hydrocracking catalyst. The content of the silica-alumina carrier is 55 to 85% by weight, the content of the hydride active metal is 15 to 45% by weight of the metal oxide, and the silica-alumina carrier is based on the total amount of the metal oxide. The modified Y-type molecular sieve of the present invention is contained, and the content of the modified Y-type molecular sieve in the silica-alumina carrier is 5 to 90% by weight.

According to the present invention, the hydroactive metal is preferably selected from Group VIII and / or Group VI metals.

Preferably, the Group VIII metal is Ni and / or Co, and the Group VI metal is W and / or Mo.

Preferably, it is a metal oxide based on the total amount of the catalyst, and the hydrocracking catalyst contains 3 to 15% by weight of the Group VIII metal and 10 to 40% by weight of the Group VI metal.

In the present invention, in order to facilitate the use, transportation and storage of the hydrocracking catalyst, the hydroactive metal in the hydrocracking catalyst is present in an oxidized state and is a sulfur-containing compound prior to the hydrocracking reaction. After being converted into a sulfide state by a vulverization reaction in contact with hydrogen, it can participate in the hydrocracking of hydrocarbon oil.

In the present invention, the hydrocracking catalyst contains the modified Y-type molecular sieve component according to the present invention, has better reaction selectivity for hydrocracking, and reduces the occurrence of secondary decomposition reactions of hydrocarbon oil molecules. It is more excellent in the selectivity of the hydrocracking reaction product. The reaction performance of the hydrogenation decomposition catalyst can be measured by a specific reaction performance evaluation experiment. In the experiment, a one-stage series one-pass process can be used in a small microreactor, the device has two reactors connected in series, and the first reactor is filled with a conventional purification catalyst according to the procedure. Then, the second reactor is filled with a hydrocracking catalyst.

In the present invention, the second reactor is filled with the hydrogenation decomposition catalyst of the present invention once and the conventional hydrogenation decomposition catalyst separately manufactured by using a conventional Y-type molecular sieve, and the reaction evaluation is performed separately. Therefore, the BMCI value of the decomposed tail oil product obtained in each of the two reactions and the yield of the liquid product of the apparatus can be compared while controlling the nitrogen content and the conversion depth of the refined oil in the same manner. Among them, the lower the BMCI value of the tail oil product and the higher the liquid yield of the product, the more the corresponding catalyst further promotes the reaction of the large molecular cyclic hydrocarbon in the process of the hydrocracking reaction, and the secondary decomposition reaction occurs. Is shown to be reduced. The difference between the two reactions is only the molecular sieve used for the catalyst, and the above result is considered to be because the acidity of the molecular sieve is more concentrated and distributed by the macropores.

A fifth aspect of the present invention provides a method for hydrocracking a hydrocarbon oil, in which the method is a step of contacting the hydrocarbon oil with the hydrocracking catalyst of the present invention to cause a hydrocracking reaction in the presence of hydrogen gas. The reaction temperature is 340 to 420 ° C., the reaction pressure is 8 to 20 MPa, the volumetric space velocity at the time of supplying the hydrocarbon oil is 0.1 to 2 h ^-1 , hydrogen gas and the hydrocarbon. The volume ratio with oil is (200-2000): 1.

In the present invention, the hydrocarbon oil may be used as a petroleum-based vacuum wax oil raw material, and the distillation range thereof is 300 to 600 ° C. and the density is 0.86 to 0.94 g / cm ³ .

When the hydrocracking reaction is carried out, the active metal in the hydrocracking catalyst is involved in a sulfurized state. However, if a catalyst containing a hydrogenated active metal in a sulfide state is directly produced, the catalyst must be easily oxidized during transport and storage and sulphurized before it can be fully involved in the hydrocracking reaction. .. Therefore, in this field, in general, a catalyst containing an active hydrogenated metal in an oxidized state is produced, and the catalyst is subjected to a sulfurization reaction before the hydrocracking reaction of the hydrocarbon oil is carried out to obtain the hydrogenated active metal in the hydrogenated state. The contained catalyst is obtained, or the sulfur-containing compound in the hydrocarbon oil is utilized to carry out sulfide decomposition of the hydride active metal and hydrocracking of the hydrogenated oil during contact between the hydrocarbon oil and the catalyst. In the method for hydrocracking hydrogen oil according to the present invention, during the hydrocracking reaction, the hydrocracking catalyst of the present invention sulfides the hydroactive metal in the presence of a sulfur-containing compound in the hydrocarbon oil. At the same time, it realizes hydrocracking of hydrocarbon oil.

Hereinafter, the present invention will be described in detail with reference to Examples.
In the following examples and comparative examples, the amount of acid by pyridine, n-butylpyridine infrared spectroscopy is determined by the Nicolet 6700 Fourier infrared spectrometer method manufactured by NICOLET, USA, by pyridine, n-butylpyridine adsorption infrared spectroscopy. Measured using, the process is as follows.

20 mg of a finely ground sample (less than 200 mesh in grain size) is pressed onto a sheet with a diameter of 20 mm, set in the sample holder of the absorption cell, and 200 mg of the sample (sheet) is placed in a cup at the lower end of the quartz spring (before adding the sample). Record the length of the spring, put it in x ₁ , mm), connect the absorption cell and the suction tube, vacuum suction and purify, and when the degree of vacuum becomes 4 x 10 ^-2 Pa, it rises to 500 ° C. It is kept warm for 1 hour to remove adsorbents on the surface of the sample (at this time, the spring length after purification of the sample, x ₂ , mm). Next, the temperature is lowered to room temperature, pyridine (or n-butylpyridine) is adsorbed to saturation, then the temperature is raised to 160 ° C., equilibrium is performed for 1 hour, and the physically adsorbed pyridine is desorbed (at this time). The total amount of acid was determined by the spring length after pyridine adsorption, _x3 , mm), and the pyridine (or n-butylpyridine) weight adsorption method.

The total acid amount is calculated by the pyridine weight adsorption method, and specifically, it is as follows.

Note: 79.1 and 136.1 are molar masses of pyridine and n-butylpyridine, respectively, in units of g / mol.

Surface area and pore volume are measured by low temperature nitrogen adsorption (BET method).
The Na ₂ O content in the molecular sieves and the SiO ₂ / Al ₂ O ₃ molar ratio of the molecular sieves were measured by the fluorescence method.
The lattice constant and relative crystallinity of the molecular sieve are measured by the XRD method, and a Rigaku Dmax-2500 X-ray diffractometer is used as an instrument, Cukα emission, graphite single crystal filter, operation tube voltage 35 KV, tube current 40 mA, scanning speed. (2θ) 2 ° / min and a scanning range of 4 ° to 35 ° are used. The standard sample is the Y-type molecular sieve raw powder used in Example 1 of the present invention.

The yield of tail oil is calculated from the cut data of the actual boiling point of the product.

BMCI measurement method: BMCI = 48640 / T + 473.7d-456.8
d: Density (15.6 ° C)
T: Average boiling point expressed in absolute temperature K.

Example 1
(1) NaY-type molecular sieve raw powder (Na ₂ O content 10% by weight, SiO ₂ / Al ₂ O ₃ mol ratio 5.0), ammonium nitrate having a concentration of 1.0 mol / L and a liquid-solid ratio of 3: 1. The sodium ion exchange was carried out at 70 ° C. for 3 hours, and this process was repeated 3 times. The obtained desodium Y-type molecular sieve had a Na ₂ O content of 2.5% by weight.

(2) The sodium-free Y-type molecular sieve and steam were brought into contact with each other at 550 ° C. and 0.1 MPa to carry out hydrothermal dealuminum for 2 hours, and this process was repeated once to obtain a product of hydrothermal dealuminum.

(3) The product of hydrothermal dealuminum is mixed with a 0.5 mol / L aluminum sulfate solution at a liquid-solidity ratio of 5: 1, and then a constant temperature reaction is carried out at 80 ° C. for 2 hours to remove sodium and dealuminum. A Y-type molecular sieve was obtained.

(4) Sodium-de-aluminum Y-type molecular sieves were added to a 0.8 mol / L NaNO ₃ aqueous solution, and sodium ion exchange was carried out at 60 ° C. for 2 hours to obtain sodium-containing Y-type molecular sieves.

(5) Sodium-containing Y-type molecular sieves were added to a benzyltributylammonium bromide aqueous solution having a concentration of 0.5 mol / L, and the cells were immersed at 70 ° C. for 3 hours.

(6) The product obtained in step (5) was dried at 120 ° C. for 4 hours and roasted at 550 ° C. for 4 hours to obtain modified Y-type molecular sieves, which were numbered Y-1.

Example 2
(1) NaY molecular sieve raw powder was mixed with ammonium chloride having a concentration of 2.0 mol / L at a liquid-solid ratio of 3: 1, ammonium ion exchange was performed at 80 ° C. for 2 hours, and this process was repeated once to obtain desorption. The Na ₂ O content of the sodium Y-type molecular sieve was 2.7% by weight.

(2) The sodium-free Y-type molecular sieve and steam were brought into contact with each other at 600 ° C. and 0.1 MPa to carry out hydrothermal dealuminum for 2 hours, and this process was repeated once to obtain a product of hydrothermal dealuminum.

(3) The product of hydrothermal dealuminum is mixed with an ammonium fluorosilate solution having a liquid-solid ratio of 5: 1 and a concentration of 0.4 mol / L, and then a constant temperature reaction is carried out at 90 ° C. for 2 hours to de-sodium and de-sodium. Aluminum Y-type molecular sieves were obtained.

(4) Desodium-dealuminum Y-type molecular sieves were added to a 2.0 mol / L NaNO ₃ aqueous solution, and sodium ion exchange was carried out at 80 ° C. for 2 hours to obtain sodium-containing Y-type molecular sieves.

(5) Sodium-containing Y-type molecular sieves were added to an aqueous solution of benzyltributylammonium chloride having a concentration of 1.5 mol / L, and the cells were immersed at 70 ° C. for 3 hours.

(6) The product obtained in step (5) was dried at 120 ° C. for 4 hours and roasted at 550 ° C. for 4 hours to obtain modified Y-type molecular sieves, which were numbered Y-2.

Example 3
(1) NaY molecular sieve raw powder was mixed with ammonium sulfate having a concentration of 3.0 mol / L at a liquid-solid ratio of 3: 1, ammonium ion exchange was performed at 80 ° C. for 2 hours, and this process was repeated once to obtain desodium Y. The Na ₂ O content of the type molecular sieve was 2.3% by weight.

(2) The sodium-free Y-type molecular sieve and steam were brought into contact with each other at 630 ° C. and 0.1 MPa, hydrothermally treated for 2 hours, and this process was repeated once to obtain a hydrothermally dealuminum product.

(3) The product of hydrothermal dealuminum is mixed with a dilute nitrate solution having a liquid-solid ratio of 5: 1 and a concentration of 0.6 mol / L, and then a constant temperature reaction is carried out at 95 ° C. for 2 hours to desodium and de-sodium. Aluminum Y-type molecular sieves were obtained.

(4) Desodium-dealuminum Y-type molecular sieves were added to a 1.5 mol / L NaNO ₃ aqueous solution, and sodium ion exchange was carried out at 70 ° C. for 2 hours to obtain sodium-containing Y-type molecular sieves.

(5) Sodium-containing Y-type molecular sieves were added to a benzyltripropylammonium bromide aqueous solution having a concentration of 1.2 mol / L, and the cells were immersed at 80 ° C. for 2 hours.

(6) The product obtained in step (5) was dried at 120 ° C. for 4 hours and roasted at 550 ° C. for 4 hours to obtain modified Y-type molecular sieves, which were designated as No. Y-3.

Example 4
(1) NaY-type molecular sieve raw powder was mixed with ammonium nitrate having a concentration of 0.5 mol / L at a liquid-solid ratio of 3: 1, ammonium ion exchange was performed at 70 ° C. for 3 hours, and this process was repeated 3 times to obtain desodium. The Na ₂ O content of the Y-type molecular sieve was 2.5% by weight.

(2) Desodium Y-type molecular sieves were mixed with a 0.2 mol / L ammonium fluorosilate-treated solution at a liquid-solid ratio of 6: 1, and then a constant temperature reaction was carried out at 80 ° C. for 2 hours.

(3) The product obtained in step (2) and steam were brought into contact with each other at 0.2 MPa and 520 ° C., hydrothermal treatment was performed for 2 hours, and this process was repeated once.

(4) The product obtained in step (3) was mixed with a 0.6 mol / L aluminum sulfate solution at a liquid-solid ratio of 5: 1 and stirred, and then a constant temperature reaction was carried out at 75 ° C. for 2 hours. De-sodium and de-aluminum Y-type molecular sieves were obtained.

(5) Sodium-de-aluminum Y-type molecular sieves were added to a 0.6 mol / L NaNO ₃ aqueous solution, and sodium ion exchange was carried out at 50 ° C. for 2 hours to obtain sodium-containing Y-type molecular sieves.

(6) Sodium-containing Y-type molecular sieves were added to a benzyltributylammonium bromide aqueous solution having a concentration of 0.5 mol / L, and the cells were immersed at 60 ° C. for 5 hours.

(7) The product obtained in step (6) was dried at 120 ° C. for 4 hours and roasted at 550 ° C. for 4 hours to obtain modified Y molecular sieves, which were numbered Y-4.

Comparative Example 1
(1) NaY-type molecular sieve raw powder was mixed with ammonium nitrate having a concentration of 0.5 mol / L at a liquid-solid ratio of 3: 1, ammonium ion exchange was performed at 70 ° C. for 3 hours, and this process was repeated 3 times to obtain desodium. The Na ₂ O content of the Y-type molecular sieve was 2.5% by weight.

(2) Ammonium exchange The Y molecular sieve and steam were brought into contact with each other at 550 ° C. and 0.1 MPa, hydrothermally treated for 2 hours, and this process was repeated once to obtain a product of hydrothermal dealuminum.

(3) The product of hydrothermal dealuminum was mixed with a 0.5 mol / L aluminum sulfate solution at a liquid-solid ratio of 5: 1, and then a constant temperature reaction was carried out at 80 ° C. for 2 hours.

(4) The product obtained in step (3) was dried at 120 ° C. for 4 hours and roasted at 550 ° C. for 4 hours to obtain modified Y-type molecular sieves, which were designated as No. B-1.

Comparative Example 2
(1) NaY-type molecular sieve raw powder was mixed with ammonium nitrate having a concentration of 0.5 mol / L at a liquid-solid ratio of 3: 1, ammonium ion exchange was performed at 70 ° C. for 3 hours, and this process was repeated 3 times to obtain desodium. The Na ₂ O content of the Y-type molecular sieve was 2.5% by weight.

(2) The product obtained in step (1) was mixed with a 0.2 mol / L ammonium fluorosilate-treated solution at a liquid-solid ratio of 6: 1, and then a constant temperature reaction was carried out at 80 ° C. for 2 hours.

(3) The product obtained in step (2) and steam were brought into contact with each other at 0.2 MPa and 520 ° C., hydrothermal treatment was performed for 2 hours, and this process was repeated once.

(4) The molecular sieves obtained in step (3) were mixed with a 0.6 mol / L aluminum sulfate solution at a liquid-solid ratio of 5: 1 and stirred, and then a constant temperature reaction was carried out at 75 ° C. for 2 hours.

(5) The product obtained in step (4) was dried at 120 ° C. for 4 hours and roasted at 550 ° C. for 4 hours to obtain modified Y-type molecular sieves, which were designated as No. B-2.

Comparative Example 3
(1) 200 g of NaY-type molecular sieve raw powder was mixed with ammonium nitrate having a concentration of 0.5 mol / L at a liquid-solid ratio of 3: 1, ammonium ion exchange was performed at 70 ° C. for 3 hours, and this process was repeated 3 times to obtain desorption. The Na ₂ O content of the sodium Y-type molecular sieve was 2.5% by weight.

(2) The sodium-free Y-type molecular sieve was subjected to hydrothermal treatment at 560 ° C. and 0.1 MPa for 2 hours.

(3) The molecular sieve obtained in step (2) is mixed with distilled water at a liquid-solid ratio of 5: 1 and stirred, then the temperature is raised to 80 ° C., and a 0.5 mol / L aluminum sulfate solution is stirred while stirring. 400 ml was added, and a constant temperature reaction was carried out for 2 hours.

(4) The molecular sieves obtained in step (3) were dried at 140 ° C. for 8 min.

(5) The molecular sieves obtained in step (4) are placed in a closed container filled with a butadiene atmosphere, sufficiently contacted for 20 minutes while controlling the pressure to 0.3 MPa, and then at 200 ° C. under an air atmosphere. It was heated for 15 hours.

(6) The molecular sieve obtained in step (5) is mixed with distilled water at a liquid-solid ratio of 5: 1, and then 100 ml of an ammonium fluorosilate solution having a concentration of 0.6 mol / L is added and the temperature is 80 ° C. Processed for 2 hours.

(7) The Y molecular sieves treated with ammonium fluorosilate in step (6) were dried at 120 ° C. for 2 hours and roasted at 550 ° C. for 4 hours to obtain modified Y molecular sieves, which were designated as No. B-3.

The characteristics of the molecular sieves produced in the above Examples and Comparative Examples are shown in Table 1.

As is clear from the data in Table 1, the modified Y-type molecular sieve manufactured by the embodiment of the technical proposal according to the present invention has a total acid amount by pyridine infrared spectroscopy and a total acid amount by n-butyl pyridine infrared spectroscopy. The ratio was 1 to 1.2, preferably 1.02 to 1.15, more preferably 1.05 to 1.12, and particularly preferably 1.03 to 1.09. On the other hand, the ratio of the total acid amount of the modified Y-type molecular sieve obtained in the comparative example by the pyridine infrared spectroscopy to the total acid amount by the n-butyl pyridine infrared spectroscopy is larger than 1.2, and is 1.4 to 1. It was 1.7.

Example 5
The hydrocracking catalysts were produced using the modified Y-type molecular sieves produced in Examples 1 to 4 and Comparative Examples 1 to 3, and the component compositions of the catalysts are shown in Table 2.

(1) A modified Y-type molecular sieve and aluminum oxide were mixed to prepare a carrier mixed material, and then an aqueous nitric acid solution having a mass percentage of 20% by mass was added to the carrier mixed material to form a slurry, which was extruded.

(2) The extruded product obtained in step (1) was dried at 100 ° C. for 3 hours and then roasted at 450 ° C. for 3 hours to obtain a silica-alumina carrier.

(3) The silica-alumina carrier was saturated and immersed in a solution containing an active metal for hydrogenation, and the obtained product was dried and roasted to obtain a hydrogenation decomposition catalyst.

The numbers corresponding to the obtained catalysts are C-1 to C-4 for the catalysts corresponding to the modified Y-type molecular sieves Y-1 to Y-4 of Examples 1 to 4, and the modified Y-types of Comparative Examples 1 to 3 are used. The catalysts corresponding to the molecular sieves B-1 to B-3 are BC-1 to BC-3. It is shown in Table 2.

Evaluation example 1
The catalysts C-1 to C-4 and BC-1 to BC-3 are evaluated and tested in a small micro-reactor (100 ml small evaluation device manufactured by xytel in the United States), and the evaluation device is equipped with a one-stage series one-pass process. The first reactor is filled with the conventional purification catalyst, the second reactor is filled with the hydrocracking catalyst shown in Table 2, the characteristics of the reaction raw material oil are shown in Table 3, and the evaluation results are shown in Tables 4 to 4. Shown in 5.

As is clear from the results in Table 5, in the hydrogenation decomposition catalysts C-1 to C-4 produced by using the modified Y-type molecular sieves according to the present invention of Examples 1 to 4, the acidic center optimized for the molecular sieve was used. When having a distribution, the amount of acidic centers in the micropores is reduced, and a hydrocracking reaction is carried out, the BMCI value of the obtained tail oil product by hydrocracking is the modified Y-type molecular sieve (pyridine) of Comparative Examples 1 to 3. The ratio of the total acid amount by infrared spectroscopy to the total acid amount by n-butylpyridine infrared spectroscopy is greater than 1.2), which is significantly lower than the reaction result by the hydrocracking catalyst produced using. Moreover, the C ₅ ⁺ liquid yield was larger than the reaction result by the catalyst of the comparative example.

Further, Comparative Example 3 provides a modified Y-type molecular sieve according to the prior art, and the silica / alumina ratio between the body phase and the surface of the modified Y-type molecular sieve particles is used. This modification method affects the acid content of the molecular sieve by changing the local silica / alumina ratio of the molecular sieve, but this method can change the distribution of acidic center sites in the macropores and micropores of the Y-type molecular sieve. The acid center site in the micropores remains exposed, and the ratio of the amount of pyridineic acid to the amount of n-butylpyridine acid is greater than 1.2, so that the hydrocarbons in the micropores remain exposed at the acid center site. The possibility of a secondary decomposition reaction could not be reduced, and when used for hydrocracking, the quality of tail oil due to hydrocracking could not be improved and the yield of the liquid product of the reaction could not be improved. rice field.

Although the preferred embodiment of the present invention has been described in detail above, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications including a combination of various technical features by other appropriate methods can be made to the technical proposal of the present invention, and these simple modifications can be made. Modifications and combinations should also be considered disclosure of the invention and are all within the scope of the invention.

Claims (21)

A modified Y-type molecular sieve,
Based on the total amount of the modified Y-type molecular sieve, the modified Y-type molecular sieve contains 0.5 to 2% by weight of Na _2O , and the total acid amount of the modified Y-type molecular sieve by pyridine infrared spectroscopy and the modification. The ratio of the Y-type molecular sieve to the total acid amount by n-butyl pyridine infrared spectroscopy is 1 to 1.2, and the total acid amount of the modified Y-type molecular sieve by pyridine infrared spectroscopy is 0.1 to 1. A modified Y-type molecular sieve characterized by 2 mmol / g. Based on the total amount of the modified Y-type molecular sieve, the modified Y-type molecular sieve contains 0.8 to 1.8% by weight of Na _2O , and the total acid amount of the modified Y-type molecular sieve by pyridine infrared spectroscopy. The ratio of the modified Y-type molecular sieve to the total acid amount by n-butyl pyridine infrared spectroscopy is 1.02 to 1.15, and the total acid content of the modified Y-type molecular sieve by pyridine infrared spectroscopy is 0. The modified Y-type molecular sieve according to claim 1, which is 2 to 1 mmol / g. Based on the total amount of the modified Y-type molecular sieve, the modified Y-type molecular sieve contains 1 to 1.5% by weight of Na _2O , and the total acid amount of the modified Y-type molecular sieve by pyridine infrared spectroscopy and the modification. The ratio of the Y-type molecular sieve to the total acid amount by n-butyl pyridine infrared spectroscopy is 1.05 to 1.12, and the total acid content of the modified Y-type molecular sieve by pyridine infrared spectroscopy is 0.3 to 1.12. The modified Y-type molecular sieve according to claim 2, which is 0.8 mmol / g. The modified Y-type molecular sieve has a specific surface area of 500 to 900 m ² / g, a pore volume of 0.28 to 0.7 ml / g, a relative crystallinity of 50% to 130%, a lattice constant of 2.425 to 2.45 nm, and SiO. ₂ / Al ₂ O ₃ molar ratio (6 to 80): 1, and the relative crystallization degree is NaY type molecular sieve raw powder (Na ₂ O content 10% by weight, SiO ₂ / Al ₂ O ₃ molar ratio) . The modified Y-type molecular sieve according to any one of claims 1 to 3 , which is the crystallinity of 5.0) as a standard sample . The modified Y-type molecular sieve has a specific surface area of 550 to 850 m ² / g, a pore volume of 0.3 to 0.65 ml / g, a relative crystallization degree of 60% to 110%, a lattice constant of 2.428 to 2.448 nm, and a SiO. The modified Y-type molecular sieve according to claim 4, which has a ₂ / Al _{2O 3} molar ratio (8 to 60): 1. The modified Y-type molecular sieve has a specific surface area of 600 to 750 m ² / g, a pore volume of 0.35 to 0.6 ml / g, a relative crystallinity of 70% to 100%, a lattice constant of 2.43 to 2.445 nm, and SiO. The modified Y-type molecular sieve according to claim 5, which has a ₂ / Al _{2O 3} molar ratio (10 to 50): 1. The method for producing a modified Y-type molecular sieve according to any one of claims 1 to 6.
Step (1) of pretreating NaY molecular sieves to obtain desodium-dealuminum-dealuminum Y-type molecular sieves,
In the step (2) of obtaining sodium-containing Y-type molecular sieves by exchanging sodium ions with the desodium-dealuminum Y-type molecular sieves.
A production method comprising the step (3) of immersing the sodium-containing Y-type molecular sieve with a large molecular ammonium salt solution, and then drying and roasting the sodium-containing Y-type molecular sieve to obtain a modified Y-type molecular sieve. In step (2), the sodium ion exchange process involves using the desodium-dealuminum Y-type molecular sieve with a NaNO ₃ aqueous solution having a mass percentage of NaNO ₃ of 0.1 to 3% by weight at 40 to 80 ° C. The method according to claim 7, wherein the reaction is carried out at a constant temperature for 1 to 4 hours. In step (3), the dipping process is to immerse the sodium-containing Y-type molecular sieve in the large-molecular-weight ammonium salt solution for 2 to 6 hours at 40 to 80 ° C., and the large-molecular-weight ammonium salt is benzyl. The method according to claim 7 or 8, which is a quaternary ammonium salt. The method according to claim 9, wherein the benzyl quaternary ammonium salt is at least one of benzyltripropylammonium bromide, benzyltributylammonium bromide, benzyltripropylammonium chloride, and benzyltributylammonium chloride. In step (3), the drying process is to dry at 100 to 150 ° C. for 1 to 4 hours, and the roasting process is to roast at 500 to 700 ° C. for 2 to 6 hours. The method described in. In step (1), the pretreatment process involves one or more combinations of ammonium ion exchange, hydrothermal dealuminum, aluminum salt dealuminum, fluorosilicate dealuminum, and acid dealuminum. The method according to any one of claims 7 to 11 , including. In step (1), the pretreatment process is
The step (a) of obtaining a desodium Y-type molecular sieve by subjecting a NaY molecular sieve and an aqueous ammonium salt solution to an ammonium ion exchange reaction,
The step (b) of obtaining the product of hydrothermally dealuminum by hydrothermally dealuminating the desodium Y-type molecular sieve.
The step (c) of chemically dealuminating the hydrothermally dealuminum product to obtain the desodium-dealuminum-dealuminum Y-type molecular sieve is included.
The method according to claim 12 , wherein the chemical dealuminum is dealuminum with an aluminum salt, dealuminum with a fluorosilicate, or dealuminum with an acid. In step (a), the ammonium salt ion exchange reaction process involves exchanging the NaY molecular sieve and the ammonium salt aqueous solution at 60 to 120 ° C. 1 to 4 times for 1 to 3 hours, and the Na ₂ O content is 3 weight by weight. Is to obtain the above-mentioned desodium Y-type molecular sieve of less than%.
The NaY molecular sieve has a SiO ₂ / Al ₂ O ₃ molar ratio (3 to 6): 1, a Na ₂ O content of 6 to 12% by weight, and the ammonium salts are ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate, and oxalate. The method according to claim 13 , wherein the method is one or more selected from ammonium acid, and the molar concentration of the ammonium salt aqueous solution is 0.3 to 6 mol / L. In step (b), the hydrothermal dealuminum process involves contacting the desodium Y-type molecular sieve with steam under the conditions of a temperature of 520 to 700 ° C. and a pressure of 0.01 to 0.5 MPa for 1 to 6 hours. The method according to claim 13 . In step (c), the chemical dealumination process takes the hydrothermal dealumination product from 0.5 to 0.5 to 120 ° C. with an aluminum salt solution, an ammonium fluorosilicate solution or a nitric acid solution. The method according to claim 13 , wherein the reaction is carried out at a constant temperature for 3 hours. It is a method for manufacturing a hydrogenation decomposition catalyst.
The modified Y-type molecular sieve, amorphous silica-alumina and / or aluminum oxide according to any one of claims 1 to 6 is weighted at (5 to 90) :( 0 to 50) :( 0.6 to 80). In step (I), the carrier mixed material is mixed by a ratio to form a slurry, and then an aqueous nitrate solution having a mass percentage of 3 to 30% by weight is added to the carrier mixed material to form a slurry, and extrusion molding is performed.
The extrusion product obtained in step (I) is dried at 80 to 120 ° C. for 1 to 5 hours and then roasted at 400 to 500 ° C. for 1 to 5 hours to obtain a silica-alumina carrier in step (II).
The silica-alumina carrier is saturated and immersed in a solution containing an active metal hydride, and the obtained product is dried and roasted to obtain a hydrocracking catalyst (III). Method for producing a catalyst. The content of the silica -alumina carrier is 55 to 85% by weight based on the total amount of the hydride decomposition catalyst, and the content of the hydride-active metal is contained. The amount is 15 to 45% by weight of the metal oxide, and the silica-alumina carrier contains the modified Y-type molecular sieve according to any one of claims 1 to 6, and the modification in the silica-alumina carrier. The production method according to claim 17, wherein the content of the Y-type molecular sieve is 5 to 90% by weight. The hydrogenated active metal is a metal selected from Group VIII and / or Group VI.
The production method according to claim 18, wherein the Group VIII metal is Ni and / or Co, and the Group VI metal is W and / or Mo. 19. Production method. It is a method of hydrocracking and decomposing hydrocarbon oil.
A step of producing a hydrocracking catalyst by performing the production method according to any one of claims 18 to 20, and
Including the step of bringing the hydrocarbon oil into contact with the hydrocracking catalyst produced in the above step to cause a hydrocracking reaction in the presence of hydrogen gas, the reaction temperature is 340 to 420 ° C., and the reaction pressure is 8 to 20 MPa. Yes, the volumetric space velocity at the time of supply of the hydrocarbon oil is 0.1 to 2h ^-1 , and the volume ratio of hydrogen gas to the hydrocarbon oil is (200 to 2000): 1. Hydrodecomposition method.