WO2019104543A1 - 改性y型分子筛及制备方法、加氢裂化催化剂及制备方法和烃油加氢裂化的方法 - Google Patents

改性y型分子筛及制备方法、加氢裂化催化剂及制备方法和烃油加氢裂化的方法 Download PDF

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WO2019104543A1
WO2019104543A1 PCT/CN2017/113629 CN2017113629W WO2019104543A1 WO 2019104543 A1 WO2019104543 A1 WO 2019104543A1 CN 2017113629 W CN2017113629 W CN 2017113629W WO 2019104543 A1 WO2019104543 A1 WO 2019104543A1
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Prior art keywords
molecular sieve
type molecular
modified
ammonium
hydrocracking
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PCT/CN2017/113629
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English (en)
French (fr)
Inventor
柳伟
关明华
杜艳泽
王凤来
秦波
高杭
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中国石油化工股份有限公司
中国石油化工股份有限公司大连石油化工研究院
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Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司大连石油化工研究院 filed Critical 中国石油化工股份有限公司
Priority to RU2020119436A priority Critical patent/RU2744001C1/ru
Priority to SG11202005027XA priority patent/SG11202005027XA/en
Priority to JP2020529328A priority patent/JP7169354B2/ja
Priority to US16/768,070 priority patent/US11179705B2/en
Priority to KR1020207018583A priority patent/KR102428229B1/ko
Priority to EP17933464.4A priority patent/EP3718629A4/en
Priority to CA3083830A priority patent/CA3083830C/en
Priority to PCT/CN2017/113629 priority patent/WO2019104543A1/zh
Publication of WO2019104543A1 publication Critical patent/WO2019104543A1/zh

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    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
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    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
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    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
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Definitions

  • the invention relates to the field of hydrocracking, in particular to a modified Y-type molecular sieve and a preparation method thereof, a hydrocracking catalyst and a preparation method thereof, and a method for hydrocracking a hydrocarbon oil.
  • Hydrocracking technology has the characteristics of strong adaptability of raw materials, high flexibility of product scheme, high selectivity of product, good product quality and high added value. It can directly convert various heavy and inferior raw materials into clean fuel oil and high-quality chemical raw materials. It has become one of the most important deep processing technologies for heavy oil in the modern refining and petrochemical industry, and has been widely used at home and abroad. Although the processing capacity of existing hydrocracking units in China has exceeded 50.0 Mt/a, the import volume of high-sulfur crude oil has increased significantly due to the deterioration of domestic crude oil quality, and the environmental protection requirements for the refining process itself and petroleum products have become stricter. The demand for fuel and chemical raw materials is increasing. Therefore, the hydrocracking technology will also be more widely used, and also put forward higher requirements for the hydrocracking technology itself.
  • the core of the hydrocracking technology is a hydrocracking catalyst.
  • the hydrocracking catalyst is a bifunctional catalyst with cracking and hydrogenation activity.
  • the cracking function is provided by an acidic carrier material such as molecular sieve, and the hydrogenation function is carried out by the element period supported on the catalyst.
  • the Group VI and Group VIII active metals are provided in the table to meet different reaction requirements through the modulation of the cracking and hydrogenation bifunctional sites.
  • the cracking component of the hydrocracking catalyst the molecular sieve plays a decisive role in the performance of the catalyst.
  • the types of molecular sieves used in hydrocracking catalysts mainly include Y type and ⁇ type.
  • Y-type molecular sieve has a three-dimensional super-cage and tetrahedral 12-membered ring macroporous and open pore structure, which has good ring opening selectivity for macromolecular cyclic hydrocarbons, and its heavy naphtha product has high aromatic potential and hydrogenation.
  • the tail oil has a low BMCI value and is currently the most widely used in hydrocracking catalysts.
  • Y-type molecular sieves are used as cracking components of hydrocracking catalysts. They are usually modified before use to improve the hydrothermal and chemical stability of the molecular sieves. At the same time, the acid properties and pore structure are improved to obtain suitable hydrocracking reactions. The acidic environment and the ideal pore structure.
  • the modification technology of the Y-type molecular sieve includes a hydrothermal modification method, a chemical dealuminization modification method such as an inorganic acid, an organic acid, a salt and a complexing agent, and a modification method such as a combination of hydrothermal and chemical dealuminization.
  • the modified Y-type molecular sieve obtained by the current modification method has an acidic center distributed in different pores of the molecular sieve (micropores and secondary pores), and on the one hand, the acid center in the micropores is less usable, on the other hand, Easy to cause excessive The secondary cracking reaction occurs, and the reaction selectivity and product liquid recovery decrease.
  • US4503023 discloses a molecular sieve modification method, which uses NaY zeolite to carry out liquid phase dealuminization and silicon supplementation with ammonium fluorosilicate, and the molecular sieve has high crystallinity and high silicon to aluminum ratio, and has certain resistance to organic nitrogen poisoning, but Because the structure is too complete, there are almost no secondary pores, and the acid center is mainly at the micropores, and the macromolecular reactants in the inferior raw materials are less accessible.
  • CN1178193A discloses a modified Y zeolite having a pore volume of more than 1.7 ⁇ 10 -10 m and a pore volume of 45% or more and a surface area of 750-900 m 2 /g; a unit cell parameter of 24.23 ⁇ 10 -10 m to 25.45 ⁇ 10 -10 Rice, crystallinity 95-110%, SiO 2 /Al 2 O 3 ratio 7-20.
  • the method comprises the following steps: using NaY zeolite as a raw material, first performing ammonium exchange to a Na 2 O content of less than 2 m%, and then steaming, characterized in that the zeolite after steam treatment is further buffered with NH + , H + and other metal cations. Solution treatment.
  • the Y molecular sieve is modified by hydrothermal desulfurization combined with buffer solution treatment.
  • the obtained molecular sieve has rich secondary pores and good diffusion performance.
  • the modified Y molecular sieve obtained by this modification still has a large amount.
  • the molecular sieve In the acidic position in the microporous structure, the molecular sieve has a large acidity dispersion degree and a poor reaction selectivity.
  • CN1178721A discloses a high silicon to aluminum ratio high crystallinity Y type molecular sieve characterized by a cell constant of 2.425-2.436 nm, a SiO 2 /Al 2 O 3 molar ratio of 15-200, and a specific surface of 700-780 m 2 /g, The relative crystallinity is 100-125%.
  • the preparation method comprises the following steps: removing the aluminum from the NH 4 NaY molecular sieve material by using ammonium hexafluorosilicate, then performing hydrothermal treatment under saturated steam, and finally treating with the aluminum salt solution.
  • the obtained modified Y-type molecular sieve has a lower secondary pore content, and at the same time, a large number of acidic centers are distributed in the micropores, resulting in an excessive cracking reaction in the reaction process, and the liquid yield is lowered.
  • US4036739 discloses a hydrocracking process in which a modification method of a Y-type molecular sieve is disclosed, which is treated at a temperature of 315-899 ° C and contacted with at least 0.5 psi of water vapor for a period of time to obtain a modified Y molecular sieve crystal.
  • the cell constant is 2.440-2.464 nm; the treated Y molecular sieve is subjected to ammonium exchange to obtain an intermediate having a sodium content of less than 1%; and then, a modified Y molecular sieve having a unit cell constant of less than 2.440 nm is obtained, however, since the treatment process is relatively The harshness of the modified Y molecular sieve obtained is severely deteriorated, and the crystallinity is low, which affects the performance of the use.
  • the Y-type molecular sieve provided by the prior art has a defect of excessive cracking in the hydrocracking reaction, and the reaction selectivity is poor.
  • the object of the present invention is to overcome the problems of excessive cracking and poor reaction selectivity of the hydrocracking reaction in the prior art, and provide the modified Y type molecular sieve and the preparation method thereof, the hydrocracking catalyst and the preparation method thereof, and the hydrocarbon oil hydrogenation.
  • the method of cracking The acidic center of the modified Y-type molecular sieve is concentrated in the large pore channel, and the prepared hydrocracking reminder is obtained.
  • the chemical agent used in the hydrocracking reaction of the wax oil can improve the selectivity of the catalytic reaction process, reduce the occurrence of secondary cracking reaction, improve the quality of the hydrocracking tail oil, and improve the yield of the reaction liquid product.
  • the inventors of the present invention found in the research that in the modified Y-type molecular sieve prepared by the prior art, a large number of acidic centers exist in the microporous structure, and the total amount of pyridine infrared acid/n-butylpyridine infrared acid is generally greater than 1.5. .
  • the presence of a large amount of the acidic center in the micropores causes an excessive cracking reaction to occur, and the reaction selectivity is deteriorated.
  • the inventors have proposed the present invention to limit the distribution of the acid center on the modified Y-type molecular sieve and to control the number of acidic centers in the micropores to solve the problem of excessive cracking of the hydrocracking reaction and poor reaction selectivity.
  • a first aspect of the present invention provides a modified Y-type molecular sieve, wherein the modified Y-type molecular sieve contains, based on the total amount of the modified Y-type molecular sieve 0.5-2% by weight of Na 2 O; the ratio of the total amount of pyridine infrared total acid of the modified Y type molecular sieve to the amount of n-butylpyridine infrared total acid of the modified Y type molecular sieve is 1-1.2; The pyridine infrared total acid amount of the Y-type molecular sieve is 0.1-1.2 mmol/g.
  • the modified Y-type molecular sieve has a specific surface area of 500-900 m 2 /g; the modified Y-type molecular sieve has a pore volume of 0.28-0.7 ml/g; and the relative crystallinity of the modified Y-type molecular sieve It is 50%-130%; the unit cell parameter of the modified Y type molecular sieve is 2.425-2.450; and the modified Y type molecular sieve has a silicon to aluminum molar ratio of (6-80):1.
  • a second aspect of the invention provides a method of preparing a modified Y-type molecular sieve of the invention, comprising the steps of:
  • the process of pretreatment in step (1) comprises a combination of one or more of ammonium ion exchange, hydrothermal dealumination, aluminum salt dealumination, fluorosilicate dealumination and acid dealumination.
  • the process of preprocessing in step (1) comprises:
  • a third aspect of the invention provides a method of preparing a hydrocracking catalyst, the method comprising:
  • step (II) drying the extruded product obtained in the step (I) at 80-120 ° C for 1-5 h, and then calcining at 400-500 ° C for 1-5 h to obtain a silica-alumina support;
  • a fourth aspect of the present invention provides a hydrocracking catalyst obtained by the method of the present invention, the hydrocracking catalyst comprising a silica-alumina support and a hydrogenation active metal, based on the total amount of the hydrocracking catalyst,
  • the content of the silicon-aluminum support is 55-85% by weight, and the content of the hydrogenation active metal is 15-45% by weight based on the metal oxide,
  • the silica-alumina carrier contains the modified Y-type molecular sieve of the invention,
  • the modified Y-type molecular sieve is contained in the silicon-aluminum carrier in an amount of from 5 to 90% by weight.
  • a method for hydrocracking a hydrocarbon oil comprising: contacting a hydrocarbon oil with a hydrocracking catalyst of the present invention in a hydrocracking reaction in the presence of hydrogen, wherein the reaction temperature
  • the reaction pressure is 8-20 MPa at 340-420 ° C
  • the volume of the hydrocarbon oil feed is 0.1-2 h -1
  • the volume ratio of hydrogen to the hydrocarbon oil is (200-2000):1.
  • the present invention provides a modified Y-type molecular sieve in which an acid center is concentrated in a large pore (ie, a secondary pore).
  • the acidic center of the micropores of the modified Y-type molecular sieve is basically occupied by sodium ions, leaving only the acidic center in the large pores, which can reduce the occurrence of secondary cracking reaction of hydrocarbon molecules into the micropores.
  • basic organic compounds of different molecular sizes such as pyridine and n-butylpyridine
  • the infrared acid content of the modified Y-type molecular sieve is determined. When the acid content of the two is equivalent, the acidic center of the modified Y-type molecular sieve is concentrated. Punch the road.
  • the invention provides a method for preparing a modified Y-type molecular sieve, which first performs sodium ion exchange on the acid center of the modified Y-type molecular sieve, so that the acid center in various pores of the Y-type molecular sieve is occupied by sodium ions; Then, the benzyl quaternary ammonium salt with a larger molecular size is used for ammonium ion exchange treatment. Since the benzyl quaternary ammonium salt has a larger molecular size, the sodium ions distributed in the macroporous channel are selectively exchanged to a benzyl group.
  • the benzyl quaternary ammonium cation can remove the acid center in the perforation of the Y-type molecular sieve, and the acid center in the micropore is still occupied by the sodium ion.
  • the acidity is manifested, so that the molecular sieve provided by the invention has the characteristic that the acidic central sites are concentrated in the large pores, and the characteristics can be identified by infrared acid determination using pyridine and n-butylpyridine having different molecular sizes to obtain the modification with the above characteristics.
  • Y type molecular sieve is the characteristic that the acidic central sites are concentrated in the large pores, and the characteristics can be identified by infrared acid determination using pyridine and n-butylpyridine having different molecular sizes to obtain the modification with the above characteristics.
  • the hydrocracking catalyst prepared by using the modified Y-type molecular sieve of the invention is used for the hydrocracking reaction process of the wax oil, which is beneficial to improving the reaction selectivity of the molecular cyclic hydrocarbons in the large wax oil and reducing the secondary cracking reaction. Occur, Improve the quality of hydrocracking tail oil and increase the yield of reaction liquid products.
  • a first aspect of the invention provides a modified Y-type molecular sieve, characterized in that the modified Y-type molecular sieve contains 0.5-2% by weight of Na 2 O based on the total amount of the modified Y-type molecular sieve.
  • the ratio of the total amount of pyridine infrared total acid of the modified Y-type molecular sieve to the total amount of n-butylpyridine infrared total acid of the modified Y-type molecular sieve is 1-1.2; the pyridine infrared total acid of the modified Y-type molecular sieve The amount is 0.1-1.2 mmol/g.
  • the modified Y-type molecular sieve refers to a molecular sieve obtained by subjecting the Y-type molecular sieve raw powder to chemical treatment (such as the method provided later in the present invention).
  • the modified Y-type molecular sieve provided by the invention has the acidic center mainly distributed in the large pores, and a small amount or even no acid center is distributed in the micropores, which can reduce the secondary cracking reaction of the hydrocarbon oil molecules into the micropores at the acidic center. .
  • the characteristic of the acidic center distribution in the above-mentioned pores of the modified Y-type molecular sieve provided by the present invention can be embodied by the results of acid measurement of the modified Y-type molecular sieve by using pyridine and n-butylpyridine as two kinds of probe molecules, respectively.
  • the n-butylpyridine has a molecular diameter of about 0.8 nm and can enter only the large pores of the modified Y-type molecular sieve provided by the present invention, reflecting the total amount of acidic centers in the large pores.
  • the pyridine has a molecular diameter of about 0.6 nm and can enter the micropores and macropores of the modified Y-type molecular sieve, reflecting the total amount of acidic centers in all the pores of the modified Y-type molecular sieve.
  • the specific test process can be: adsorption of infrared spectroscopy by pyridine and n-butylpyridine, using Nicolet 6700 Fourier infrared spectrometer of NICOLET Company of the United States,
  • the total acid amount is calculated by the pyridine weight adsorption method, as follows:
  • Infra-butyl pyridine total acid amount C' (unit: mmol / g): according to the above formula, 79.1 was replaced by 136.1;
  • 79.1 and 136.1 are the molar masses of pyridine and n-butylpyridine, respectively, and the unit is g/mol.
  • the invention adjusts the concentrated distribution of the acidic central position in the micropores and large pores of the Y-type molecular sieve, thereby realizing the control of the reaction of the hydrocarbon oil molecules on the molecular sieve.
  • the distribution of the acid center position is reflected by the total amount of infrared acidity of pyridine and n-butylpyridine.
  • the ratio of the total amount of pyridine infrared total acid to the amount of n-butylpyridine in total infrared acid will be greater than 1.2. This makes it possible to distinguish whether or not the acid center in the micropores of the Y-type molecular sieve is controlled.
  • the modified Y-type molecular sieve uses n-butylpyridine, pyridine, respectively, the total amount of acid measured is slightly smaller than the total amount of acid of n-butylpyridine, that is, the above-mentioned pyridine infrared total acid which defines the modified Y-type molecular sieve.
  • the ratio of the amount to the total amount of n-butylpyridine in the modified Y-type molecular sieve is 1-1.2, it indicates that the acidic center contained in the modified Y-type molecular sieve is mainly concentrated in the large pore.
  • the modified Y-type molecular sieve contains 0.8-1.8% by weight of Na 2 O based on the total amount of the modified Y-type molecular sieve; the total infrared pyridine of the modified Y-type molecular sieve
  • the ratio of the amount of acid to the amount of the total amount of n-butylpyridine in the modified Y-type molecular sieve is 1.02-1.15.
  • the modified Y-type molecular sieve contains 1-1.5% by weight of Na 2 O based on the total amount of the modified Y-type molecular sieve; the total amount of pyridine infrared total acid of the modified Y-type molecular sieve The ratio of the total amount of n-butylpyridine in the modified Y-type molecular sieve to the total amount of infrared acid is 1.05-1.12.
  • the modified Y-type molecular sieve has a total amount of pyridine infrared total acid of 0.2 to 1 mmol/g.
  • the modified Y-type molecular sieve has a total amount of pyridine infrared total acid of 0.3 to 0.8 mmol/g.
  • the modified Y-type molecular sieve has other characteristics, and is also beneficial for use in the hydrocracking reaction process of the wax oil, improving the quality of the hydrocracking tail oil, and improving the yield of the reaction liquid product.
  • the modified Y-type molecular sieve has a specific surface area of from 500 to 900 m 2 /g; preferably from 550 to 850 m 2 /g; more preferably from 600 to 750 m 2 /g.
  • the modified Y-type molecular sieve has a pore volume of from 0.28 to 0.7 ml/g; preferably from 0.3 to 0.65 ml/g; more preferably from 0.35 to 0.6 ml/g.
  • the modified Y-type molecular sieve has a relative crystallinity of 50% to 130%; 60% to 110%; more preferably 70% to 100%.
  • the modified Y-type molecular sieve has a unit cell parameter of 2.425-2.45 nm; preferably 2.428-2.448 nm; more preferably 2.43-2.445 nm.
  • the modified Y-type molecular sieve has a silica-alumina molar ratio of (6-80):1; preferably (8-60):1; more preferably (10-50):1.
  • a second aspect of the invention provides a method of preparing a modified Y-type molecular sieve of the invention, comprising the steps of:
  • step (1) is used to form large pores in the NaY molecular sieve, which facilitates subsequent modification of the large pores and the small pores, respectively.
  • the pretreatment process in the step (1) comprises a combination of one or more of ammonium ion exchange, hydrothermal dealumination, aluminum salt dealumination, fluorosilicate dealumination and acid dealumination.
  • the pretreatment of the NaY molecular sieve may be one or several steps of subjecting the NaY molecular sieve to ammonium ion exchange, hydrothermal dealumination, aluminum salt dealumination, fluorosilicate dealumination and acid dealumination,
  • the order between the steps may be not limited as long as the desodium-de-aluminized Y-type molecular sieve can be provided, for example, the Na 2 O content of the de-sodium-de-aluminized Y-type molecular sieve is less than 3% by weight, SiO 2 /Al 2 O
  • the molar ratio of 3 is (6-80): 1, and the unit cell constant is 2.425-2.450.
  • the NaY molecular sieve is desalted by ammonium ion exchange, and then the desalted product is dealuminated, and one or several of hydrothermal aluminizing, aluminum salt dealuminization, fluorosilicate dealumination and acid aluminizing can be selected. Combination of one.
  • the process of the preprocessing in the step (1) includes:
  • the chemical dealumination is aluminide dealuminization, fluorosilicate dealumination or acid dealumination.
  • step (a) is used to remove Na ions from the NaY molecular sieve so that the subsequent dealumination process proceeds smoothly.
  • the ammonium salt ion exchange reaction in the step (a) is carried out by exchanging the NaY molecular sieve with the ammonium salt aqueous solution at 60-120 ° C, preferably 60-90 ° C for 1-3 h, and the number of exchanges is 1- Four times, the desodium Y-type molecular sieve was obtained.
  • the desodarated Y-type molecular sieve has a Na 2 O content of less than 3% by weight.
  • the NaY molecular sieve has a SiO 2 /Al 2 O 3 molar ratio of (3-6):1 and a Na 2 O content of 6-12% by weight.
  • the ammonium salt is selected from one or more of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate and ammonium oxalate, and the molar concentration of the aqueous ammonium salt solution is from 0.3 to 6 mol/L, preferably from 1 to 3 mol. /L.
  • step (b) is used for the dealuminization of the desodium-type Y molecular sieve to form a large pore.
  • the hydrothermal dealuminization process in the step (b) is: contacting the desodium-type Y molecular sieve with water vapor at a temperature of 520-700 ° C and a pressure of 0.01-0.5 MPa. 6h.
  • the number of times of hydrothermal dealumination is 1-3 times.
  • step (c) is used for chemical dealumination of molecular sieves to form large pores.
  • the chemical dealuminization process in the step (c) is: the thermothermal dealuminization product is subjected to a constant temperature reaction with an aluminum salt solution, an ammonium fluorosilicate solution or a nitric acid solution at a temperature of 50-120 ° C. 0.5-3h.
  • the aluminum salt solution is an aqueous solution of at least one of aluminum chloride, aluminum sulfate, and aluminum nitrate.
  • the molar concentration of the aluminum salt solution, the ammonium fluorosilicate solution or the nitric acid solution is 0.05-2 mol/L.
  • the aluminum salt is dealuminated when the hydrothermally dealuminated product is subjected to the constant temperature reaction with the aluminum salt solution.
  • the fluorosilicate is dealuminated.
  • the acid is dealuminated when the hydrothermally dealuminated product is subjected to the constant temperature reaction with the nitric acid solution.
  • the step (2) is for neutralizing the acidic center vacated in the large and microporous channels of the desalted dealuminized Y-type molecular sieve with sodium ions.
  • the sodium ion exchange process in the step (2) is: the desalting and dealuminating Y type molecular sieve and the NaNO 3 aqueous solution are subjected to a constant temperature reaction at 40-80 ° C for 1-4 h; wherein the mass of NaNO 3 in the NaNO 3 aqueous solution The fraction is from 0.1 to 3% by weight.
  • the immersion treatment in the step (3) is carried out by using a macromolecular ammonium salt for exchanging sodium ions occupying the acidic center in the large pores of the Y-type molecular sieve, so that the acid center in the large pores is present.
  • the macromolecular ammonium salt cannot enter the microporous channel of the Y-type molecular sieve, and the sodium ion may still occupy the acidic center in the microporous channel.
  • the finally obtained modified Y-type molecular sieve of the present invention can provide an acidic center in a large pore channel, but there are few or even no acidic centers in the microporous channel, and when the hydrocracking reaction is applied, the secondary cracking reaction of the hydrocarbon oil is reduced.
  • the immersion treatment in the step (3) is carried out by immersing the sodium-containing Y-type molecular sieve in the macromolecular ammonium salt solution at 40-80 ° C for 2-6 h.
  • the macromolecular ammonium salt is a benzyl quaternary ammonium salt.
  • the benzyl quaternary ammonium salt is at least one of benzyl tripropyl ammonium bromide, benzyl tributyl ammonium bromide, benzyl tripropyl ammonium chloride, and benzyl tributyl ammonium chloride.
  • benzyl tripropyl ammonium bromide benzyl tributyl ammonium bromide
  • benzyl tripropyl ammonium chloride benzyl tributyl ammonium chloride.
  • the macromolecular ammonium salt solution has a molar concentration of the macromolecular ammonium salt solution of 0.2 to 2 mol/L, based on the concentration of the bromine or chlorine element.
  • the distribution of the acid center in the prepared modified Y-type molecular sieve can be measured by infrared absorption of pyridine and infrared adsorption of n-butylpyridine.
  • the specific methods and test results are as described above and will not be described again.
  • the drying process in the step (3) is carried out at 100-150 ° C for 1-4 h; the calcination process is carried out at 500-700 ° C for 2-6 h.
  • a third aspect of the invention provides a method for preparing a hydrocracking catalyst, the method comprising:
  • step (II) drying the extruded product obtained in the step (I) at 80-120 ° C for 1-5 h, and then calcining at 400-500 ° C for 1-5 h to obtain a silica-alumina support;
  • the solid content of the slurry is suitable for extrusion molding to obtain a strip-shaped extruded product.
  • the slurry has a solids content of from 30 to 60% by weight.
  • the amount of the solution containing the hydrogenation-active metal added to the step (III) is such that the obtained hydrocracking catalyst contains the hydrogenation-active metal in an amount of from 15 to 45% by weight based on the metal oxide.
  • the concentration of the hydrogenation-active metal in terms of metal oxide may be 20 to 70 mol/L.
  • the solution containing a hydrogenation-active metal may be a solution of a compound containing a metal element of Group VIII and/or Group VI.
  • it may be a solution of a compound containing Ni and/or Co, a solution of a compound containing W and/or Mo.
  • the solution containing a hydrogenation active metal may be a solution containing nickel nitrate, cobalt nitrate, ammonium metatungstate, ammonium molybdate, or molybdenum oxide.
  • the drying of the step (III) may be carried out at 90 to 150 ° C for 2 to 20 hours.
  • the calcination can be carried out at 400-600 ° C for 2-10 h. Converting the hydrogenation-active metal to an oxide form in the hydrocracking In the catalyst.
  • a fourth aspect of the present invention provides a hydrocracking catalyst obtained by the method of the present invention, the hydrocracking catalyst comprising a silica-alumina support and a hydrogenation active metal, based on the total amount of the hydrocracking catalyst,
  • the content of the silicon-aluminum support is 55-85% by weight, and the content of the hydrogenation active metal is 15-45% by weight based on the metal oxide,
  • the silica-alumina carrier contains the modified Y-type molecular sieve of the invention,
  • the modified Y-type molecular sieve is contained in the silicon-aluminum carrier in an amount of from 5 to 90% by weight.
  • the hydrogenation-active metal is selected from the group VIII and/or Group VI metals.
  • the Group VIII metal is Ni and/or Co and the Group VI metal is W and/or Mo.
  • 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, based on the total amount of the catalyst.
  • the hydrogenation active metal in the hydrocracking catalyst exists in an oxidized state, and may be combined with a sulfur-containing compound before the hydrocracking reaction. After the contact is converted into a sulfided state by the sulfurization reaction, it participates in the hydrocracking of the hydrocarbon oil.
  • the hydrocracking catalyst comprises the modified Y-type molecular sieve component provided by the invention, which can have better hydrocracking reaction selectivity, reduce secondary cracking reaction of hydrocarbon oil molecules, and hydrocracking reaction product.
  • the selectivity is better.
  • the reaction performance of the hydrocracking catalyst can be determined by a specific reaction performance evaluation experiment. The experiment can be carried out in a single-stage series one-pass process on a small micro-reverse device. The device has two reactors connected in series. In the process sequence, the first reactor is charged with a conventional refining catalyst, and the second reactor is charged with a hydrocracking catalyst.
  • the reaction can be separately evaluated by first loading the hydrocracking catalyst of the present invention in the second reactor and the hydrocracking catalyst prepared by filling the conventional Y-type molecular sieve, and comparing the same refined oil nitrogen content. And the conversion BMCI value of the cracked tail oil product obtained by the two reactions and the liquid product yield of the device. Among them, the lower the BMCI value of the tail oil product and the higher the product liquid level, the higher the reaction of the corresponding catalyst in the hydrocracking reaction, thereby promoting the reaction of the macromolecular cyclic hydrocarbon and reducing the occurrence of the secondary cracking reaction. The difference between the two reactions is only that the molecular sieves used in the catalyst are different. The above results can be attributed to the fact that the molecular sieves are more concentrated in the macropores.
  • a fifth aspect of the invention provides a method for hydrocracking a hydrocarbon oil, the method comprising: contacting a hydrocarbon oil with a hydrocracking catalyst of the invention in a hydrocracking reaction in the presence of hydrogen, wherein the reaction temperature is 340 At -420 ° C, the reaction pressure is 8-20 MPa, the volume of the hydrocarbon oil feed is 0.1-2 h -1 , and the volume ratio of hydrogen to the hydrocarbon oil is (200-2000): 1.
  • the hydrocarbon oil may be a petroleum-based vacuum wax oil raw material having a distillation range of from 300 to 600 ° C and a density of from 0.86 to 0.94 g/cm 3 .
  • the hydrogenation-active metal in the hydrocracking catalyst participates in the form of a sulfided state.
  • a catalyst containing a hydrogenation-active metal in a sulfided state is directly prepared, the catalyst is easily oxidized during transportation and storage, and vulcanization is still required before it is officially involved in the hydrocracking reaction. Therefore, in the art, it is generally selected to prepare a hydrogenation active metal having an oxidation state in a catalyst, and then the catalyst is subjected to a sulfurization reaction before the hydrocracking reaction of the hydrocarbon oil to obtain a hydrogenation active metal in a sulfide state of the catalyst, or in a hydrocarbon oil.
  • the sulfur-containing compound completes the vulcanization of the hydrogenation-active metal and achieves hydrocracking of the hydrocarbon oil during the contact of the hydrocarbon oil with the catalyst.
  • the hydrocracking catalyst of the present invention in the process of the hydrocracking reaction, is converted into a sulfided state in the presence of a sulfur-containing compound in a hydrocarbon oil and Achieve hydrocracking of hydrocarbon oils.
  • the amount of pyridine and n-butylpyridine in infrared acid was determined by pyridine and n-butylpyridine adsorption infrared spectroscopy, and was measured by the NICOLET 6700 Fourier infrared spectrometer method of the United States, and the process was as follows:
  • pyridine n-butylpyridine
  • the total acid amount was determined by a pyridine (n-butylpyridine) weight adsorption method.
  • the total acid amount is calculated by the pyridine weight adsorption method, as follows:
  • Infra-butyl pyridine total acid amount C' (unit: mmol / g): according to the above formula, 79.1 was replaced by 136.1;
  • 79.1 and 136.1 are the molar masses of pyridine and n-butylpyridine, respectively, and the unit is g/mol.
  • the surface area and pore volume are determined by a low temperature nitrogen adsorption method (BET method);
  • the Na 2 O content in the molecular sieve, the molecular sieve SiO 2 /Al 2 O 3 molar ratio is determined by a fluorescence method
  • the unit cell parameters and relative crystallinity of the molecular sieve were determined by XRD method.
  • the instrument was a Rigaku Dmax-2500 X-ray diffractometer using Cuk ⁇ radiation, graphite single crystal filtering, operating tube voltage of 35KV, tube current of 40mA, and scanning speed (2 ⁇ ) of 2°. /min, scanning range is 4 ° ⁇ 35 °.
  • the standard is the Y-type molecular sieve raw powder used in Example 1 of the present invention.
  • the tail oil yield is calculated from the product's real boiling point cutting data
  • T average boiling point expressed in absolute temperature K.
  • NaY type molecular sieve raw powder Na 2 O content is 10% by weight, SiO 2 /Al 2 O 3 molar ratio is 5.0
  • the ammonium ion exchange was carried out at 70 ° C for 3 h, the process was repeated 3 times; the de-sodium Y-type molecular sieve was obtained, the Na 2 O content was 2.5% by weight;
  • the sodium-containing Y-type molecular sieve is added to a concentration of 0.5 mol / L benzyl tributyl ammonium bromide aqueous solution, immersion treatment at 70 ° C for 3h;
  • step (5) The product obtained in the step (5) is dried at 120 ° C for 4 h and calcined at 550 ° C for 4 h to obtain a modified Y-type molecular sieve, numbered Y-1.
  • the sodium-containing Y-type molecular sieve was added to a concentration of 1.5 mol / L of benzyltributy ammonium chloride aqueous solution, immersion treatment at 70 ° C for 3h;
  • step (5) The product obtained in the step (5) is dried at 120 ° C for 4 h and calcined at 550 ° C for 4 h to obtain a modified Y-type molecular sieve, numbered Y-2.
  • the sodium-containing Y-type molecular sieve was added to a concentration of 1.2 mol / L of benzyl tripropyl ammonium bromide aqueous solution, immersion treatment at 80 ° C for 2h;
  • step (5) The product obtained in the step (5) is dried at 120 ° C for 4 h and calcined at 550 ° C for 4 h to obtain a modified Y-type molecular sieve, numbered Y-3.
  • step (3) The product obtained in the step (2) is contacted with water vapor at 0.2 MPa, 520 ° C for hydrothermal treatment for 2 h, and the process is repeated once;
  • step (3) The product obtained in the step (3) is stirred and mixed according to a liquid-solid ratio of 5:1 and 0.6 mol/L of an aluminum sulfate solution, and then subjected to a constant temperature reaction at 75 ° C for 2 hours to obtain a desodium-de-aluminized Y-type molecular sieve;
  • the sodium-containing Y-type molecular sieve is added to a concentration of 0.5 mol / L benzyl tributyl ammonium bromide aqueous solution, immersion treatment at 60 ° C for 5h;
  • step (6) The product obtained in the step (6) is dried at 120 ° C for 4 h and calcined at 550 ° C for 4 h to obtain a modified Y molecular sieve, numbered Y-4.
  • step (3) The product obtained in the step (3) is dried at 120 ° C for 4 h and calcined at 550 ° C for 4 h to obtain a modified Y-type molecular sieve, numbered B-1.
  • step (1) The product obtained in the step (1) is mixed with a 0.2 mol/L ammonium fluorosilicate treatment solution according to a liquid-solid ratio of 6:1, and then subjected to a constant temperature reaction at 80 ° C for 2 h;
  • step (3) The product obtained in the step (2) is contacted with water vapor at 0.2 MPa, 520 ° C for hydrothermal treatment for 2 h, and the process is repeated once;
  • the obtained molecular sieve obtained in the step (3) is stirred and mixed according to a liquid-solid ratio of 5:1 and a 0.6 mol/L aluminum sulfate solution, and then subjected to a constant temperature reaction at 75 ° C for 2 h;
  • step (4) The product obtained in the step (4) is dried at 120 ° C for 4 h and calcined at 550 ° C for 4 h to obtain a modified Y-type molecular sieve, numbered B-2.
  • the de-sodium Y-type molecular sieve is hydrothermally treated at 560 ° C, 0.1 MPa for 2 h;
  • step (3) The molecular sieve obtained in the step (2) is stirred and mixed with distilled water according to a liquid-solid ratio of 5:1, and then heated to 80 ° C, 400 ml of 0.5 mol / L aluminum sulfate solution is added during the stirring, and the reaction is kept at a constant temperature for 2 h;
  • step (4) taking the molecular sieve obtained in step (4) is placed in a closed container filled with butadiene atmosphere, the control pressure of 0.3MPa full contact for 20min, and then heated in an air atmosphere at 200 ° C for 15h;
  • the molecular sieve obtained in the step (5) is mixed with distilled water according to a liquid-solid ratio of 5:1, and then 100 ml of an ammonium fluorosilicate solution having a concentration of 0.6 mol/L is added, and treated at 80 ° C for 2 hours;
  • the modified Y-type molecular sieve prepared by using the embodiment of the technical solution provided by the present invention has a ratio of the total amount of pyridine infrared acid to the amount of n-butylpyridine infrared total acid of 1-1.2, preferably 1.02-1.15, more preferably 1.05-1.12, particularly preferably 1.03-1.09.
  • the ratio of the total amount of pyridine infrared total acid to the n-butylpyridine infrared total acid amount of the modified Y-type molecular sieve obtained in the comparative example was more than 1.2, which was 1.4-1.7.
  • the hydrocracking catalyst was prepared by using the modified Y molecular sieve prepared in Examples 1-4 and Comparative Examples 1-3, and the catalyst composition was as shown in Table 2:
  • the obtained catalysts are correspondingly numbered: the catalysts corresponding to the modified Y-type molecular sieves Y-1 to Y-4 of Examples 1-4 are C-1 to C-4; and the modified Y-type molecular sieves B corresponding to Comparative Examples 1-3
  • the catalyst of -1 to B-3 is BC-1 to BC-3. See Table 2.
  • Catalysts C-1 to C-4 and BC-1 to BC-3 were evaluated on a small micro-reverse device (100 ml small evaluation device of xytel, USA).
  • the evaluation device adopts a single-stage serial one-pass process flow, first reactor The conventional refining catalyst was charged, and the second reactor was separately charged with the hydrocracking catalysts in Table 2.
  • the properties of the reaction raw materials were listed in Table 3, and the evaluation results are shown in Tables 4 to 5.
  • Raw material oil Raw material oil Density, g/cm 3 0.9024 Distillation range, °C 321 ⁇ 528 C, m% 86.68 H,m% 12.30 S, m% 1.54 N,% 1138 BMCI value 40.3
  • the hydrocracking catalysts C-1 to C-4 prepared by using the modified Y-type molecular sieve provided by the present invention in Examples 1-4 have an optimized acid center distribution on the molecular sieve and reduce micropores.
  • the amount of the inner acid center, when the hydrocracking reaction is carried out, the BMCI value of the obtained hydrocracking tail oil product is significantly lower than that of the modified Y type molecular sieve (the total amount of pyridine infrared acid and n-butylpyridine) used in Comparative Example 1-3.
  • the ratio of the total amount of infrared acid is greater than 1.2) of the obtained hydrocracking catalyst, and the C 5 + liquid is larger than the reaction result of the catalyst of the comparative example.
  • Comparative Example 3 a prior art modified Y-type molecular sieve was provided in which a silica-alumina ratio which changed the bulk phase and surface of the Y-type molecular sieve particles was employed. Although the modification method changes the local silica-alumina ratio of the molecular sieve, the effect will be affected.
  • the amount of acid in the sub-screen can not change the distribution of the acid center in the macropores and micropores on the Y-type molecular sieve, still revealing the acid center position in the micropores, the amount of pyridine acid and the amount of n-butylpyridine acid
  • the ratio of more than 1.2 can not reduce the possibility of secondary cracking reaction of hydrocarbon molecules entering the microporous channel at the acid center.
  • the hydrocracking can not improve the quality of the hydrocracking tail oil and improve the yield of the reaction liquid product.

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Abstract

一种改性Y型分子筛及其制备方法、加氢裂化催化剂及其制备方法和烃油加氢裂化的方法。以改性Y型分子筛的总量为基准，改性Y型分子筛含有0.5-2重量％的Na 2O，改性Y型分子筛的吡啶红外总酸量与改性Y型分子筛的正丁基吡啶红外总酸量的比值为1-1.2，改性Y型分子筛的吡啶红外总酸量为0.1～1.2mmol/g。改性Y型分子筛的分子筛酸性中心位集中分布于大孔道内，将该分子筛用于蜡油加氢裂化反应过程，有利于提高蜡油中大分子环状烃类物质的反应选择性，减少二次裂化反应发生，改善加氢裂化尾油质量，提高反应液体产品收率。

Description

改性Y型分子筛及制备方法、加氢裂化催化剂及制备方法和烃油加氢裂化的方法 技术领域
本发明涉及一种加氢裂化领域，具体地，涉及改性Y型分子筛及制备方法、加氢裂化催化剂及制备方法和烃油加氢裂化的方法。
背景技术
加氢裂化技术具有原料适应性强、产品方案灵活性大、目的产品选择性高、产品质量好、附加值高等特点，可将各种重质、劣质原料直接转化清洁燃油和优质的化工原料，已成为现代炼油和石油化学工业最重要的重油深度加工工艺之一，在国内外获得日益广泛的应用。虽然我国现有加氢裂化装置加工能力已超过50.0Mt/a，但由于国内原油质量逐年变差，高硫原油进口量大幅增加，环保对炼油工艺本身及石油产品质量要求日趋严格，市场对清洁燃油和化工原料需求量不断增加。因此，加氢裂化技术还将得到更为广泛的应用，同时也对加氢裂化技术本身提出了更高的要求。
加氢裂化技术的核心是加氢裂化催化剂，加氢裂化催化剂是具有裂化和加氢活性的双功能催化剂，裂化功能由分子筛等酸性载体材料提供，加氢功能则由负载于催化剂上的元素周期表中第Ⅵ族和第Ⅷ族活性金属提供，通过裂化和加氢双功能位的调变来满足不同的反应需求。分子筛作为加氢裂化催化剂裂化组分，其性能对催化剂的反应性能起着决定性的作用。目前，加氢裂化催化剂所用分子筛类型主要有Y型和β型等。Y型分子筛具有三维超笼和四面体走向的12元环大孔、开放的孔道结构，对大分子环状烃具有很好的开环选择性，其重石脑油产品芳潜含量高，加氢尾油的BMCI值低，目前在加氢裂化催化剂中应用最为广泛。
Y型分子筛作为加氢裂化催化剂的裂化组分，其使用前通常需要进行改性处理，提高分子筛的水热及化学稳定性，同时，改善其酸性质及孔结构，以获得适合加氢裂化反应的酸性环境和理想的孔道结构。通常Y型分子筛的改性技术包括水热改性法，无机酸、有机酸、盐和络合剂等化学脱铝改性法，以及水热与化学脱铝相结合等改性方法。但是目前改性方法获得的改性Y型分子筛，酸性中心在分子筛不同孔道内均有分布(微孔和二次孔)，一方面处于微孔中的酸性中心可利用性较差，另一方面容易引起过度的 二次裂化反应发生，反应选择性及产品液收下降。
US4503023公开了一种分子筛改性方法，采用NaY沸石用氟硅酸铵进行液相的脱铝补硅方式，制备分子筛结晶度高，硅铝比高，具有一定的耐有机氮中毒的能力，但由于其结构过于完整，几乎没有二次孔，酸性中心主要处于微孔处，劣质原料中大分子反应物可接近性较差。
CN1178193A公开了一种改性Y沸石，孔径大于1.7×10-10米的孔体积占45％以上，表面积750-900m2/g；晶胞参数在24.23×10-10米-25.45×10-10米，结晶度95-110％，SiO2/Al2O3比为7-20。其方法为以NaY沸石为原料，首先进行铵交换，至Na2O含量小于2m％，然后水蒸气处理，特征在于水蒸气处理后的沸石再用含NH+、H+及其它金属阳离子的缓冲溶液处理。采用水热脱硫结合缓冲溶液处理的方式对Y分子筛进行改性处理，获得的分子筛具有较为丰富二次孔，扩散性能较好，但是，此种改性方式获得的改性Y型分子筛仍然有大量处于微孔结构中的酸性位，分子筛酸性位分散度较大，反应选择性较差。
CN1178721A公开了一种高硅铝比高结晶度Y型分子筛，其特征在于晶胞常数2.425-2.436nm，SiO2/Al2O3摩尔比为15-200，比表面700-780m2/g，相对结晶度100-125％。其制备方法为：NH4NaY分子筛原料用六氟硅酸铵脱铝补硅，然后进行饱和水蒸汽下水热处理，最后再用铝盐溶液处理。但是，所得改性Y型分子筛的二次孔含量较低，同时，在微孔中分布了大量酸性中心，导致反应过程过度裂化反应发生，液体收率下降。
US4036739公开了一种加氢裂化方法，其中公开了一种Y型分子筛的改性方法，在315-899℃的温度下，并与至少0.5psi水蒸气接触处理一段时间，所得改性Y分子筛晶胞常数为2.440-2.464nm；将处理后的Y分子筛进行铵交换，得到钠含量小于1％的中间物；然后，得到晶胞常数小于2.440nm的改性Y分子筛，但是，由于该处理过程较为苛刻，使得获得的改性Y分子筛结晶度破坏严重，结晶度较低，影响了其使用性能。
现有技术提供的Y型分子筛用于加氢裂化反应存在过度裂化的缺陷，且反应选择性较差。
发明内容
本发明的目的是为了克服现有技术中加氢裂化反应存在过度裂化和反应选择性较差的问题，提供了改性Y型分子筛及制备方法、加氢裂化催化剂及制备方法和烃油加氢裂化的方法。该改性Y型分子筛的酸性中心位集中分布于大孔道内，制得的加氢裂化催 化剂用于蜡油加氢裂化反应可以提高催化反应过程的选择性，减少二次裂化反应发生，改善加氢裂化尾油质量，提高反应液体产品收率。
本发明的发明人在研究中发现，现有技术制备的改性Y型分子筛中，大量的酸性中心存在于微孔结构中，其吡啶红外酸总量/正丁基吡啶红外酸比值一般大于1.5。但是，微孔内酸性中心的大量存在使得发生过度裂化反应，反应选择性变差。对此，发明人提出本发明，限定改性Y型分子筛上酸性中心的分布，控制微孔内的酸性中心的数量，以解决加氢裂化反应存在过度裂化和反应选择性较差的问题。
针对现有技术中存在的不足之处，本发明的第一方面提供一种改性Y型分子筛，其中，以所述改性Y型分子筛的总量为基准，所述改性Y型分子筛含有0.5-2重量％的Na2O；所述改性Y型分子筛的吡啶红外总酸量与所述改性Y型分子筛的正丁基吡啶红外总酸量的比值为1-1.2；所述改性Y型分子筛的吡啶红外总酸量为0.1-1.2mmol/g。
优选地，所述改性Y型分子筛的比表面积为500-900m2/g；所述改性Y型分子筛的孔容为0.28-0.7ml/g；所述改性Y型分子筛的相对结晶度为50％-130％；所述改性Y型分子筛的晶胞参数为2.425-2.450；所述改性Y型分子筛的硅铝摩尔比为(6-80)：1。
本发明的第二方面提供一种制备本发明的改性Y型分子筛的方法，其中，包括如下步骤：
(1)将NaY分子筛进行预处理，得到脱钠脱铝Y型分子筛；
(2)将所述脱钠脱铝Y型分子筛进行钠离子交换，得到含钠Y型分子筛；
(3)将所述含钠Y型分子筛与大分子铵盐溶液进行浸渍处理，再经干燥、焙烧得到改性Y型分子筛。
优选地，步骤(1)中所述预处理的过程包括：铵离子交换、水热脱铝、铝盐脱铝、氟硅酸盐脱铝和酸脱铝中的一个或几个的组合。
优选地，步骤(1)中所述预处理的过程包括：
(a)将NaY分子筛与铵盐水溶液进行铵离子交换反应，得到脱钠Y型分子筛；
(b)将所述脱钠Y型分子筛进行水热脱铝，得到水热脱铝产物；
(c)将所述水热脱铝产物进行化学脱铝，得到所述脱钠脱铝Y型分子筛，其中，所述化学脱铝为铝盐脱铝、氟硅酸盐脱铝或酸脱铝。
本发明第三方面提供一种制备加氢裂化催化剂的方法，该方法包括：
(I)将本发明的改性Y型分子筛、无定型硅铝和/或氧化铝按照重量比为(5-90)：(0-50)：(0.6-80)进行混合为载体混料，然后向所述载体混料中加入质量分数为3-30 重量％的硝酸水溶液制成浆料进行挤条成型；
(II)将步骤(I)得到的挤条产物在80-120℃下干燥1-5h，再在400-500℃下焙烧1-5h得到硅铝载体；
(III)将所述硅铝载体在含有加氢活性金属的溶液中进行饱和浸渍，并将得到的产物经干燥、焙烧后得到加氢裂化催化剂。
本发明第四方面提供一种本发明的方法制得的加氢裂化催化剂，所述加氢裂化催化剂包含硅铝载体和加氢活性金属，以所述加氢裂化催化剂的总量为基准，所述硅铝载体的含量为55-85重量％，所述加氢活性金属以金属氧化物计的含量为15-45重量％，其中，所述硅铝载体含有本发明的改性Y型分子筛，所述改性Y型分子筛在所述硅铝载体中的含量为5-90重量％。
本发明第五方面，提供一种烃油加氢裂化的方法，该方法包括：在氢气存在下下，将烃油与本发明的加氢裂化催化剂相接触进行加氢裂化反应，其中，反应温度为340-420℃，反应压力为8-20MPa，所述烃油进料的体积空为速0.1-2h-1，氢气与所述烃油的体积比为(200-2000)：1。
通过上述技术方案，本发明提供了一种酸性中心位集中分布于大孔道(即二次孔)内的改性Y型分子筛。改性Y型分子筛的微孔内酸性中心位基本上被钠离子占据，仅剩下大孔道内的酸性中心，可以减少烃类分子进入微孔发生二次裂化反应的发生。通过使用不同分子大小的碱性有机物如吡啶和正丁基吡啶测定改性Y型分子筛上的红外酸含量，当两者的酸含量数值相当时可以说明改性Y型分子筛中分布的酸性中心集中在打孔道中。
本发明提供了制备改性Y型分子筛的方法，经过先将改性处理好的Y型分子筛酸性中心进行钠离子交换，使Y型分子筛具有的各种孔道内的酸性中心位被钠离子占据；然后，选用分子尺寸较大的苄基季铵盐对其进行铵离子交换处理，由于苄基季铵盐具有较大的分子尺寸，选择性地将分布于大孔道内的钠离子交换为苄基季铵阳离子，当再进行干燥和焙烧后，仅能苄基季铵阳离子脱除裸露出Y型分子筛的打孔道内的酸性中心位，而微孔内的酸性中心位仍然被钠离子占据而不显现酸性，使得本发明提供的分子筛具有酸性中心位集中分布于大孔道内特征，该特征可以通过使用具有不同分子尺寸的吡啶和正丁基吡啶进行红外酸性测定进行鉴别，得到具有上述特征的改性Y型分子筛。
进一步使用本发明的改性Y型分子筛制得加氢裂化催化剂，用于蜡油加氢裂化反应过程，有利于提高大蜡油中分子环状烃类物质的反应选择性，减少二次裂化反应发生， 改善加氢裂化尾油质量，提高反应液体产品收率。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明的第一方面提供一种改性Y型分子筛，其特征在于，以所述改性Y型分子筛的总量为基准，所述改性Y型分子筛含有0.5-2重量％的Na2O；所述改性Y型分子筛的吡啶红外总酸量与所述改性Y型分子筛的正丁基吡啶红外总酸量的比值为1-1.2；所述改性Y型分子筛的吡啶红外总酸量为0.1-1.2mmol/g。
本发明中，所述改性Y型分子筛是指将Y型分子筛原粉进行了化学处理(如本发明中后续提供的方法)之后得到的分子筛。
本发明提供的改性Y型分子筛，具有的酸性中心主要分布在大孔道内，而微孔内分布少量甚至没有酸性中心，可以减少烃油分子进入微孔中在酸性中心上发生二次裂化反应。
本发明提供的改性Y型分子筛所具有的上述孔道中酸性中心分布的特征可以通过使用吡啶和正丁基吡啶作为两种探针分子分别对改性Y型分子筛进行酸性测量的结果来体现。正丁基吡啶的分子直径大约为0.8nm，可以仅进入本发明提供的改性Y型分子筛的大孔道中，反映出大孔道中酸性中心的总量。吡啶的分子直径大约为0.6nm，可以进入改性Y型分子筛的微孔和大孔道中，反映出改性Y型分子筛所有孔道中酸性中心的总量。具体的测试过程可以为：通过吡啶、正丁基吡啶吸附红外光谱法，采用美国NICOLET公司Nicolet 6700傅立叶红外光谱仪，
取磨细(粒度小于200目)样品20mg压成直径为20mm的薄片，装在吸收池的样品架上；取200mg样品(片状)装入石英弹簧下端的吊杯中(在加样品之前记录弹簧长度，x1，mm)，将吸收池和吸附管连接好，开始抽空净化，真空度达4×10-2Pa时，升温至500℃保持1h，以除去样品的表面吸附物(此时，记为样品净化后弹簧长度，x2，mm)。然后降至室温，吸附吡啶(或正丁基吡啶)至饱和，再升温到160℃，平衡1小时，脱附物理吸附的吡啶(此时，记为吸附吡啶后弹簧长度，x3，mm)，利用吡啶(或正丁基吡啶)重量吸附法求得总酸量；其中，
总酸量采用吡啶重量吸附法计算，具体如下：
胡克定律(Hooke's law)(弹簧伸长长度与受力关系)：f＝kΔx
当弹簧竖直放置时：m＝kΔx
其中，m为样品质量，g；Δx为弹簧伸长长度，mm；k为弹簧倔强系数。
Figure PCTCN2017113629-appb-000001
Figure PCTCN2017113629-appb-000002
吡啶红外总酸量C(单位：mmol/g)：
Figure PCTCN2017113629-appb-000003
正丁基吡啶红外总酸量C’(单位：mmol/g)：按上式，将79.1替换为136.1后求得；
注：79.1、136.1分别为吡啶、正丁基吡啶的摩尔质量，单位为g/mol。
本发明调整酸性中心位在Y型分子筛的微孔和大孔道中的集中分布，从而实现控制烃油分子在分子筛上的反应。而酸性中心位的分布通过吡啶和正丁基吡啶的红外酸性总量测量来体现。对于常规的未经过孔道中酸性中心位调整的Y型分子筛，一般吡啶红外总酸量与正丁基吡啶红外总酸量的比值将大于1.2。由此可以区分Y型分子筛的微孔中酸性中心位是否被控制。
当改性Y型分子筛使用正丁基吡啶、吡啶分别测量出的酸总量相比相等或正丁基吡啶的酸总量略小时，即上述限定所述改性Y型分子筛的吡啶红外总酸量与所述改性Y型分子筛的正丁基吡啶红外总酸量的比值为1-1.2时，则说明所述改性Y型分子筛含有的酸性中心主要集中在大孔道中。
根据本发明，优选地，以所述改性Y型分子筛的总量为基准，所述改性Y型分子筛含有0.8-1.8重量％的Na2O；所述改性Y型分子筛的吡啶红外总酸量与所述改性Y型分子筛的正丁基吡啶红外总酸量的比值为1.02-1.15。
更优选，以所述改性Y型分子筛的总量为基准，所述改性Y型分子筛含有1-1.5重量％的Na2O；所述改性Y型分子筛的吡啶红外总酸量与所述改性Y型分子筛的正丁基吡啶红外总酸量的比值为1.05-1.12。
根据本发明，优选地，所述改性Y型分子筛的吡啶红外总酸量为0.2-1mmol/g。
更优选，所述改性Y型分子筛的吡啶红外总酸量为0.3～0.8mmol/g。
根据本发明，所述改性Y型分子筛还具有其他特征，也有利于用于蜡油加氢裂化反应过程中，改善加氢裂化尾油质量，提高反应液体产品收率。优选情况下，所述改性Y型分子筛的比表面积为500-900m2/g；优选为550-850m2/g；更优选为600-750m2/g。
优选地，所述改性Y型分子筛的孔容为0.28-0.7ml/g；优选为0.3-0.65ml/g；更优选为0.35-0.6ml/g。
优选地，所述改性Y型分子筛的相对结晶度为50％-130％；60％-110％；更优选为70％-100％。
优选地，所述改性Y型分子筛的晶胞参数为2.425-2.45nm；优选为2.428-2.448nm；更优选为2.43-2.445nm。
优选地，所述改性Y型分子筛的硅铝摩尔比为(6-80)：1；优选为(8-60)：1；更优选为(10-50)：1。
本发明的第二方面提供一种制备本发明的改性Y型分子筛的方法，其中包括如下步骤：
(1)将NaY分子筛进行预处理，得到脱钠脱铝Y型分子筛；
(2)将所述脱钠脱铝Y型分子筛进行钠离子交换，得到含钠Y型分子筛；
(3)将所述含钠Y型分子筛与大分子铵盐溶液进行浸渍处理，再经干燥、焙烧得到改性Y型分子筛。
根据本发明，步骤(1)用于在NaY分子筛中形成大孔道，有助于后续分别修饰大孔道和小孔道。优选情况下，步骤(1)中所述预处理的过程包括：铵离子交换、水热脱铝、铝盐脱铝、氟硅酸盐脱铝和酸脱铝中的一个或几个的组合。本发明中，将NaY分子筛进行所述预处理可以是将NaY分子筛进行铵离子交换、水热脱铝、铝盐脱铝、氟硅酸盐脱铝和酸脱铝中的一个或几个步骤，步骤之间的顺序可以不限，只要能提供所述脱钠脱铝Y型分子筛即可，例如所述脱钠脱铝Y型分子筛的Na2O含量小于3重量％，SiO2/Al2O3摩尔比为(6-80)：1，晶胞常数2.425-2.450。一般先将NaY分子筛通过铵离子交换进行脱钠，然后将脱钠的产物进行脱铝，可以选用水热脱铝、铝盐脱铝、氟硅酸盐脱铝和酸脱铝中的一个或几个的组合。
本发明一种优选实施方式，步骤(1)中所述预处理的过程包括：
(a)将NaY分子筛与铵盐水溶液进行铵离子交换反应，得到脱钠Y型分子筛；
(b)将所述脱钠Y型分子筛进行水热脱铝，得到水热脱铝产物；
(c)将所述水热脱铝产物进行化学脱铝，得到所述脱钠脱铝Y型分子筛，
其中，所述化学脱铝为铝盐脱铝、氟硅酸盐脱铝或酸脱铝。
根据本发明，步骤(a)用于脱除NaY分子筛中的Na离子，以便后续脱铝过程顺利进行。优选情况下，步骤(a)中所述铵盐离子交换反应的过程为：将NaY分子筛与铵盐水溶液在60-120℃，优选60-90℃下进行交换1-3h，交换次数为1-4次，得到所述脱钠Y型分子筛。
优选地，所述脱钠Y型分子筛的Na2O含量小于3重量％。
优选地，NaY分子筛的SiO2/Al2O3摩尔比为(3-6)：1，Na2O含量为6-12重量％。
优选地，铵盐选自氯化铵、硝酸铵、硫酸铵、醋酸铵和草酸铵中的一种或几种，所述铵盐水溶液的摩尔浓度为0.3-6mol/L，优选为1-3mol/L。
根据本发明，步骤(b)用于所述脱钠Y型分子筛脱铝，形成大孔道。优选地，步骤(b)中所述水热脱铝的过程为：将所述脱钠Y型分子筛与水蒸气在温度为520-700℃、压力为0.01-0.5MPa的条件下相接触1-6h。
优选地，所述水热脱铝的次数为1-3次。
根据本发明，步骤(c)用于分子筛的化学脱铝，形成大孔道。优选地，步骤(c)中所述化学脱铝的过程为：将所述水热脱铝的产物与铝盐溶液、氟硅酸铵溶液或硝酸溶液在温度为50-120℃下进行恒温反应0.5-3h。
优选地，所述铝盐溶液为氯化铝、硫酸铝和硝酸铝中的至少一种的水溶液。
优选地，所述铝盐溶液、氟硅酸铵溶液或硝酸溶液的摩尔浓度为0.05-2mol/L。当所述水热脱铝的产物与所述铝盐溶液进行所述恒温反应时即为所述铝盐脱铝。当所述水热脱铝的产物与所述氟硅酸铵溶液进行所述恒温反应时即为所述氟硅酸盐脱铝。当所述水热脱铝的产物与所述硝酸溶液进行所述恒温反应时即为所述酸脱铝。
根据本发明，步骤(2)用于将所述脱钠脱铝Y型分子筛的大、微孔道中所空出的酸性中心用钠离子中和。步骤(2)中所述钠离子交换的过程为：将所述脱钠脱铝Y型分子筛与NaNO3水溶液在40-80℃下进行恒温反应1-4h；其中NaNO3水溶液中NaNO3的质量分数为0.1-3重量％。
根据本发明，步骤(3)中的所述浸渍处理是通过大分子铵盐用于将Y型分子筛的大孔道中占领酸性中心的钠离子交换下来，使大孔道中的酸性中心呈现出来。而大分子铵盐不能进入Y型分子筛的微孔道，微孔道中可以仍然存在钠离子占领酸性中心。最终获得的本发明的改性Y型分子筛可以提供大孔道中具有酸性中心，但微孔道中极少、甚至不存在酸性中心，应用于加氢裂化反应时，减少烃油发生二次裂化反应。优选情况下 步骤(3)中所述浸渍处理的过程为：在40-80℃下，将所述含钠Y型分子筛浸渍在所述大分子铵盐溶液中2-6h。
本发明中，优选地，大分子铵盐为苄基季铵盐。
优选地，所述苄基季铵盐为苄基三丙基溴化铵、苄基三丁基溴化铵、苄基三丙基氯化铵和苄基三丁基氯化铵中的至少一种。
优选地，所述大分子铵盐溶液中以溴或氯元素的浓度计，大分子铵盐溶液的摩尔浓度为0.2-2mol/L。
本发明中，可以采用吡啶红外吸附和正丁基吡啶红外吸附的方法测定制备的改性Y型分子筛中酸性中心的分布。具体方法和测试结果如前所述，不再赘述。
根据本发明，优选情况下，步骤(3)中所述干燥的过程为在100-150℃下进行干燥1-4h；所述焙烧的过程为在500-700℃下进行焙烧处理2-6h。
本发明第三方面提供一种加氢裂化催化剂的制备方法，该方法包括：
(I)将本发明的改性Y型分子筛、无定型硅铝和/或氧化铝按照重量比为(5-90)：(0-50)：(0.6-80)进行混合为载体混料，然后向所述载体混料中加入质量分数为3-30重量％的硝酸水溶液制成浆料进行挤条成型；
(II)将步骤(I)得到的挤条产物在80-120℃下干燥1-5h，再在400-500℃下焙烧1-5h得到硅铝载体；
(III)将所述硅铝载体在含有加氢活性金属的溶液中进行饱和浸渍，并将得到的产物经干燥、焙烧后得到加氢裂化催化剂。
本发明提供的催化剂制备方法的步骤(I)中，所述浆料的固含量适于挤条成型得到条形的挤条产物即可。优选地，所述浆料的固含量为30-60重量％。
本发明中，步骤(III)加入含有加氢活性金属的溶液的量，可以满足得到的加氢裂化催化剂中含有以金属氧化物计的含量为15-45重量％的加氢活性金属。所述含有加氢活性金属的溶液中，加氢活性金属以金属氧化物计的浓度可以为20～70mol/L。
本发明中，所述含有加氢活性金属的溶液可以是含有第VIII族和/或第VI族的金属元素的化合物的溶液。优选地，可以是含有Ni和/或Co的化合物的溶液，含有W和/或Mo的化合物的溶液。更优选地，所述含有加氢活性金属的溶液可以是含有硝酸镍、硝酸钴、偏钨酸铵、钼酸铵、氧化钼的溶液。
本发明中，步骤(III)的干燥可以是在90-150℃下进行2-20h完成。焙烧可以是在400-600℃下进行2-10h完成。使所述加氢活性金属转变为氧化物形式存在于所述加氢裂 化催化剂中。
本发明第四方面提供一种本发明的方法制得的加氢裂化催化剂，所述加氢裂化催化剂包含硅铝载体和加氢活性金属，以所述加氢裂化催化剂的总量为基准，所述硅铝载体的含量为55-85重量％，所述加氢活性金属以金属氧化物计的含量为15-45重量％，其中，所述硅铝载体含有本发明的改性Y型分子筛，所述改性Y型分子筛在所述硅铝载体中的含量为5-90重量％。
根据本发明，优选情况下，所述加氢活性金属选自第VIII族和/或第VI族的金属。
优选地，所述第VIII族金属为Ni和/或Co，第VI族金属为W和/或Mo。
优选地，以所述催化剂的总量为基准，按金属氧化物计，所述加氢裂化催化剂含有所述第VIII族金属3-15重量％，所述第VI族金属10-40重量％。
本发明中，为方便加氢裂化催化剂的使用，以便运输和储存，所述加氢裂化催化剂中的所述加氢活性金属以氧化态形式存在，在进行加氢裂化反应前可以与含硫化合物接触经硫化反应转变为硫化态后，参与烃油的加氢裂化。
本发明中，所述加氢裂化催化剂含有本发明提供的改性Y型分子筛组分，可以具有更好的加氢裂化反应选择性，减少烃油分子发生二次裂化反应，加氢裂化反应产物的选择性更好。可以通过具体的反应性能评价实验测定所述加氢裂化催化剂的反应性能。实验可以在小型微反装置上采用单段串联一次通过工艺流程，装置上有两个串联的反应器，沿流程顺序，第一反应器装填常规精制催化剂，第二反应器装填加氢裂化催化剂。
本发明中，可以通过在第二反应器内一次装填本发明的加氢裂化催化剂和另一次装填常规Y型分子筛制备的加氢裂化催化剂，分别进行反应评价，比较在控制相同的精制油氮含量和转化深度下，两次反应分别得到的裂化尾油产品BMCI值以及装置液体产品收率。其中，尾油产品BMCI值越低、产品液收越高说明对应的催化剂在进行加氢裂化反应过程中，进而促进了大分子环状烃的反应、减少了二次裂化反应的发生。两次反应的区别仅在于催化剂中使用的分子筛不同，上述结果可以归功于分子筛酸性更集中分布于大孔道内。
本发明第五方面提供一种烃油加氢裂化的方法，该方法包括：在氢气存在下，将烃油与本发明的加氢裂化催化剂相接触进行加氢裂化反应，其中，反应温度为340-420℃，反应压力为8-20MPa，所述烃油进料的体积空为速0.1-2h-1，氢气与所述烃油的体积比为(200-2000)：1。
本发明中，所述烃油可以是石油基减压蜡油原料，其馏程在300-600℃、密度 0.86-0.94g/cm3。
进行所述加氢裂化反应时，所述加氢裂化催化剂中的加氢活性金属以硫化态的形式参与。但是如果直接制备含有硫化态的加氢活性金属的催化剂，催化剂在运输和储存过程中容易被氧化，在正式参与加氢裂化反应前仍然需要硫化。因此，本领域通常选择制备催化剂含有氧化态的加氢活性金属，然后在进行烃油加氢裂化反应前将催化剂进行硫化反应，得到催化剂含有硫化态的加氢活性金属，或者利用烃油中的含硫化合物，在烃油与催化剂接触的过程中完成加氢活性金属的硫化并实现烃油的加氢裂化。本发明提供的烃油加氢裂化的方法中，所述加氢裂化反应的过程中，本发明的加氢裂化催化剂在烃油中的含硫化合物存在下，加氢活性金属转变为硫化态并实现烃油的加氢裂化。
以下将通过实施例对本发明进行详细描述。
以下实施例和对比例中，吡啶、正丁基吡啶红外酸量通过吡啶、正丁基吡啶吸附红外光谱法测定，采用美国NICOLET公司Nicolet 6700傅立叶红外光谱仪方法测得，其过程如下：
取磨细(粒度小于200目)样品20mg压成直径为20mm的薄片，装在吸收池的样品架上，取200mg样品(片状)装入石英弹簧下端的吊杯中(在加样品之前记录弹簧长度，x1，mm)，将吸收池和吸附管连接好，开始抽空净化，真空度达4×10-2Pa时，升温至500℃保持1h，以除去样品的表面吸附物(此时，记为样品净化后弹簧长度，x2，mm)。然后降至室温，吸附吡啶(正丁基吡啶)至饱和，再升温到160℃，平衡1小时，脱附物理吸附的吡啶(此时，记为吸附吡啶后弹簧长度，x3，mm)，利用吡啶(正丁基吡啶)重量吸附法求得总酸量。
其中总酸量采用吡啶重量吸附法计算，具体如下：
胡克定律(Hooke's law)(弹簧伸长长度与受力关系)：f＝kΔx
当弹簧竖直放置时：m＝kΔx
其中，m为样品质量，克；Δx为弹簧伸长长度，mm；k为弹簧倔强系数。
Figure PCTCN2017113629-appb-000004
Figure PCTCN2017113629-appb-000005
总酸C(单位：mmol/g)：
Figure PCTCN2017113629-appb-000006
正丁基吡啶红外总酸量C’(单位：mmol/g)：按上式，将79.1替换为136.1后求得；
注：79.1、136.1分别为吡啶、正丁基吡啶的摩尔质量，单位为g/mol。
表面积和孔体积通过采用低温氮吸附法(BET法)方法测定；
分子筛中Na2O含量，分子筛SiO2/Al2O3摩尔比通过荧光法测定；
分子筛的晶胞参数、相对结晶度通过XRD方法测定，仪器为Rigaku Dmax-2500X射线衍射仪，采用Cukα辐射，石墨单晶滤波，操作管电压35KV，管电流40mA，扫描速度(2θ)为2°/min，扫描范围为4°～35°。标样为本发明实施例1使用的Y型分子筛原粉。
尾油收率通过产品实沸点切割数据计算而得；
BMCI测定方法：BMCI＝48640/T+473.7d-456.8
d：密度(15.6℃)
T：以绝对温度K表示的平均沸点。
实施例1
(1)取NaY型分子筛原粉(Na2O含量为10重量％，SiO2/Al2O3摩尔比为5.0)，用浓度为1.0mol/L的硝酸铵按照液固比3:1混合，在70℃下进行铵离子交换3h，重复此过程3次；得到脱钠Y型分子筛中，Na2O含量为2.5重量％；
(2)将脱钠Y型分子筛与水蒸汽在550℃、0.1MPa下相接触进行水热脱铝2h，重复此过程一次，得到水热脱铝产物；
(3)将水热脱铝产物按照液固比为5:1与0.5mol/L的硫酸铝溶液混合，然后在80℃下进行恒温反应2h，得到脱钠脱铝Y型分子筛；
(4)将脱钠脱铝Y型分子筛加入到0.8mol/L的NaNO3水溶液中，在60℃下进行钠离子交换2h，得到含钠Y型分子筛；
(5)将含钠Y型分子筛加入浓度为0.5mol/L的苄基三丁基溴化铵水溶液中，在70℃下进行浸渍处理3h；
(6)将步骤(5)得到的产物，经120℃干燥4h、550℃焙烧4h后获得改性Y型分子筛，编号为Y-1。
实施例2
(1)取NaY分子筛原粉，用浓度为2.0mol/L的氯化铵按照液固比3:1混合，在 80℃进行铵离子交换2h，重复此过程1次；得到脱钠Y型分子筛中，Na2O含量为2.7重量％；
(2)将脱钠Y型分子筛与水蒸汽在600℃、0.1MPa下相接触进行水热脱铝2h，重复此过程一次，得到水热脱铝产物；
(3)将水热脱铝产物按照液固比5:1与浓度为0.4mol/L的氟硅酸铵溶液混合，然后在90℃下进行恒温反应2h，得到脱钠脱铝Y型分子筛；
(4)将脱钠脱铝Y型分子筛加入到2.0mol/L的NaNO3水溶液中，在80℃下进行钠离子交换2h，得到含钠Y型分子筛；
(5)将含钠Y型分子筛加入浓度为1.5mol/L的苄基三丁基氯化铵水溶液中，在70℃下进行浸渍处理3h；
(6)将步骤(5)得到的产物，经120℃干燥4h、550℃焙烧4h后获得改性Y型分子筛，编号为Y-2。
实施例3
(1)取NaY分子筛原粉，用浓度为3.0mol/L的硫酸铵按照液固比3:1混合，在80℃进行铵离子交换2h，重复此过程1次；得到脱钠Y型分子筛中，Na2O含量为2.3重量％；
(2)将脱钠Y型分子筛与水蒸汽在630℃、0.1MPa下相接触进行水热处理2h，重复此过程一次，得到水热脱铝产物；
(3)将水热脱铝产物按照液固比5:1与浓度为0.6mol/L的稀硝酸溶液混合，然后在95℃下进行恒温反应2h，得到脱钠脱铝Y型分子筛；
(4)将脱钠脱铝Y型分子筛加入到1.5mol/L的NaNO3水溶液中，在70℃下进行钠离子交换2h，得到含钠Y型分子筛；
(5)将含钠Y型分子筛加入浓度为1.2mol/L的苄基三丙基溴化铵水溶液中，在80℃下进行浸渍处理2h；
(6)将步骤(5)得到的产物，经120℃干燥4h、550℃焙烧4h后获得改性Y型分子筛，编号为Y-3。
实施例4
(1)取NaY型分子筛原粉，用浓度为0.5mol/L的硝酸铵按照液固比3:1混合，在 70℃下进行铵离子交换3h，重复此过程3次；得到脱钠Y型分子筛中，Na2O含量为2.5重量％；
(2)将脱钠Y型分子筛按照液固比6:1与0.2mol/L氟硅酸铵处理溶液混合，然后在80℃下进行恒温反应2h；
(3)将步骤(2)得到的产物与水蒸汽在0.2MPa、520℃下相接触进行水热处理2h，重复此过程1次；
(4)将步骤(3)得到的产物按照液固比5:1与0.6mol/L的硫酸铝溶液搅拌混合，然后在75℃下进行恒温反应2h，得到脱钠脱铝Y型分子筛；
(5)将脱钠脱铝Y型分子筛加入到0.6mol/L的NaNO3水溶液中，在50℃下进行钠离子交换2h，得到含钠Y型分子筛；
(6)将含钠Y型分子筛加入浓度为0.5mol/L的苄基三丁基溴化铵水溶液中，在60℃下进行浸渍处理5h；
(7)将步骤(6)得到的产物，经120℃干燥4h、550℃焙烧4h后获得改性Y分子筛，编号为Y-4。
对比例1
(1)取NaY型分子筛原粉，用浓度为0.5mol/L的硝酸铵按照液固比3:1混合，在70℃下进行铵离子交换3h，重复此过程3次；得到脱钠Y型分子筛中，Na2O含量为2.5重量％；
(2)将铵交换Y分子筛与水蒸汽在550℃、0.1MPa下相接触进行水热处理2h；重复此过程一次，得到水热脱铝产物；
(3)将水热脱铝产物按照液固比为5:1与0.5mol/L的硫酸铝溶液混合，然后在80℃下进行恒温反应2h；
(4)将步骤(3)得到的产物，经120℃干燥4h、550℃焙烧4h后获得改性Y型分子筛，编号为B-1。
对比例2
(1)取NaY型分子筛原粉，用浓度为0.5mol/L的硝酸铵按照液固比3:1混合，在70℃下进行铵离子交换3h，重复此过程3次；得到脱钠Y型分子筛中，Na2O含量为2.5重量％；
(2)将步骤(1)得到的产物按照液固比6:1与0.2mol/L氟硅酸铵处理溶液混合，然后在80℃下进行恒温反应2h；
(3)将步骤(2)得到的产物与水蒸汽在0.2MPa、520℃下相接触进行水热处理2h，重复此过程1次；
(4)将步骤(3)得到的所得分子筛按照液固比5:1与0.6mol/L的硫酸铝溶液搅拌混合，然后在75℃下进行恒温反应2h；
(5)将步骤(4)得到的产物，经120℃干燥4h、550℃焙烧4h后获得改性Y型分子筛，编号为B-2。
对比例3
(1)取NaY型分子筛原粉200g，用浓度为0.5mol/L的硝酸铵按照液固比3:1混合，在70℃下进行铵离子交换3h，重复此过程3次；得到脱钠Y型分子筛中，Na2O含量为2.5重量％；
(2)将脱钠Y型分子筛在560℃，0.1MPa下水热处理2h；
(3)将步骤(2)得到的分子筛按照液固比5:1与蒸馏水搅拌混合，然后升温至80℃，在搅拌的过程中加入0.5mol/L的硫酸铝溶液400ml，恒温反应2h；
(4)将步骤(3)所得的分子筛在140℃干燥8min；
(5)取步骤(4)所得的分子筛放置于充满丁二烯气氛的密闭容器内，控制压力0.3MPa充分接触20min，然后，在空气气氛在200℃加热15h；
(6)步骤(5)所得的分子筛按照液固比5：1与蒸馏水混合，然后，加入浓度为0.6mol/L的氟硅酸铵溶液100ml，80℃处理2h；
(7)经步骤(6)氟硅酸铵处理后的Y分子筛，120℃干燥2h，550℃焙烧4h后，得到改性Y分子筛，编号B-3。
上述实施例及对比例制备的分子筛的性质见表1。
表1
Figure PCTCN2017113629-appb-000007
Figure PCTCN2017113629-appb-000008
从表1的数据可以看出，使用本发明提供的技术方案的实施例制备的改性Y型分子筛，吡啶红外总酸量与正丁基吡啶红外总酸量的比为1-1.2，优选为1.02-1.15，更优选为1.05-1.12，特别优选为1.03-1.09。而对比例得到的改性Y型分子筛的吡啶红外总酸量与正丁基吡啶红外总酸量的比则大于1.2，在1.4-1.7。
实施例5
用实施例1-4与对比例1-3制备的改性Y型分子筛制备加氢裂化催化剂，催化剂配方组成如表2所示：
(1)将改性Y型分子筛和氧化铝进行混合物为载体混料，然后向载体混料中加入质量分数为20重量％的硝酸水溶液制成浆料进行挤条成型；
(2)将步骤(1得到的挤条产物在100℃下干燥3h，再在450℃下焙烧3h得到硅铝载体；
(3)将硅铝载体在含有加氢活性金属的溶液中进行饱和浸渍，并将得到的产物经干燥、焙烧后得到加氢裂化催化剂。
得到的催化剂对应编号为：对应实施例1-4的改性Y型分子筛Y-1至Y-4的催化剂为C-1到C-4；对应对比例1-3的改性Y型分子筛B-1至B-3的催化剂为BC-1到BC-3。见表2。
表2
Figure PCTCN2017113629-appb-000009
评测例1
将催化剂C-1到C-4和BC-1到BC-3在小型微反装置(美国xytel公司100ml小型评价装置)上进行了评价试验，评价装置采用单段串联一次通过工艺流程，第一反应器 装填常规精制催化剂，第二反应器分别装填表2中加氢裂化催化剂，反应原料油性质列于表3，评价结果列于表4-表5。
表3
原料油 原料油
密度，g/cm3 0.9024
馏程，℃ 321～528
C，m％ 86.68
H，m％ 12.30
S，m％ 1.54
N，％ 1138
BMCI值 40.3
表4
催化剂 C-1 C-2 C-3 C-4 BC-1 BC-2 BC-3
反应温度，℃ 365 370 370 360 362 355 372
反应压力，MPa 15.0 15.0 15.0 15.0 15.0 15.0 15.0
体积空速，h-1 1.0 1.8 1.5 1.0 1.8 1.5 1.5
氢油体积比 1200 1200 1200 1200 1200 1200 1200
精制油氮含量，ppm 6 6 6 6 6 6 6
单程转化率，m％ 65 70 74 65 65 65 75
化学氢耗，m％ 2.30 2.35 2.40 2.34 2.43 2.50 2.48
表5
催化剂 C-1 C-2 C-3 C-4 BC-1 BC-2 BC-3
产品分布，m％              
C5+液收，m％ 97.8 98.2 97.9 97.4 95.5 94.0 95.80
尾油收率(＞350℃)，m％ 35 30 25 35 35 35 25
产品性质              
尾油(>350℃)              
BMCI 5.5 4.4 4.2 6.0 7.3 8.5 6.8
通过表5的结果可以看出，采用实施例1-4本发明提供的改性Y型分子筛制备的加氢裂化催化剂C-1到C-4，分子筛上具有优化的酸性中心分布，减少微孔内酸性中心的量，进行加氢裂化反应时，得到的加氢裂化尾油产品BMCI值明显低于使用由对比例1-3的改性Y型分子筛(吡啶红外总酸量与正丁基吡啶红外总酸量的比大于1.2)制得的加氢裂化催化剂进行反应的结果，同时C5 +液收大于对比例的催化剂的反应结果。
另外，对比例3中提供了一种现有技术改性Y型分子筛，其中采用了改变Y型分子筛颗粒的体相和表面的硅铝比。虽然该改性方法改变了分子筛局部的硅铝比将影响分 子筛的酸量，但是该方法无法改变Y型分子筛上大孔道和微孔道中酸性中心位的分布情况，仍然裸露出微孔内的酸中心位，吡啶酸量与正丁基吡啶酸量的比值大于1.2，不能减少进入微孔道的烃分子在酸中心位上发生二次裂化反应的可能，用于加氢裂化不能改善加氢裂化尾油质量，提高反应液体产品收率。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (19)

  1. 一种改性Y型分子筛，其特征在于，以所述改性Y型分子筛的总量为基准，所述改性Y型分子筛含有0.5-2重量％的Na2O；所述改性Y型分子筛的吡啶红外总酸量与所述改性Y型分子筛的正丁基吡啶红外总酸量的比值为1-1.2；所述改性Y型分子筛的吡啶红外总酸量为0.1-1.2mmol/g。
  2. 根据权利要求1所述的改性Y型分子筛，其中，以所述改性Y型分子筛的总量为基准，所述改性Y型分子筛含有0.8-1.8重量％的Na2O；所述改性Y型分子筛的吡啶红外总酸量与所述改性Y型分子筛的正丁基吡啶红外总酸量的比值为1.02-1.15；所述改性Y型分子筛的吡啶红外总酸量为0.2-1mmol/g。
  3. 根据权利要求2所述的改性Y型分子筛，其中，以所述改性Y型分子筛的总量为基准，所述改性Y型分子筛含有1-1.5重量％的Na2O；所述改性Y型分子筛的吡啶红外总酸量与所述改性Y型分子筛的正丁基吡啶红外总酸量的比值为1.05-1.12；所述改性Y型分子筛的吡啶红外总酸量为0.3-0.8mmol/g。
  4. 根据权利要求1-3中任意一项所述的改性Y型分子筛，其中，所述改性Y型分子筛的比表面积为500-900m2/g；所述改性Y型分子筛的孔容为0.28-0.7ml/g；所述改性Y型分子筛的相对结晶度为50％-130％；所述改性Y型分子筛的晶胞参数为2.425-2.45nm；所述改性Y型分子筛的SiO2/Al2O3摩尔比为(6-80)：1。
  5. 根据权利要求4所述的改性Y型分子筛，其中，所述改性Y型分子筛的比表面积为550-850m2/g；所述改性Y型分子筛的孔容为0.3-0.65ml/g；所述改性Y型分子筛的相对结晶度为60％-110％；所述改性Y型分子筛的晶胞参数为2.428-2.448nm；所述改性Y型分子筛的SiO2/Al2O3摩尔比为(8-60)：1。
  6. 根据权利要求5所述的改性Y型分子筛，其中，所述改性Y型分子筛的比表面积为600-750m2/g；所述改性Y型分子筛的孔容为0.35-0.6ml/g；所述改性Y型分子筛的相对结晶度为70％-100％；所述改性Y型分子筛的晶胞参数为2.43-2.445nm；所述改性Y型分子筛的SiO2/Al2O3摩尔比为(10-50)：1。
  7. 一种制备权利要求1-6中任意一项所述改性Y型分子筛的方法，其特征在于， 包括如下步骤：
    (1)将NaY分子筛进行预处理，得到脱钠脱铝Y型分子筛；
    (2)将所述脱钠脱铝Y型分子筛进行钠离子交换，得到含钠Y型分子筛；
    (3)将所述含钠Y型分子筛与大分子铵盐溶液进行浸渍处理，再经干燥、焙烧得到改性Y型分子筛。
  8. 根据权利要求7所述的方法，其中，步骤(2)中所述钠离子交换的过程为：将所述脱钠脱铝Y型分子筛与NaNO3水溶液在40-80℃下进行恒温反应1-4h；其中NaNO3水溶液中NaNO3的质量分数为0.1-3重量％。
  9. 根据权利要求7或8所述的方法，其中，步骤(3)中所述浸渍处理的过程为：在40-80℃下，将所述含钠Y型分子筛浸渍在所述大分子铵盐溶液中2-6h；其中，大分子铵盐为苄基季铵盐；
    优选地，所述苄基季铵盐为苄基三丙基溴化铵、苄基三丁基溴化铵、苄基三丙基氯化铵和苄基三丁基氯化铵中的至少一种；
    优选地，所述大分子铵盐溶液中以溴或氯元素的浓度计，大分子铵盐溶液的摩尔浓度为0.2-2mol/L。
  10. 根据权利要求7所述的方法，其中，步骤(3)中所述干燥的过程为在100-150℃下进行干燥1-4h；所述焙烧的过程为在500-700℃下进行焙烧处理2-6h。
  11. 根据权利要求7-10中任意一项所述的方法，其中，步骤(1)中所述预处理的过程包括：铵离子交换、水热脱铝、铝盐脱铝、氟硅酸盐脱铝和酸脱铝中的一个或几个的组合。
  12. 根据权利要求11所述的方法，其中，步骤(1)中所述预处理的过程包括：
    (a)将NaY分子筛与铵盐水溶液进行铵离子交换反应，得到脱钠Y型分子筛；
    (b)将所述脱钠Y型分子筛进行水热脱铝，得到水热脱铝产物；
    (c)将所述水热脱铝产物进行化学脱铝，得到所述脱钠脱铝Y型分子筛，
    其中，所述化学脱铝为铝盐脱铝、氟硅酸盐脱铝或酸脱铝。
  13. 根据权利要求12所述的方法，其中，步骤(a)中所述铵盐离子交换反应的过程为：将NaY分子筛与铵盐水溶液在60-120℃，优选60-90℃下进行交换1-3h，交换 次数为1-4次，得到所述脱钠Y型分子筛，所述脱钠Y型分子筛的Na2O含量小于3重量％；
    其中，NaY分子筛的SiO2/Al2O3摩尔比为(3-6)：1，Na2O含量为6-12重量％；铵盐选自氯化铵、硝酸铵、硫酸铵、醋酸铵和草酸铵中的一种或几种，所述铵盐水溶液的摩尔浓度为0.3-6mol/L，优选为1-3mol/L。
  14. 根据权利要求12所述的方法，其中，步骤(b)中所述水热脱铝的过程为：将所述脱钠Y型分子筛与水蒸气在温度为520-700℃、压力为0.01-0.5MPa的条件下相接触1-6h；优选地，所述水热脱铝的次数为1-3次。
  15. 根据权利要求12所述的方法，其中，步骤(c)中所述化学脱铝的过程为：将所述水热脱铝的产物与铝盐溶液、氟硅酸铵溶液或硝酸溶液在温度为50-120℃下进行恒温反应0.5-3h；优选地，所述铝盐溶液、氟硅酸铵溶液或硝酸溶液的摩尔浓度为0.05-2mol/L。
  16. 一种制备加氢裂化催化剂的方法，该方法包括：
    (I)将权利要求1-6中任意一项所述的改性Y型分子筛、无定型硅铝和/或氧化铝按照重量比为(5-90)：(0-50)：(0.6-80)进行混合为载体混料，然后向所述载体混料中加入质量分数为3-30重量％的硝酸水溶液制成浆料进行挤条成型；
    (II)将步骤(I)得到的挤条产物在80-120℃下干燥1-5h，再在400-500℃下焙烧1-5h得到硅铝载体；
    (III)将所述硅铝载体在含有加氢活性金属的溶液中进行饱和浸渍，并将得到的产物经干燥、焙烧后得到加氢裂化催化剂。
  17. 一种权利要求16所述的方法制得的加氢裂化催化剂，所述加氢裂化催化剂包含硅铝载体和加氢活性金属，以所述加氢裂化催化剂的总量为基准，所述硅铝载体的含量为55-85重量％，所述加氢活性金属以金属氧化物计的含量为15-45重量％，其中，所述硅铝载体含有权利要求1-6中任意一项所述的改性Y型分子筛，所述改性Y型分子筛在所述硅铝载体中的含量为5-90重量％。
  18. 根据权利要求17所述的加氢裂化催化剂，其中，所述加氢活性金属选自第VIII族和/或第VI族的金属；优选所述第VIII族金属为Ni和/或Co，第VI族金属为W 和/或Mo；优选地，以所述催化剂的总量为基准，按金属氧化物计，所述加氢裂化催化剂含有所述第VIII族金属3-15重量％，所述第VI族金属10-40重量％。
  19. 一种烃油加氢裂化的方法，该方法包括：在氢气存在下，将烃油与权利要求17或18所述的加氢裂化催化剂相接触进行加氢裂化反应，其中，反应温度为340-420℃，反应压力为8-20MPa，所述烃油进料的体积空为速0.1-2h-1，氢气与所述烃油的体积比为(200-2000)：1。
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