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WO2015078256A1 - β分子筛及其制备方法和含有该β分子筛的加氢催化剂 - Google Patents

β分子筛及其制备方法和含有该β分子筛的加氢催化剂 Download PDF

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Publication number
WO2015078256A1
WO2015078256A1 PCT/CN2014/089699 CN2014089699W WO2015078256A1 WO 2015078256 A1 WO2015078256 A1 WO 2015078256A1 CN 2014089699 W CN2014089699 W CN 2014089699W WO 2015078256 A1 WO2015078256 A1 WO 2015078256A1
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Prior art keywords
molecular sieve
hours
catalyst
carrier
alumina
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PCT/CN2014/089699
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English (en)
French (fr)
Inventor
刘昶
王凤来
王珂琦
杜艳泽
赵红
关明华
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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抚顺石油化工研究院
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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抚顺石油化工研究院 filed Critical 中国石油化工股份有限公司
Priority to CA2931532A priority Critical patent/CA2931532C/en
Priority to US15/036,368 priority patent/US10112186B2/en
Priority to DK14865118.5T priority patent/DK3056272T3/da
Priority to KR1020167016935A priority patent/KR101840773B1/ko
Priority to RU2016122895A priority patent/RU2641702C2/ru
Priority to EP14865118.5A priority patent/EP3056272B1/en
Priority to JP2016554779A priority patent/JP6230721B2/ja
Publication of WO2015078256A1 publication Critical patent/WO2015078256A1/zh

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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
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    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C—CHEMISTRY; METALLURGY
    • 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
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    • C10G47/12—Inorganic carriers
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    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

Definitions

  • the present invention relates to a beta molecular sieve, a process for the preparation thereof and a hydrogenation catalyst comprising the beta molecular sieve.
  • the ⁇ molecular sieve can be used as an active component of a hydrocracking catalyst and can be used as an active component of a diesel hydrotreating catalyst.
  • the hydrocracking technology has the characteristics of strong raw material adaptability, 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 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. It has been widely used in countries all over the world. Hydrocracking technology has become the core technology of the oil-chemical-fiber combination in the modern refining industry. The hydro-upgrading technology converts various inferior diesel fractions into high-quality diesel products or their blending components under relatively mild process conditions, which can effectively improve the quality of diesel products, especially the density of diesel products and aromatics.
  • the hydro-upgrading technology is ideal for upgrading the inferior diesel of refining and chemical enterprises. technology.
  • Y-type molecular sieves Compared with Y-type molecular sieves, ⁇ -molecular sieves have a three-dimensional 12-membered ring-hole structure, but there is no super-cage structure like Y-type molecular sieve.
  • the main features are two 4-membered ring units of four 4-membered rings and four 5-membered rings.
  • the crystal hole structure belongs to the cubic crystal system.
  • the molecular sieve silica-alumina structure is diverse and complex.
  • the skeleton structure of the ⁇ molecular sieve is more complicated than the Y-type molecular sieve.
  • the two linear channels in the three intersecting pore systems are orthogonal to each other and perpendicular to the [001] direction, and the channel size is 0.57 nm ⁇ 0.75 nm, and the third
  • the binary ring channel system is parallel to the [001] direction and is a nonlinear channel with a channel size of 0.56 nm ⁇ 0.65 nm.
  • the crystallized ⁇ zeolite molecular sieve has a diversified structure.
  • the skeleton silicon aluminum structure is a tetracoordinate structure.
  • This structure occupies the main form of the existence of silicon-aluminum in the molecular sieve, and its basic structure is composed of Si(4Al), Si(3Al), Si(2Al), Si(1Al) and Si(0Al) structural units with different contents. And Si(3Al) and Si(2Al) structures are dominant, and there are also six-coordinated non-framework aluminum in the molecular sieve. The existence and content of these various structures of silica-alumina in subsequent different modification processes Different changes occur, which will result in different catalytic properties.
  • ⁇ molecular sieves such as CN 1105646A
  • ammonium exchange for desodiumification followed by high temperature calcination to remove the templating agent (organic amine), followed by dealuminization and constant pressure hydrothermal treatment, which can greatly Lift The silicon to aluminum ratio of high beta molecular sieves.
  • the staged roasting and deamination is especially emphasized, which not only makes the preparation process complicated, but also the sodium salt before the ammonium salt is exchanged in the ammonium salt before the staged ammonium burning.
  • a method of modifying a beta molecular sieve is disclosed in CN 101450318A.
  • the method comprises the following steps: exchanging sodium type ⁇ molecular sieve with ammonium salt, and impregnating the molecular sieve with the phosphorus compound solution and the solution containing the transition metal compound, and the obtained ⁇ molecular sieve has higher specific surface area and higher relative crystallinity. It can be further shape-selectively cracked to form low-carbon olefins.
  • CN 1393522 A discloses a modification method of ⁇ molecular sieve.
  • the process of the method is as follows: (1) the crystallized ⁇ zeolite is directly subjected to ammonium salt exchange, (2) the ammonium salt exchanged ⁇ molecular sieve is filtered, washed, dried and calcined, and (3) the demineralized ⁇ molecular sieve is carried out. Acid treatment, filtration, and (4) acid-treated ⁇ molecular sieves are subjected to pressurized hydrothermal treatment.
  • the zeolite beta is first subjected to acid treatment and then hydrothermally treated, and is treated with a mineral acid in the acid treatment process, in which the skeleton structure of a part of the molecular sieve is destroyed, and the crystallinity of the molecular sieve is decreased, forming
  • the large non-framework structure remains in the pores of the molecular sieve and is difficult to remove, affecting the acid distribution and acid strength of the modified molecular sieve.
  • high temperature hydrothermal treatment after acid treatment also forms a certain amount of non-framework aluminum in the molecular sieve, which will directly affect the pore structure and acid properties of the molecular sieve.
  • the acid distribution and acid properties of the molecular sieve will directly affect the molecular sieve.
  • the performance of the molecular sieve as a catalyst for the cracking component affects the properties of the hydrocracked diesel and chemical materials.
  • the method of modifying the molecular sieve is longer, the yield of the molecular sieve in the preparation process is low, and the multi-step modification treatment greatly improves the modification cost and energy consumption.
  • a catalyst comprising a beta molecular sieve and a Y molecular sieve is described in US 5,350,501, US 5,447,623, US 5,279,726, US 5,536,687.
  • the composition is: Y molecular sieve (1 ⁇ 15wt%), ⁇ molecular sieve (1 ⁇ 15wt%), dispersed silicoalumino, alumina, metal W and Ni.
  • the ⁇ molecular sieve used therein is a method of removing the template by ion exchange and calcination. A hydrogen type beta molecular sieve is obtained.
  • the catalyst reactivity and medium oil selectivity are not very high, and it is difficult to meet the needs of manufacturers to increase the processing capacity of the device and further increase the middle distillate.
  • CN 1393521A discloses a medium oil type hydrocracking catalyst and a preparation method thereof, and the carrier used for the catalyst is a composite molecular sieve of amorphous silicon aluminum, aluminum oxide, Y and ⁇ .
  • the composite molecular sieve is obtained by mixing the original molecular sieve of the ⁇ molecular sieve with the templating agent and mixing with the modified Y molecular sieve, and then treating with the mixed solution of H + and NH 4 + .
  • the method is to first burn the original molecular sieve of the ⁇ molecular sieve to the templating agent, which affects the skeleton structure of the molecular sieve, and greatly reduces the crystallinity of the molecular sieve, and also affects the acidity of the molecular sieve, and the catalytic activity of the catalyst prepared by the method is not high.
  • the quality of the middle distillate of jet fuel and diesel oil still needs to be further improved.
  • the present invention provides a ⁇ -molecular sieve having a uniform silica-alumina structure, a preparation method thereof, and a hydrogenation catalyst containing the ⁇ molecular sieve.
  • the ⁇ molecular sieve further has the characteristics of suitable acidity and reasonable pore structure.
  • the method has fewer modification steps, high yield of the modified molecular sieve of interest and low preparation cost.
  • the hydrocracking catalyst prepared by the ⁇ molecular sieve of the invention as a cracking component is suitable for the production of low-condensed diesel oil by heavy distillate hydrocracking and improving the properties of the hydrogenated tail oil.
  • the hydrocracking catalyst prepared by the ⁇ molecular sieve of the present invention and the Y molecular sieve together as a cracking component is suitable for producing high quality middle distillate by heavy distillate hydrocracking.
  • the diesel hydrotreating catalyst is prepared by using the ⁇ molecular sieve of the invention as a cracking component, and is used for upgrading the inferior diesel raw material to produce high quality diesel oil with high cetane number, large density reduction and low freezing point.
  • a ⁇ molecular sieve having the following properties: a SiO 2 /Al 2 O 3 molar ratio of 30 to 150, preferably 40 to 150, and a non-framework aluminum accounting for 2% of total aluminum.
  • a SiO 2 /Al 2 O 3 molar ratio of 30 to 150 preferably 40 to 150
  • a non-framework aluminum accounting for 2% of total aluminum.
  • the silicon atom coordinated to the Si(0Al) structure accounts for 95% or more, preferably 95% to 99%, and more preferably 96% to 99% of the silicon atom in the skeleton structure.
  • a method of preparing a beta molecular sieve comprising:
  • step (2) The product obtained in the step (1) is contacted with ammonium fluorosilicate, and then filtered, washed with water and dried to obtain a ⁇ molecular sieve.
  • a hydrogenation catalyst comprising a hydrogenation-active metal component and a carrier, wherein the carrier comprises the above-mentioned ⁇ molecular sieve provided by the present invention.
  • the support of the hydrogenation catalyst further contains alumina.
  • the support of the hydrogenation catalyst further contains a Y-type molecular sieve and/or an amorphous silica-alumina.
  • the ⁇ molecular sieve provided by the invention has the characteristics of uniform structure, reasonable acidity and reasonable pore structure of the framework silicon aluminum, and as the cracking component, the catalyst can have higher catalytic activity and heterogeneity.
  • the cracking catalyst with ⁇ molecular sieve as the acidic component and the suitable amorphous silicon aluminum as the second cracking component not only fully exert their respective performance characteristics, but also produce better synergistic catalysis to make the hydrocracking catalyst. While the activity is improved, it has good cycloalkyl selective ring opening, paraffin isomerization, heavy fraction moderate hydrocracking, aromatic saturation and hetero atom removal performance.
  • the hydrocracking catalyst has high activity, can produce low-condensation point diesel oil at the maximum amount, and can simultaneously produce high-quality hydrogenated tail oil.
  • a hydrogenation catalyst using a ⁇ -molecular sieve together with a Y-type molecular sieve as a cracking center can be used as a hydrocracking catalyst, which can fully exert its respective performance characteristics and can synergistically catalyze two molecular sieves, namely, ⁇ .
  • Molecular sieves have a good isomerization effect on long side chains on paraffins or aromatic hydrocarbons, which can effectively reduce the freezing point of products.
  • Y-type molecular sieves have high ring opening selectivity for aromatic hydrocarbons and improve the product properties of the target products. Therefore, the hydrocracking catalyst has high activity, can produce high-quality middle distillate products (air coal + diesel), and can simultaneously produce high-quality hydrogenated tail oil.
  • the diesel hydrotreating catalyst prepared by the ⁇ molecular sieve of the invention as a cracking component is very suitable for the high quality diesel oil with high cetane number, large density reduction and low freezing point for the upgrading of inferior diesel raw materials.
  • Figure 1 is a 27 Al MAS NMR spectrum of the ⁇ molecular sieve of the present invention in Example 6, wherein the abscissa is ppm;
  • Figure 2 is a comparison of the comparative molecular sieve 27 Al MAS NMR spectrum of Comparative Example 1, wherein the abscissa is ppm.
  • a ⁇ molecular sieve having the following properties: a SiO 2 /Al 2 O 3 molar ratio of 30 to 150, preferably 40 to 150, further preferably 60 to 120, non-framework
  • the aluminum accounts for 2% or less, preferably 1% or less of the total aluminum
  • the silicon atom coordinated to the Si(0Al) structure accounts for 95% or more, preferably 95% to 99%, and more preferably 96% of the silicon atoms in the skeleton structure. ⁇ 99%.
  • the ⁇ molecular sieve provided by the present invention preferably has the following properties: a relative crystallinity of 100% to 140%.
  • the ⁇ molecular sieve provided by the present invention preferably has the following properties: the amount of infrared acid is 0.1-0.5 mmol/g, preferably 0.15-0.45 mmol/g, and the acid amount of the medium-strong acid measured by the NH 3 -TPD method accounts for 80% of the total acid amount. % or more is preferably 80% to 95%, and more preferably 85% to 95%.
  • the ⁇ molecular sieve provided by the present invention preferably has the following properties: Na 2 O ⁇ 0.15 wt%, preferably Na 2 O ⁇ 0.10 wt%.
  • the present invention provides a zeolite ⁇ , which is preferably the following properties: specific surface area of 400m 2 / g ⁇ 800m 2 / g, preferably from 500m 2 / g ⁇ 700m 2 / g, a total pore volume of 0.30mL / g ⁇ 0.50mL / g .
  • total aluminum refers to the sum of aluminum in the framework aluminum in the molecular sieve and aluminum in the non-framework aluminum.
  • Non-framework aluminum refers to aluminum in the molecular sieve in the form of a six-coordinate structure.
  • Skeleton aluminum refers to aluminum in the molecular sieve in the form of a tetracoordinate structure.
  • a silicon atom also referred to as a skeleton silicon atom in a skeleton structure, that is, a sum of silicon atoms coordinated by Si (4Al), Si (3Al), Si (2Al), Si (1Al), and Si (0Al) structures.
  • Si(4Al), Si(3Al), Si(2Al), Si(1Al), and Si(0Al) are tetracoordinate structures (ie, skeleton structures) that are in different coordination states with silicon atoms in the silicon oxytetrahedron.
  • Si(4Al) refers to a tetracoordinate structure in which a silicon atom in a silicon tetrahedron is directly connected to only four aluminoxytetrahedrons, that is, Si[(OAl) 4 ], and Si(3Al) refers to a silicon tetrahedron.
  • the tetracoordinate structure in which silicon atoms are directly connected to three aluminum oxytetrahedrons and one silicon oxytetrahedron is Si[(OAl) 3 (OSi) 1 ], and Si(2Al) is silicon in silicon oxytetrahedron
  • the tetracoordinate structure in which an atom is directly connected to two aluminum oxytetrahedrons and two siloxane tetrahedra is Si[(OAl) 2 (OSi) 2 ], and Si (1Al) refers to a silicon atom in a silicon oxytetrahedron.
  • a 27 Al MAS NMR spectrum is obtained by a nuclear magnetic resonance spectroscopy (NMR method) to obtain a ratio of framework aluminum to non-framework aluminum, which is calculated as an atom of Al.
  • the 29 Si MAS NMR spectrum was obtained by NMR spectroscopy (NMR) to obtain silicon atoms in different coordination states (Si(4Al), Si(3Al), Si(2Al), Si(1Al) and Si(0Al )) The proportion of the form present, in terms of Si atom.
  • the preparation method of the ⁇ molecular sieve of the invention comprises the following steps:
  • step (2) The product obtained in the step (1) is contacted with ammonium fluorosilicate, and then filtered, washed with water and dried to obtain a ⁇ molecular sieve.
  • the raw material of the ⁇ molecular sieve is contacted with the normal pressure and the dynamic water vapor, preferably, the original molecular sieve of the ⁇ molecular sieve is placed in the container, and then the water vapor is introduced from one end of the container, and the raw powder is passed through the ⁇ molecular sieve. The other end of the container is discharged.
  • the pressure inside the vessel is maintained at a normal pressure
  • the treatment temperature is maintained at 500 to 650 ° C
  • the treatment time is 5 to 10 hours.
  • step (1) is programmed to increase the temperature by 50 to 150 ° C / hour and rise to 250 to 450 ° C. At the beginning, the introduction of water vapor is started, and the temperature is further raised to 500 to 650 ° C, and then left at this temperature for 5 to 10 hours.
  • the step (1) ⁇ molecular sieve raw powder is synthesized by a conventional hydrothermal method, usually using an organic amine as a template, and the commonly used organic amine template can be tetraethylammonium hydroxide or tetramethyl hydroxide. One or more of ammonium, tetraethylammonium bromide, and the like.
  • the ⁇ -molecular sieve raw powder usually contains a templating agent, and the weight of the templating agent is generally 10% to 15%.
  • the properties of the ⁇ molecular sieve raw powder are as follows: the SiO 2 /Al 2 O 3 molar ratio is 22.5 to 28.5, and the Na 2 O content is 1.0 wt% to 3.0 wt%.
  • the content of the template in the original molecular sieve of ⁇ -molecular sieve can be obtained by differential scanning calorimetry (DSC)-thermogravimetry (TG), wherein the thermogravimetric method is a device of the German company Netzsch STA449C-QMS403C, which is under an argon atmosphere.
  • the gas flow rate is 25 mL/min
  • the heating rate is 10 ° C/min
  • the temperature is raised from room temperature to 600 ° C
  • the sample mass is about 10 mg
  • the weight loss of the ⁇ molecular sieve raw powder between 150 ° C and 500 ° C is taken as the amount of the template.
  • Step (1) The original molecular sieve of ⁇ molecular sieve is treated under normal pressure and dynamic water vapor condition, and 100% by weight of water vapor is used, and water vapor is passed through the molecular sieve raw powder per 50 g of the original molecular sieve of the molecular sieve of 50-100 L/h.
  • Step (2) The product obtained in the step (1) is contacted with ammonium fluorosilicate.
  • the conditions for the contact include a temperature of 40 to 120 ° C, preferably 70 to 100 ° C, and a time of 0.5 to 8.0 hours, preferably 1.0 to 3.0 hours.
  • step (2) is contacted with the ⁇ molecular sieve obtained in the step (1) by using an aqueous solution of ammonium fluorosilicate, and the concentration of the aqueous solution of ammonium fluorosilicate is 10 g to 60 g/100 mL of the solution, and the aqueous solution of ammonium fluorosilicate and the solution of ⁇ zeolite.
  • the solid product ratio is from 3:1 to 15:1.
  • the slurry after the contact with the step (2) is directly filtered, and the filtered cake is washed with water several times.
  • the water washing is generally carried out using deionized water until the pH of the washing liquid is near neutral.
  • the washing temperature may be 50 to 100 ° C, preferably 60 to 90 ° C, the liquid solid content ratio is generally 5:1 to 15:1, and the washing time is 0.5 to 1.0 hour, so that the pH of the washing liquid is near neutral.
  • the drying is preferably carried out at 100 to 120 ° C for 3 to 6 hours.
  • the yield of the ⁇ molecular sieve modified by the method of the present invention is 85 wt% or more.
  • the ⁇ molecular sieve of the invention has the characteristics of uniform structure, moderate acidity, reasonable pore structure, and the like, and is suitable as a cracking component, so that the catalyst has higher catalytic activity and heterogeneous ability.
  • the method of the invention firstly adopts the normal pressure and dynamic hydrothermal treatment of the molecular sieve original powder, and does not need to undergo a pretreatment process such as ammonium exchange, and can realize the descreening of the molecular sieve (de-templating agent) and the selective reduction of the framework aluminum under the action of dynamic high-temperature steam.
  • the activation energy avoids the damage to the molecular sieve skeleton structure, maintains the uniformity of the molecular sieve skeleton structure, and cooperates with the subsequent ammonium hexafluorosilicate modification process to effectively remove the low-energy skeleton aluminum uniformly and in the skeleton.
  • the silicon atom is supplemented to make the molecular structure of the molecular sieve more uniform and stable, and the sodium ions in the molecular sieve are also taken out together, and the sodium content in the molecular sieve can be removed to 0.15 wt% or less, thereby overcoming the prior art.
  • the method of the invention can further improve the channel junction by ammonium hexafluorosilicate
  • the structure can remove the generated non-framework aluminum from the molecular sieve pores, thereby achieving the purpose of extracting non-framework aluminum and making the molecular sieve pores more smooth.
  • the invention optimizes the modification method, so that the modified molecular sieve has a uniform structure of the silica-alumina structure, a reasonable pore structure, a more uniform distribution of the acid center strength and the acid density, and is favorable for providing a uniform cracking center and improving the target product selectivity of the catalyst. .
  • the hydrogenation catalyst of the present invention comprises a hydrogenation-active metal component and a support, wherein the support comprises the above-mentioned ⁇ molecular sieve, amorphous silica-alumina and/or Y-type molecular sieve, and alumina, the hydrogenation catalyst has hydrogenation
  • the cracking function is thus a hydrocracking catalyst.
  • the hydrocracking catalyst has a specific surface area of 200 to 400 m 2 /g and a pore volume of 0.35 to 0.60 mL/g.
  • the present invention refers to a hydrogenation catalyst containing the above-mentioned ⁇ molecular sieve, amorphous silica alumina and alumina as a first hydrocracking catalyst, and the carrier comprises the above-mentioned ⁇ molecular sieve, Y-type molecular sieve, and hydrogenation of alumina.
  • the catalyst is referred to as a second hydrocracking catalyst.
  • the content of the ⁇ molecular sieve is 3% to 20%, and the content of the amorphous silicon aluminum is 10% to 70%, preferably 25%, based on the weight of the carrier. ⁇ 55%, the content of alumina is 15% to 70%, preferably 25% to 62%.
  • the amorphous silica-alumina has a SiO 2 content of 5% to 40% by weight, and the amorphous silica-alumina has a pore volume of 0.6 to 1.1 mL/g and a specific surface area of 300 to 500 m 2 /g.
  • the alumina is macroporous alumina and/or small pore alumina, and the macroporous alumina has a pore volume of 0.7 to 1.0 mL/g, a specific surface area of 200 to 500 m 2 /g, and a pore volume of the small pore alumina. It is 0.3 to 0.5 mL/g and has a specific surface area of 200 to 400 m 2 /g.
  • the weight content of the Group VIB metal in terms of oxide is 10.0% to 30.0% based on the total amount of the catalyst, and the weight content of the Group VIII metal in terms of oxide It is 4.0% to 8.0%.
  • the hydrogenation-active metal component is a metal of Group VIB and/or Group VIII
  • the metal of Group VIB is molybdenum and/or tungsten
  • the metal of Group VIII is cobalt and/or nickel.
  • the first hydrocracking catalyst adopts ⁇ molecular sieve as an acidic component, in particular, adding suitable amorphous silicon aluminum as the second cracking component, which fully exerts its respective performance characteristics and produces better synergistic catalytic action.
  • ⁇ molecular sieve as an acidic component
  • suitable amorphous silicon aluminum as the second cracking component
  • it has good cycloalkane selective opening, paraffin isomerization, heavy fraction moderate hydrocracking, aromatic saturation and hetero atom removal performance, so that the hydrocracking catalyst It has high activity and can produce high-quality low-condensation diesel oil at the same time. It can also produce high-quality hydrogenated tail oil.
  • the above first hydrocracking catalyst can be used for producing low-condensation diesel oil by hydrocracking heavy oil as a feedstock oil, and at the same time can produce high-quality hydrogenated tail oil.
  • the hydrocracking adopts a single-stage process, the total reaction pressure is 12-20 MPa, the volume space velocity is 0.5-3.0 h -1 , the hydrogen oil volume ratio is 800:1-2000:1, and the reaction temperature is 365-435 °C.
  • the content of the ⁇ molecular sieve is 5% to 20%
  • the content of the Y molecular sieve is 10% to 40%
  • the content of the alumina is based on the weight of the carrier. 40% to 85%.
  • the specific surface area of the zeolite Y was 850m 2 / g ⁇ 950m 2 / g, a total pore volume of 2 / Al 2 O 3 molar ratio of 0.43mL / g ⁇ 0.55mL / g, SiO is from 20 to 150
  • the unit cell parameter is 2.425 to 2.433 nm, and the infrared acid amount is 0.1 to 0.4 mmol/g.
  • the alumina is macroporous alumina and/or small pore alumina, and the pore volume of the macroporous alumina is 0.7 to 1.0 mL/g, the specific surface area is 200 to 500 m 2 /g, and the pores of the small pore alumina are used.
  • the content is 0.3 to 0.5 mL/g, and the specific surface area is 200 to 400 m 2 /g.
  • the hydrogenation-active metal component is a metal of Group VIB and/or Group VIII
  • the metal of Group VIB is molybdenum and/or tungsten
  • the metal of Group VIII is cobalt and/or nickel.
  • the content of the Group VIB metal is from 10.0% to 30.0% based on the weight of the catalyst, and the content of the Group VIII metal in terms of the oxide is 4.0. % ⁇ 8.0%.
  • the above second hydrocracking catalyst can be used in a process for producing middle distillate (air coal + diesel) from hydrocracking of heavy distillate oil.
  • the hydrocracking operating conditions include a total reaction pressure of 12.0 to 20.0 MPa, a volumetric space velocity of 1.0 to 3.0 h -1 , a hydrogen oil volume ratio of 800:1 to 2000:1, and a reaction temperature of 365 ⁇ . 435 ° C.
  • the preparation method of the hydrocracking catalyst of the invention comprises the preparation of a carrier and the loading of the hydrogenation active metal component, wherein the preparation process of the carrier is as follows: the ⁇ molecular sieve, the amorphous silicon aluminum or the Y molecular sieve, the alumina are mechanically mixed and shaped, It is then dried and calcined to form a catalyst support, wherein the preparation method of the beta molecular sieve is as described above.
  • the carrier can be dried and calcined under conventional conditions, generally at 100 ° C to 150 ° C for 1 to 12 hours, and then at 450 ° C to 550 ° C for 2.5 to 6.0 hours.
  • the hydrocracking catalyst carrier of the present invention supports a hydrogenation active metal component (Group VIB and Group VIII metal components such as Co, Ni, Mo, W, etc.) by a conventional means such as kneading, dipping, and the like.
  • a hydrogenation active metal component Group VIB and Group VIII metal components such as Co, Ni, Mo, W, etc.
  • the dipping method may be saturated dipping, excessive dipping or complex dipping, that is, the catalyst carrier is impregnated with a solution containing the desired active component, and the impregnated carrier is dried at 100 ° C to 150 ° C for 1 to 12 hours, and then at 450 ° C to 550.
  • the final catalyst was obtained by calcination at ° C for 2.5 to 6.0 hours.
  • the alumina in the hydrocracking catalyst support of the present invention may be alumina used in a conventional hydrocracking catalyst such as macroporous alumina and/or small pore alumina.
  • the macroporous alumina used has a pore volume of 0.7 to 1.0 mL/g and a specific surface area of 200 to 500 m 2 /g.
  • the small pore alumina used has a pore volume of 0.3 to 0.5 mL/g and a specific surface area of 200 to 400 m 2 /g.
  • a conventional molding aid such as a peptizing acid, a squeezing agent or the like may be added.
  • the hydrocracking catalyst of the present invention can be used in the hydrocracking process of heavy distillates (VGO, CGO and DAO), and raw materials such as inferior diesel (coking diesel and catalytic diesel, etc.) can also be added.
  • VGO heavy distillates
  • CGO and DAO low distillates
  • inferior diesel coking diesel and catalytic diesel, etc.
  • the hydrogenation catalyst when the carrier comprises the above-mentioned ⁇ molecular sieve and alumina, can be used as a hydro-upgrading catalyst after being combined with the hydrogenation-active metal component.
  • the hydrotreating catalyst has a specific surface area of 200 to 400 m 2 /g and a pore volume of 0.35 to 0.60 mL/g.
  • the content of the ⁇ molecular sieve is 5% to 40%, and the content of the alumina is 60% to 95% based on the weight of the carrier.
  • the alumina is macroporous alumina and/or small pore alumina, and the macroporous alumina has a pore volume of 0.7 to 1.0 mL/g, a specific surface area of 200 to 500 m 2 /g, and a small pore alumina.
  • the pore volume is 0.3 to 0.5 mL/g, and the specific surface area is 200 to 400 m 2 /g.
  • the hydrogenation-active metal component is a metal of Group VIB and Group VIII
  • the metal of Group VIB is molybdenum and/or tungsten
  • the metal of Group VIII is cobalt and/or nickel.
  • the content of the Group VIB metal is from 10.0% to 30.0% based on the weight of the catalyst, and the content of the Group VIII metal in terms of the oxide is 4.0%. 8.0%.
  • the hydro-upgrading operating conditions include a total reaction pressure of 4 to 12 MPa, a volumetric space velocity of 1 to 3 h -1 , and a hydrogen to oil volume ratio. 400:1 to 2000:1, and the reaction temperature is 365 to 435 °C.
  • the preparation method of the hydrogenation upgrading catalyst of the invention comprises the preparation of a carrier and the loading of a hydrogenation active metal component, wherein the preparation process of the carrier is as follows: the zeolite molecular sieve and the alumina are mechanically mixed, shaped, then dried and calcined to prepare a catalyst.
  • the carrier can be dried and calcined under conventional conditions, generally at 100 ° C to 150 ° C for 1 to 12 hours, and then at 450 ° C to 550 ° C for 2.5 to 6.0 hours.
  • the hydro-modified catalyst carrier of the present invention supports a hydrogenation-active metal component (Group VIB and Group VIII metal components such as Co, Ni, Mo, W, etc.) by a conventional means such as kneading, dipping, and the like.
  • a hydrogenation-active metal component Group VIB and Group VIII metal components such as Co, Ni, Mo, W, etc.
  • the impregnation method may be saturated dip, excess dip or complex immersion, that is, impregnating the catalyst carrier with a solution containing the desired active component,
  • the impregnated support is dried at 100 ° C to 150 ° C for 1 to 12 hours, and then calcined at 450 ° C to 550 ° C for 2.5 to 6.0 hours to obtain a final catalyst.
  • the alumina in the hydro-modified catalyst support of the present invention may be alumina used in a conventional hydro-upgrading catalyst such as macroporous alumina and/or small-pore alumina.
  • the macroporous alumina used has a pore volume of 0.7 to 1.0 mL/g and a specific surface area of 200 to 500 m 2 /g.
  • the small pore alumina used has a pore volume of 0.3 to 0.5 mL/g and a specific surface area of 200 to 400 m 2 /g.
  • molding aids such as peptizing acid, co-extruding agents and the like may also be added during the preparation of the catalyst carrier of the present invention.
  • the ⁇ molecular sieve selected by the hydrogenation upgrading catalyst of the invention has suitable cracking action and good isomerization action on long-chain alkyl groups of long-chain alkanes and aromatic hydrocarbons and cycloalkanes, so that the catalyst maintains high diesel yield while maintaining high diesel yield.
  • the condensation point of the diesel fraction is greatly reduced, and the cetane number of the modified diesel oil is greatly increased, and the density and sulfur content of the diesel product are effectively reduced.
  • the hydrogenation upgrading catalyst of the invention is used for upgrading of inferior diesel fuel, especially in medium pressure conditions (4-12 MPa) and processing inferior diesel oil (catalytic diesel and coking diesel oil) with high catalytic activity and diesel yield, and diesel oil
  • inferior diesel oil catalytic diesel and coking diesel oil
  • the condensation point of the fraction is greatly reduced, and the cetane number of the modified diesel oil is greatly increased.
  • the density of the diesel product is effectively reduced, which can satisfy the refinery's increased operational flexibility, increase the processing capacity of the device, and further increase the quality of diesel produced. need.
  • the operating conditions of the hydrogenation upgrading catalyst of the invention for upgrading the inferior diesel oil are as follows: the total reaction pressure is 4.0 to 12.0 MPa, the volumetric space velocity is 1.0 to 3.0 h -1 , and the volume ratio of hydrogen to oil is 400:1 to 1000: 1, the reaction temperature is 345 ⁇ 435 ° C.
  • wt% is a mass fraction.
  • the specific surface area described in the present invention is measured by a low temperature liquid nitrogen adsorption method in accordance with the ASTM D3663-2003 standard.
  • the pore volume described in the present invention is determined by a low temperature liquid nitrogen adsorption method in accordance with the ASTM D4222-2003 standard.
  • the NH 3 -TPD method is a commonly used method for measuring the amount of molecular sieve acid
  • the instrument used is a Micro-Chem II 2920 chemical adsorption apparatus.
  • Ammonia gas was used as the adsorption and desorption medium, and helium gas (purity of 99.99 v%) was used as the carrier gas.
  • the acidity of different desorption temperature zones namely the weak acid amount, the medium strong acid amount and the strong acid amount, and the total amount were obtained by temperature-programmed desorption and chromatographic analysis. The amount of acid.
  • the specific operation procedure is as follows: 0.1 g of 20-40 mesh molecular sieve sample is taken, in the presence of helium gas (helium gas flow rate is 30 mL/min), the temperature is raised to 500 ° C, the temperature is kept for 1 hour, then lowered to 150 ° C, and the temperature is kept for 5 minutes. After that, the ammonia gas is introduced until the molecular sieve adsorption is saturated, and the helium gas is continuously purged (the helium gas flow rate is 30 mL/min), the temperature increase rate is 10 ° C / min, the temperature is raised to 250 ° C, the temperature is maintained for 1 hour, and then the temperature is further increased to 400.
  • helium gas flow rate is 30 mL/min
  • the ammonia desorption spectrum was recorded by a chromatograph.
  • the desorption temperature is divided into three temperature zones, namely, 150 ° C to 250 ° C, 250 ° C to 400 ° C, and 400 ° C to 500 ° C, respectively, corresponding to the acidity of weak acid, medium strong acid and strong acid, weak acid, The sum of the acid amounts of the medium strong acid and the strong acid is the total acid amount.
  • the unit of acid quantity is: mmol/g, that is, the amount of ammonia gas adsorbed per gram of molecular sieve.
  • the infrared acid amount of the invention is determined by infrared spectroscopy using pyridine as an adsorbent, and the instrument is a Nicolet 6700 Fourier infrared spectrometer of the American NICOLET company, and the process is as follows:
  • the pyridine was adsorbed to saturation, and the temperature was raised to 160 ° C, and the mixture was equilibrated for 1 hour to desorb the physically adsorbed pyridine (in this case, the length of the spring after adsorption of pyridine, x 3 , mm), and the pyridine weight adsorption method was used.
  • the total acid amount was obtained, and the infrared spectrum obtained under the above conditions was recorded, wherein the band corresponding to B acid was 1545 cm -1 and the band corresponding to L acid was 1455 cm -1 .
  • the amount of B acid was calculated according to the peak area ratio of each band. a ratio of the amount of L acid, thereby obtaining a total acid amount, a B acid amount, and an L acid amount;
  • the total acid amount is calculated by the pyridine weight adsorption method, as follows:
  • the relative crystallinity is determined by the XRD method, the instrument is a Rigaku Dmax-2500 X-ray diffractometer, using Cuk ⁇ radiation, graphite single crystal filtering, operating tube voltage 35 KV, tube current 40 mA, scanning speed (2 ⁇ ) is 2°/min and the scanning range is 4°-35°.
  • the standard is the ? molecular sieve original powder used in Example 1 of the present invention.
  • the silicon-aluminum molar ratio is chemically used; the sodium content is determined by plasma emission spectroscopy.
  • a 27 Al MAS NMR spectrum is obtained by a nuclear magnetic resonance spectroscopy (NMR method) to obtain a ratio of framework aluminum to non-framework aluminum, which is calculated as an atom of Al.
  • the 29 Si MAS NMR spectrum was obtained by NMR spectroscopy (NMR) to obtain silicon atoms in different coordination states (Si(4Al), Si(3Al), Si(2Al), Si(1Al) and Si(0Al )) The proportion of the form present, in terms of Si atom.
  • Nuclear magnetic resonance spectroscopy (NMR) was performed using a Bruker AVANCE III 500 NMR spectrometer with software using Topspin 2.0.
  • the standard material used in the measurement of the 29 Si MAS NMR spectrum was tetramethylsilane (TMS) with a resonance frequency of 99 MHz. Experimental conditions: 4-6 microsecond pulse width, 60-120 second relaxation delay.
  • the standard material used was aluminum trichloride, the resonance frequency was 133 MHz, and the experimental conditions were: 4-6 microsecond pulse width, 60-120 second relaxation delay.
  • Si(4Al) corresponds to a chemical shift of -81 to -96 ppm
  • Si(3Al) corresponds to a chemical shift of -96 to -100 ppm
  • Si(2Al) corresponds to a chemical shift of -100.
  • the chemical shift corresponding to Si(1Al) is -106 to -109 ppm
  • the chemical shift corresponding to Si(0Al) is -109 to -115 ppm).
  • the chemical shift of the framework aluminum is 40 to 65 ppm
  • the chemical shift of the non-framework aluminum is -10 to 10 ppm.
  • the weight of the template in the original molecular sieve of ⁇ zeolite is about 11.8%, provided by Sinopec Catalyst Fushun Branch), its chemistry
  • the SiO 2 /Al 2 O 3 molar ratio is 25.5, and the Na 2 O content is 2.45 wt%.
  • Si ( 4Al) was 7.6%
  • Si(3Al) was 30.6%
  • Si(2Al) was 32.3%
  • Si(1Al) was 21.0%
  • Si(0Al) was 8.5%.
  • the original zeolite molecular sieve powder was taken as in Example 1. 1000 g of the above molecular sieve was taken and placed in a tube furnace, and a temperature-programmed method (heating rate of 100 ° C / hour) was used. When the temperature of the tube furnace was raised to 300 ° C, 100 wt% of water vapor was introduced, and the flow rate of water vapor was At 70 L/hour, the tube furnace was heated to 600 ° C for a constant temperature of 8 hours.
  • the molecular sieve obtained was numbered BS-2.
  • the original zeolite molecular sieve powder was taken as in Example 1. Take 1000g of the above molecular sieve, put it into the tube furnace, and use the program temperature The method (heating rate is 100 ° C / hour), when the temperature of the tube furnace rises to 300 ° C, the introduction of 100 wt% of water vapor, the flow rate of water vapor is 70 L / hour, the tube furnace is heated to 650 ° C, constant temperature time It is 10 hours.
  • the molecular sieve obtained was numbered BS-3.
  • the weight of the template in the original molecular sieve of ⁇ zeolite is about 10.6%, provided by Sinopec Catalyst Fushun Branch), its chemistry
  • the SiO 2 /Al 2 O 3 molar ratio is 22.5, and the Na 2 O content is 2.35 wt%.
  • Si ( 4Al) was 7.7%
  • Si(3Al) was 31.5%
  • Si(2Al) was 30.9%
  • Si(1Al) was 21.9%
  • Si(0Al) was 8.0%.
  • the above-mentioned ⁇ -molecular sieve original powder 1000g was taken into a tube furnace, and a temperature-programmed method (temperature rising rate of 80 ° C / hour) was used, and when the temperature of the tube furnace was raised to 400 ° C, 100 wt% of water vapor was introduced, and water vapor was introduced.
  • the flow rate was 80 L/hour
  • the tube furnace was heated to 600 ° C for a constant temperature of 5 hours.
  • the molecular sieve obtained was numbered BS-4.
  • the weight of the template in the original molecular sieve of ⁇ zeolite is about 13.2%, provided by Sinopec Catalyst Fushun Branch), its chemistry
  • the SiO 2 /Al 2 O 3 molar ratio is 28.5, and the Na 2 O content is 2.75 wt%.
  • Si ( 4Al) was 8.8%
  • Si(3Al) was 28.7%
  • Si(2Al) was 31.3%
  • Si(1Al) was 23.5%
  • Si(0Al) was 7.7%.
  • the modified ⁇ molecular sieve was prepared by the method disclosed in CN 1393522A, and the number was BD-1, and the physicochemical properties are listed in Table 1. The specific process is as follows:
  • Molecular sieve BD-0 400 g of the ⁇ -molecular sieve BD-0 obtained by the above method was weighed and pulverized, and 4000 mL of 0.4 M HCl was added thereto, and the mixture was stirred and heated to 90° C., stirred at a constant temperature for 2 hours, and cooled and filtered for washing. The acid-treated ⁇ molecular sieve was washed by filtration, and then dried at 110 to 120 ° C for 6 hours (dry basis > 80 wt%).
  • the dried sample was uniformly sprayed with a predetermined amount of purified water, placed in a closed hydrothermal oven, heated to 650 ° C, controlled at 450 kPa, and baked at a constant temperature and constant pressure for 2.5 hours, and then naturally cooled to room temperature to obtain a ⁇ molecular sieve BD-1.
  • the ⁇ molecular sieve BSS-1 obtained in Example 6 of the present invention and the ⁇ molecular sieve BD-1 obtained in Comparative Example 1 were characterized by solid phase nuclear magnetic resonance of 500 MHz, and the respective 27 Al MAS NMR spectra were as shown in Fig. 1 and Fig. 2, respectively. Shown. In Fig. 1 and Fig. 2, the peak near 0 ppm corresponds to the six-coordinated non-framework aluminum, and the peak near 60 ppm corresponds to the tetracoordinated framework aluminum, and the peak area can be regarded as the ratio of the two aluminum structures. It can be seen from Fig.
  • the aluminum structure in the molecular sieve of Fig. 2 has a large number of six-coordinate non-framework aluminum structures, which almost reach more than 20% of the aluminum content in the molecular sieve.
  • the molecular sieve is prepared by the method of removing the template by using the ⁇ molecular sieve of CN 1166560C through ammonium exchange, and then removing the template.
  • the original zeolite molecular sieve powder was taken as in Example 1. Take the above-mentioned ⁇ -molecular sieve original powder 1000g, and put it into a closed hydrothermal treatment furnace. The temperature is programmed (heating rate is 100 ° C / hour), the hydrothermal treatment temperature is 600 ° C, the hydrothermal treatment pressure is 0.2 MPa, the treatment time is 3 hours, and the molecular sieve is used as the raw material for acidification after hydrothermal treatment, and the treatment condition is water intake. After heat treatment, 200 g of molecular sieve was treated with a hydrochloric acid solution having a concentration of 0.4 mol/L. The liquid solid ratio was 10:1, the treatment temperature was 95 ° C, and the treatment time was 2 hours.
  • the slurry was filtered to obtain a filter cake.
  • the liquid to solid ratio was 10:1
  • the washing time was 40 minutes
  • the washing was stopped after the pH of the washing liquid was close to 7.
  • the filter cake was dried in an oven at 120 ° C for 5 hours to obtain a ⁇ molecular sieve, numbered BD-3, and the physicochemical properties are listed in Table 1.
  • the ⁇ molecular sieve was prepared by the method of Example 6, except that the BS-1 molecular sieve was replaced by a BDS-4 molecular sieve prepared by the following method to obtain a ⁇ molecular sieve, numbered BD-4, and the physicochemical properties are shown in Table 1.
  • BDS-4 molecular sieve The original zeolite molecular sieve was taken as in Example 1. Take the above-mentioned ⁇ -molecular sieve original powder 1000g, and put it into a closed hydrothermal treatment furnace, using a temperature-programmed method (heating rate of 100 ° C / hour), hydrothermal treatment temperature of 550 ° C, hydrothermal treatment pressure of 0.2 MPa, and treatment time of 6 hours.
  • the sample number is BDS-4.
  • the BS-1 molecular sieve is subjected to vapor phase extraction of silicon.
  • 200 g of BS-1 molecular sieve was placed in a closed vessel, and vaporized silicon tetrachloride was introduced, the reaction temperature was 95 ° C, the reaction time was 2 hours, and the amount of silicon tetrachloride introduced was 9.8 g of SiCl 4 /100 g of molecular sieve.
  • the sample number is BD-5, and the physicochemical properties are listed in Table 1.
  • Example 6 The procedure of Example 6 was followed except that ammonium fluorosilicate was replaced with the same amount (mole) of tetraethyl orthosilicate, sample number BD-6, and the physicochemical properties are listed in Table 1.
  • the ⁇ molecular sieve was prepared according to the method of Example 6, except that the ⁇ molecular sieve raw powder was replaced by the same weight of the ⁇ -molecular sieve BD-0 prepared by the high-temperature calcination demineralization prepared in Comparative Example 1, to obtain a ⁇ molecular sieve, and the number was BD-7.
  • the physical and chemical properties are listed in Table 1.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst HC-1.
  • the properties of the support and the corresponding catalyst are shown in Table 2.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst HC-2.
  • the properties of the support and the corresponding catalyst are shown in Table 2.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst HC-3.
  • the properties of the support and the corresponding catalyst are shown in Table 2.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst HC-4.
  • the properties of the support and the corresponding catalyst are shown in Table 2.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst HC-5.
  • the properties of the support and the corresponding catalyst are shown in Table 2.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst HC-6.
  • the properties of the support and the corresponding catalyst are shown in Table 2.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst HC-7.
  • the properties of the support and the corresponding catalyst are shown in Table 2.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst HC-8.
  • the properties of the support and the corresponding catalyst are shown in Table 2.
  • the carrier was prepared according to the method of Example I-2 except that the BSS-1 molecular sieve was replaced by the same weight of zeolite molecular sieve BD-2 to obtain the carrier ZDS-1, and the properties are shown in Table 2.
  • the catalyst was prepared according to the method of Example I-2 using the above-mentioned carrier to obtain a catalyst HCD-1.
  • the properties of the support and the corresponding catalyst are shown in Table 2.
  • the carrier was prepared according to the method of Example I-3 except that the BSS-5 molecular sieve was replaced by the same weight of zeolite molecular sieve BD-3 to obtain the carrier ZDS-2, and the properties are shown in Table 2.
  • the catalyst was prepared by the method of Example I-3 using the above carrier to obtain a catalyst HCD-2.
  • the properties of the support and the corresponding catalyst are shown in Table 2.
  • the carrier was prepared according to the method of Example I-4 except that the BSS-5 molecular sieve was replaced by the same weight of zeolite molecular sieve BD-1 to obtain the carrier ZDS-3, and the properties are shown in Table 2.
  • the catalyst was prepared by the method of Example I-4 using the above carrier to obtain a catalyst HCD-3.
  • the properties of the support and the corresponding catalyst are shown in Table 2.
  • the carrier was prepared according to the method of Example I-2 except that the BSS-1 molecular sieve was replaced by the same weight of zeolite molecular sieve BD-4 to obtain the carrier ZDS-4, and the properties are shown in Table 2.
  • the catalyst was prepared according to the method of Example I-2 using the above-mentioned carrier to obtain a catalyst HCD-4, and the properties of the support and the corresponding catalyst are shown in Table 2.
  • the carrier was prepared according to the method of Example I-2 except that the BSS-1 molecular sieve was replaced by the same weight of zeolite molecular sieve BD-5 to obtain the carrier ZDS-5, and the properties are shown in Table 2.
  • the catalyst was prepared according to the method of Example I-2 using the above carrier to obtain a catalyst HCD-5.
  • the properties of the support and the corresponding catalyst are shown in Table 2.
  • the carrier was prepared according to the method of Example I-2 except that the BSS-1 molecular sieve was replaced by the same weight of zeolite molecular sieve BD-6 to obtain the carrier ZDS-6, and the properties are shown in Table 2.
  • the catalyst was prepared according to the method of Example I-2 using the above carrier to obtain a catalyst HCD-6.
  • the properties of the support and the corresponding catalyst are shown in Table 2.
  • the carrier was prepared according to the method of Example I-2 except that the BSS-1 molecular sieve was replaced by the same weight of zeolite molecular sieve BD-7 to obtain the carrier ZDS-7, and the properties are shown in Table 2.
  • the catalyst was prepared according to the method of Example I-2 using the above-mentioned carrier to obtain a catalyst HCD-7.
  • the properties of the support and the corresponding catalyst are shown in Table 2.
  • Example number I-1 I-2 I-3 I-4 I-5 I-6 I-7 I-8 Carrier Numbering ZS-1 ZS-2 ZS-3 ZS-4 ZS-5 ZS-6 ZS-7 ZS-8 Beta molecular sieve, wt% 7 15 10 20 5 10 15 7 Amorphous silicon aluminum, wt% 40 30 25 50 45 40 50 20 Alumina margin margin margin margin margin margin margin margin margin margin margin Porosity, mL/g 0.74 0.73 0.75 0.68 0.76 0.72 0.67 0.78 Specific surface area, m 2 /g 415 440 431 456 428 430 416 443 catalyst Numbering HC-1 HC-2 HC-3 HC-4 HC-5 HC-6 HC-7 HC-8 WO 3 , wt% 17.5 21.5 22.9 27.6 21.6 23.5 21.8 27.0 NiO, wt% 4.3 5.3 5.6 7.5 5.4 5.5 5.4 6.7 Porosity, mL/g 0.58 0.55 0.52 0.44 0.53 0.51 0.38 0.49
  • the evaluation was carried out on a fixed bed hydrogenation test apparatus under the following conditions: a total reaction pressure of 15.0 MPa, a hydrogen oil volume ratio of 1500, a liquid hour volume space velocity of 0.9 h -1 , and a vacuum distillate oil (VGO) as a raw material oil, a raw material.
  • the oil properties are listed in Table 3.
  • the catalysts HC-1 to HC-8 and HCD-1 to HCD-7 were evaluated under the same process conditions, and the evaluation results obtained are shown in Table 4.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst FC-1.
  • the properties of the support and the corresponding catalyst are shown in Table 5.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst FC-2.
  • the properties of the support and the corresponding catalyst are shown in Table 5.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst FC-3.
  • the properties of the support and the corresponding catalyst are shown in Table 5.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst FC-4.
  • the properties of the support and the corresponding catalyst are shown in Table 5.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst FC-5.
  • the properties of the support and the corresponding catalyst are shown in Table 5.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst FC-6.
  • the properties of the support and the corresponding catalyst are shown in Table 5.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst FC-7.
  • the properties of the support and the corresponding catalyst are shown in Table 5.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst FCD-1.
  • the properties of the support and the corresponding catalyst are shown in Table 5.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst FCD-2.
  • the properties of the support and the corresponding catalyst are shown in Table 5.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst FDC-3.
  • the properties of the support and the corresponding catalyst are shown in Table 5.
  • the carrier was prepared according to the method of Example II-4 except that the BSS-3 molecular sieve was replaced by the same weight of the zeolite molecular sieve BD-2 to obtain the carrier DS-4, and the properties are shown in Table 5.
  • the catalyst was prepared according to the method of Example II-4 using the above carrier to obtain a catalyst FCD-4.
  • the properties of the support and the corresponding catalyst are shown in Table 5.
  • the carrier was prepared according to the method of Example II-2 except that the BSS-1 molecular sieve was replaced by the same weight of zeolite molecular sieve BD-4 to obtain the carrier DS-5, and the properties are shown in Table 5.
  • the catalyst was prepared according to the method of Example II-2 using the above carrier to obtain a catalyst FCD-5.
  • the properties of the support and the corresponding catalyst are shown in Table 5.
  • the carrier was prepared according to the method of Example II-2 except that the BSS-1 molecular sieve was replaced by the same weight of the ⁇ molecular sieve BD-5 to obtain the carrier DS-6, and the properties are shown in Table 5.
  • the catalyst was prepared according to the method of Example II-2 using the above carrier to obtain a catalyst FCD-6.
  • the properties of the support and the corresponding catalyst are shown in Table 5.
  • the carrier was prepared according to the method of Example II-2 except that the BSS-1 molecular sieve was replaced by the same weight of the ⁇ molecular sieve BD-6 to obtain the carrier DS-7, and the properties are shown in Table 5.
  • the catalyst was prepared according to the method of Example II-2 using the above carrier to obtain a catalyst FCD-7.
  • the properties of the support and the corresponding catalyst are shown in Table 5.
  • the carrier was prepared according to the method of Example II-2 except that the BSS-1 molecular sieve was replaced by the same weight of zeolite molecular sieve BD-7 to obtain the carrier DS-8, and the properties are shown in Table 5.
  • the catalyst was prepared according to the method of Example II-2 using the above carrier to obtain a catalyst FCD-8.
  • the properties of the support and the corresponding catalyst are shown in Table 5.
  • Example number II-1 II-2 II-3 II-4 II-5 II-6 II-7 Carrier Numbering S-1 S-2 S-3 S-4 S-5 S-6 S-7 Beta molecular sieve, wt% 10 15 5 20 15 5 15 Y type molecular sieve, wt% 20 20 30 25 30 35 15 Alumina margin margin margin margin margin margin margin Porosity, mL/g 435 452 463 489 496 486 443 Specific surface area, m 2 /g 0.68 0.65 0.66 0.67 0.65 0.64 0.69 catalyst Numbering FC-1 FC-2 FC-3 FC-4 FC-5 FC-6 FC-7 WO 3 , wt% 22.36 21.63 22.06 22.18 24.36 26.78 22.36 NiO, wt% 5.4 5.5 5.3 5.5 5.9 6.3 5.2 Specific surface area, m 2 /g 330 327 332 349 365 357 352
  • the evaluation was carried out on a fixed bed hydrogenation test apparatus under the following conditions: a total reaction pressure of 15.0 MPa, a hydrogen oil volume ratio of 1500, a volumetric space velocity of 1.5 h -1 , and a vacuum distillate oil (VGO) as a feedstock oil. As shown in Table 3 above. Catalysts FC-1 to FC-7 and FCD-1 to FCD-8 were evaluated under the same process conditions, and the evaluation results obtained are shown in Table 6.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst LC-1.
  • the properties of the support and the corresponding catalyst are shown in Table 7.
  • BSS-2 molecular sieve dry basis 90 wt%), 171.4 g of macroporous alumina (pore volume 1.0 mL/g, specific surface area 400 m 2 /g, dry basis 70 wt%), 133.3 g of binder (dry basis 30 wt%) %, the molar ratio of nitric acid to small pore alumina is 0.4), mixed in a roller compactor, added with water, crushed into a paste, extruded, extruded strips dried at 110 ° C for 4 hours, then baked at 550 ° C 4 In hours, the carrier CS-2 was obtained, and the properties are shown in Table 7.
  • the support was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, 120 (2 dry for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst LC-2.
  • the properties of the support and the corresponding catalyst are shown in Table 7.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst LC-3.
  • the properties of the support and the corresponding catalyst are shown in Table 7.
  • BSS-6 molecular sieve dry basis 90 wt%), 128.6 g of macroporous alumina (pore volume 1.0 mL/g, specific surface area 400 m 2 /g, dry basis 70 wt%), 133.3 g of binder (dry basis 30 wt %, the molar ratio of nitric acid to small pore alumina is 0.4), mixed in a roller compactor, added with water, crushed into a paste, extruded, extruded strips dried at 110 ° C for 4 hours, then baked at 550 ° C 4 In hours, the carrier CS-4 was obtained, and the properties are shown in Table 7.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst LC-4.
  • the properties of the support and the corresponding catalyst are shown in Table 7.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst LC-5.
  • the properties of the support and the corresponding catalyst are shown in Table 7.
  • BSS-7 molecular sieve dry basis 90 wt%), 114.2 g of macroporous alumina (pore volume 1.0 mL/g, specific surface area 400 m 2 /g, dry basis 70 wt%), 133.3 g of binder (dry basis 30 wt %, the molar ratio of nitric acid to small pore alumina is 0.4), mixed in a roller compactor, added with water, crushed into a paste, extruded, extruded strips dried at 110 ° C for 4 hours, then baked at 550 ° C 4 In hours, the carrier CS-6 was obtained, and the properties are shown in Table 7.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst LC-6.
  • the properties of the support and the corresponding catalyst are shown in Table 7.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst LC-7.
  • the properties of the support and the corresponding catalyst are shown in Table 7.
  • the carrier was immersed in an impregnation solution containing tungsten and nickel at room temperature for 2 hours, dried at 120 ° C for 4 hours, and calcined at 500 ° C for 4 hours to obtain a catalyst LC-8.
  • the properties of the support and the corresponding catalyst are shown in Table 7.
  • the carrier was prepared according to the procedure of Example III-2 except that the BSS-2 molecular sieve was replaced by the same weight of zeolite molecular sieve BD-2 to obtain the carrier CDS-1, and the properties are shown in Table 7.
  • the catalyst was prepared according to the method of Example III-2 using the above-mentioned carrier to obtain a catalyst LCD-1, and the properties of the support and the corresponding catalyst are shown in Table 7.
  • the carrier was prepared according to the procedure of Example III-3 except that the BSS-6 molecular sieve was replaced by the same weight of zeolite molecular sieve BD-3 to obtain the carrier CDS-2, and the properties are shown in Table 7.
  • the catalyst was prepared according to the procedure of Example III-3 using the above-mentioned carrier to obtain a catalyst LCD-2.
  • the properties of the support and the corresponding catalyst are shown in Table 7.
  • the carrier was prepared according to the procedure of Example III-7, except that the BSS-8 molecular sieve was replaced by the same weight of zeolite molecular sieve BD-1 to obtain the carrier CDS-3, and the properties are shown in Table 7.
  • the catalyst was prepared according to the procedure of Example III-3 using the above-mentioned carrier to obtain a catalyst LCD-3.
  • the properties of the support and the corresponding catalyst are shown in Table 7.
  • the carrier was prepared according to the procedure of Example III-8 except that the BSS-1 molecular sieve was replaced by the same weight of zeolite molecular sieve BD-4 to obtain the carrier CDS-4, and the properties are shown in Table 7.
  • the catalyst was prepared according to the procedure of Example III-8 using the above-mentioned carrier to obtain the catalyst LCD-4, and the properties of the support and the corresponding catalyst are shown in Table 7.
  • the carrier was prepared according to the procedure of Example III-8, except that the BSS-1 molecular sieve was replaced by the same weight of zeolite molecular sieve BD-5 to obtain the carrier CDS-5, and the properties are shown in Table 7.
  • the catalyst was prepared according to the procedure of Example III-8 using the above-mentioned carrier to obtain the catalyst LCD-5.
  • the properties of the support and the corresponding catalyst are shown in Table 7.
  • the carrier was prepared according to the procedure of Example III-8, except that the BSS-1 molecular sieve was replaced by the same weight of zeolite molecular sieve BD-6 to obtain the carrier CDS-6, and the properties are shown in Table 7.
  • the catalyst was prepared according to the procedure of Example III-8 using the above carrier to obtain the catalyst LCD-6.
  • the properties of the support and the corresponding catalyst are shown in Table 7.
  • the carrier was prepared according to the procedure of Example III-8 except that the BSS-1 molecular sieve was replaced by the same weight of zeolite molecular sieve BD-7 to obtain the carrier CDS-7, and the properties are shown in Table 7.
  • the catalyst was prepared according to the method of Example III-8 using the above carrier to obtain a catalyst LCD-7.
  • the properties of the support and the corresponding catalyst are shown in Table 7.
  • Beta molecular sieve wt% 20 30 10 15 15 15 15 Alumina margin margin margin margin margin margin margin margin margin Specific surface area, m 2 /g 385 406 355 421 369 388 369 Porosity, mL/g 0.64 0.59 0.68 0.54 0.62 0.58 0.57 catalyst Numbering LCD-1 LCD-2 LCD-3 LCD-4 LCD-5 LCD-6 LCD-7 WO 3 , wt% 25.3 22.9 22.5 23.6 23.8 23.7 23.5 NiO, wt% 6.5 6.0 6.4 6.2 6.3 6.1 6.2
  • the evaluation was carried out on a fixed bed hydrogenation test apparatus under the following conditions: a total reaction pressure of 10.0 MPa, a hydrogen oil volume ratio of 600, and a volumetric space velocity of 2.0 h -1 .
  • Catalytic diesel was used as a feedstock oil, and the properties of the feedstock oil are shown in Table 8.
  • Catalysts LC-1 to LC-8 and LCD-1 to LCD-7 were evaluated under the same process conditions, and the evaluation results obtained are shown in Table 9.

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Abstract

本发明公开了一种β分子筛及其制备方法和含有该β分子筛的加氢催化剂。该β分子筛的性质如下：SiO2/Al2O3摩尔比30∼150，非骨架铝占总铝的2%以下，以Si(0Al)结构配位的硅原子占骨架结构中的硅原子的95%以上。制备方法包括：将β分子筛原粉与常压、动态的水蒸汽条件接触，然后与氟硅酸铵接触。本发明β分子筛具有骨架硅铝结构均一、酸性适宜、孔结构合理的特点，适宜作为柴油加氢改质催化剂以及加氢裂化催化剂的酸性组分。

Description

β分子筛及其制备方法和含有该β分子筛的加氢催化剂 技术领域
本发明涉及一种β分子筛及其制备方法和含有该β分子筛的加氢催化剂。该β分子筛可作为加氢裂化催化剂的活性组分，可以作为柴油加氢改质催化剂的活性组分。
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、劣质原料直接转化为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，在世界各国获得日益广泛的应用，加氢裂化技术已成为现代炼油行业“油-化-纤”结合的核心技术。加氢改质技术是在较为缓和的工艺条件下，将各种劣质柴油馏分转化为高品质的柴油产品或其调和组分，能够有效改善柴油产品质量，尤其是大幅度降低柴油产品密度、芳烃含量、硫氮含量和T95点，同时柴油产品的十六烷值获得大幅度提升，个别催化剂还具有降低柴油产品凝点的能力，加氢改质技术是炼化企业劣质柴油改质理想的技术。
目前在加氢催化剂中起裂化作用的关键组分多为Y型分子筛和β分子筛。相对于Y型分子筛，β分子筛具有三维十二元环孔结构，但没有像Y型分子筛那样的超笼结构，其主要特点是两个4元环和四个5元环的双6元环单位晶穴结构，属于立方晶系。β分子筛硅铝结构具有多样性和复杂性。β分子筛的骨架结构相比于Y型分子筛更加复杂，三个相互交叉的孔道体系中两个线性孔道相互正交并垂直于[001]方向，孔道尺寸为0.57nm×0.75nm，第三个十二元环孔道体系平行于[001]方向，是非线性孔道，孔道尺寸为0.56nm×0.65nm；晶化完全的β分子筛骨架硅铝结构也存在多样性，骨架硅铝结构是四配位结构且这种结构占分子筛中总的硅铝存在形式的主体，其基本结构是由含量不同的Si(4Al)、Si(3Al)、Si(2Al)、Si(1Al)和Si(0Al)结构单元组成，并且以Si(3Al)和Si(2Al)结构形式为主，另外分子筛中还存在着六配位的非骨架铝，这些各种结构的硅铝存在方式及含量在后续的不同改性过程中发生不同的变化，从而将产生不同的催化性能。
现有对β分子筛的改性方法(比如CN 1105646A)中，一般是先进行铵交换脱钠，然后高温焙烧除去模板剂(有机胺)，再进行脱铝和恒压水热处理，这样可以大幅度提 高β分子筛的硅铝比。尤其是高温焙烧除胺的过程，在CN 1157258C、CN 1166560C等专利中特别强调分段焙烧脱胺，这样不但制备过程复杂，而且在分段烧铵前分子筛要先经过铵盐交换钠，钠离子是用于平衡分子筛骨架中的负电荷(一般为骨架铝形成的)，而脱钠后再进行的烧铵处理(无论是一步高温处理还是多步不同温度处理)将使分子筛骨架脱铝加剧，并存在无选择性骨架脱铝，使改性后分子筛的骨架结构不均一，存在非常大的缺陷，并在孔道中形成了大量的六配位的非骨架铝结构(堵塞孔道，部分掩蔽骨架酸中心，易发生非理想裂化反应)，而后续的酸处理或水热处理，都将继续对分子筛的骨架结构进一步破坏，使分子筛骨架结构中存在着比例不同的Si(X-Al)结构和分子筛中存在一定量的非骨架铝结构，使得分子筛具有不同强度酸中心，表现出不同的裂化性能，将大大影响催化剂目的产物的选择性。正是由于β分子筛中硅铝结构的复杂性，采用上述不同的改性方法使得改性后分子筛骨架结构不均一，直接影响改性分子筛的酸强度和酸密度，进而影响催化剂的性能。
CN 101450318A中公开了一种β分子筛的改性方法。该方法是将钠型β分子筛与铵盐交换，再用含磷化合物溶液和含有过渡金属化合物的溶液对分子筛进行浸渍改性，得到的β分子筛具有更高的比表面积和更高的相对结晶度，能够进一步择形裂化生成低碳烯烃。
CN 1393522A公开了一种β分子筛的改性方法。该方法过程如下：(1)晶化完全的β分子筛直接进行铵盐交换，(2)铵盐交换后的β分子筛进行过滤、水洗、干燥和焙烧，(3)焙烧脱铵后的β分子筛进行酸处理、过滤，(4)酸处理完的β分子筛进行加压水热处理。该方法中，先对β沸石进行酸处理，然后再进行水热处理，在酸处理过程中是采用无机酸处理的，在这一过程中将会破坏部分分子筛的骨架结构，分子筛结晶度下降，形成大块的非骨架结构留在分子筛孔道中，难以被除去，影响改性分子筛的酸分布和酸强度。另外，在酸处理后还进行了高温水热处理，也会在分子筛中形成一定量的非骨架铝，这将直接影响分子筛的孔结构和酸性质，分子筛的酸分布和酸性质的变化将直接影响由此分子筛作为裂化组分的催化剂的性能，尤其是影响加氢裂化柴油和化工料的性质。另外该方法改性分子筛的步骤较长，制备过程中目的分子筛的收率较低，同时多步骤的改性处理使得改性成本和能耗大大提高。US 5,350,501、US 5,447,623、US 5,279,726、US 5,536,687介绍了一种含β分子筛和Y分子筛的催化剂。用于生产中间馏分油时，其组成为：Y分子筛(1～15wt％)，β分子筛(1～15wt％)，分散型硅铝，氧化铝，金属W和Ni。其中所用的β分子筛是经离子交换和焙烧除去模板剂的方 式得到氢型β分子筛。该催化剂反应活性和中油选择性都不是很高，难以满足生产厂家增大装置处理能力，进一步增产中间馏分油的需要。
CN 1393521A公开了一种中油型加氢裂化催化剂及其制备方法，催化剂所用载体为无定形硅铝、氧化铝、Y和β的复合型分子筛。其中复合分子筛是将β分子筛原粉高温烧去模板剂后与改性Y分子筛混合后，再经H+和NH4 +混合溶液处理而得。该方法是将β分子筛原粉先高温烧去模板剂，这样会影响分子筛的骨架结构，并大幅度降低分子筛的结晶度，同时也影响分子筛的酸性，由此方法制备的催化剂的催化活性不高，航煤和柴油的中间馏分油的产品质量仍需进一步提高。
发明内容
为了克服现有技术中的不足之处，本发明提供了一种骨架硅铝结构均一的β分子筛及其制备方法和还有含该β分子筛的加氢催化剂。该β分子筛进一步还具有酸性适宜、孔结构合理的特点。该方法改性步骤少、目的改性分子筛的收率高和制备成本低。由本发明β分子筛为裂化组分制备的加氢裂化催化剂，适用于重质馏分油加氢裂化生产低凝柴油和改善加氢尾油性质。由本发明β分子筛与Y型分子筛共同作为裂化组分制备的加氢裂化催化剂，适用于重质馏分油加氢裂化生产优质中间馏分油。由本发明β分子筛为裂化组分制备柴油加氢改质催化剂，用于劣质柴油原料改质生产具有十六烷值高、密度降低幅度大和凝点低等特点的优质柴油。
根据本发明的第一方面，本发明提供了一种β分子筛，其性质如下：SiO2/Al2O3摩尔比为30～150，优选为40～150，非骨架铝占总铝的2％以下，优选为1％以下，以Si(0Al)结构配位的硅原子占骨架结构中硅原子的95％以上，优选为95％～99％，进一步优选为96％～99％。
根据本发明的第二方面，本发明提供了一种β分子筛的制备方法，该方法包括：
(1)将β分子筛原粉与常压、动态的水蒸汽接触，接触的温度为500～650℃，时间为5～10小时；
(2)将步骤(1)所得的产物与氟硅酸铵接触，然后过滤、水洗和干燥，得到β分子筛。
根据本发明的第三方面，本发明提供了一种加氢催化剂，该加氢催化剂包含加氢活性金属组分和载体，其中载体包含本发明提供的上述β分子筛。
优选地，所述加氢催化剂的载体还含有氧化铝。
优选地，所述加氢催化剂的载体还含有Y型分子筛和/或无定形硅铝。
本发明提供的β分子筛具有骨架硅铝结构均一、酸性适宜、孔结构合理等特点，作为裂化组分时，能够使催化剂具有更高的催化活性和异构能力。
以β分子筛为酸性组分的裂化催化剂，添加适宜的无定形硅铝为第二裂化组分，既充分发挥了其各自的性能特点，又产生了较好的协同催化作用，使加氢裂化催化剂在活性提高的同时，又具有良好的环烷烃选择性开环、链烷烃异构化、重馏分适度加氢裂化、芳烃饱和及杂原子脱除性能。使加氢裂化催化剂具有活性高，可最大量生产低凝点柴油，同时可兼产优质的加氢尾油。
采用β分子筛与Y型分子筛共同作为裂化中心的加氢催化剂可以作为加氢裂化催化剂使用，该加氢裂化催化剂既能够充分发挥各自的性能特点，又能够使两种分子筛产生协同催化作用，即β分子筛对链烷烃或芳烃上的长侧链有很好的异构作用，可以有效降低产品的凝点，同时Y型分子筛对芳烃有很高开环选择性，提高目的产品的产品性质。由此该加氢裂化催化剂具有活性高，可多产优质中间馏分油产品(航煤+柴油)，同时可兼产优质的加氢尾油。
由本发明β分子筛为裂化组分制备的柴油加氢改质催化剂，非常适合用于劣质柴油原料改质生产具有十六烷值高、密度降低幅度大和凝点低等特点的优质柴油。
附图说明
图1为：实施例6中本发明β分子筛的27Al MAS NMR谱图，其中横坐标为ppm；
图2为：比较例1中对比分子筛27Al MAS NMR谱图，其中横坐标为ppm。
具体实施方式
(一)β分子筛
根据本发明的第一方面，本发明提供了一种β分子筛，其性质如下：SiO2/Al2O3摩尔比为30～150，优选为40～150，进一步优选为60～120，非骨架铝占总铝的2％以下，优选为1％以下，以Si(0Al)结构配位的硅原子占骨架结构中硅原子的95％以上，优选为95％～99％，进一步优选为96％～99％。
本发明提供的β分子筛，其性质优选如下：相对结晶度为100％～140％。
本发明提供的β分子筛，其性质优选如下：红外酸量为0.1～0.5mmol/g，优选0.15～0.45mmol/g，NH3-TPD方法测得的中强酸的酸量占总酸量的80％以上，优选为80％～95％，进一步优选为85％～95％。
本发明提供的β分子筛，其性质优选如下：Na2O≤0.15wt％，优选为Na2O≤0.10wt％。
本发明提供的β分子筛，其性质优选如下：比表面积为400m2/g～800m2/g，优选为500m2/g～700m2/g，总孔容为0.30mL/g～0.50mL/g。
本发明的β分子筛中，总铝是指分子筛中骨架铝中的铝和非骨架铝中的铝的总和。非骨架铝是指分子筛中以六配位结构形式存在的铝。骨架铝是指分子筛中以四配位结构形式存在的铝。骨架结构中的硅原子(也称骨架硅原子)，即以Si(4Al)、Si(3Al)、Si(2Al)、Si(1Al)和Si(0Al)结构配位的硅原子的总和。其中，Si(4Al)、Si(3Al)、Si(2Al)、Si(1Al)和Si(0Al)是与硅氧四面体中的硅原子呈不同配位状态的四配位结构(即骨架结构)，Si(4Al)是指硅氧四面体中的硅原子只与4个铝氧四面体直接相连的四配位结构即Si[(OAl)4]，Si(3Al)是指硅氧四面体中的硅原子与3个铝氧四面体和1个硅氧四面体直接相连的四配位结构即Si[(OAl)3(OSi)1]，Si(2Al)是硅氧四面体中的硅原子与2个铝氧四面体和2个硅氧四面体直接相连的四配位结构即指Si[(OAl)2(OSi)2]，Si(1Al)是指硅氧四面体中的硅原子与1个铝氧四面体和3个硅氧四面体直接相连的四配位结构Si[(OAl)1(OSi)3]，Si(0Al)是指硅氧四面体中的硅原子只与4个硅氧四面体直接相连的四配位结构Si[(OSi)4]。
本发明中，采用核磁共振波谱法(NMR法)得到27Al MAS NMR谱图，从而得到骨架铝及非骨架铝的比例，以Al原子计。采用核磁共振波谱法(NMR法)得到29Si MAS NMR谱图，从而得到硅原子以不同配位状态(Si(4Al)、Si(3Al)、Si(2Al)、Si(1Al)和Si(0Al))形式存在的比例，以Si原子计。
本发明β分子筛的制备方法，包括以下步骤：
(1)将β分子筛原粉与常压、动态的水蒸汽接触，接触的温度为500～650℃，时间为5～10小时；
(2)将步骤(1)所得的产物与氟硅酸铵接触，然后过滤、水洗和干燥，得到β分子筛。
步骤(1)中，β分子筛原粉与常压、动态的水蒸汽接触的方式，优选为将β分子筛原粉置于容器中，然后从容器的一端引入水蒸汽，通过β分子筛原粉后从容器的另一端排出。为了使分子筛处理的更均匀，最好将分子筛置于转动容器比如管式炉中，水蒸汽从容器的一端进入经过分子筛后再从容器的另一端出去。容器内的压力保持常压状态，处理温度保持在500～650℃，处理时间为5～10小时。
优选情况下，步骤(1)采用程序升温，升温速率为50～150℃/小时，升至250～450℃ 时，开始引入水蒸汽，并继续升温至500～650℃，然后在此温度下停留5～10小时。
优选情况下，步骤(1)β分子筛原粉是采用常规的水热法合成的，通常采用有机胺为模板剂，常用的有机胺模板剂可以采用四乙基氢氧化铵、四甲基氢氧化铵、四乙基溴化铵等中的一种或多种。β分子筛原粉中通常含有模板剂，且模板剂的重量含量一般为10％～15％。β分子筛原粉的性质如下：SiO2/Al2O3摩尔比为22.5～28.5，Na2O含量为1.0wt％～3.0wt％。β分子筛原粉中模板剂含量可以采用差示扫描量热法(DSC)-热重法(TG)得到，其中热重法是采用德国Netzsch公司STA449C-QMS403C型仪器，是在氩气气氛下，气体流量为25mL/min，升温速率为10℃/min，温度从室温升至600℃，样品质量约10mg，取150℃～500℃间β分子筛原粉的减重量计为模板剂的量。
步骤(1)β分子筛原粉在常压、动态的水蒸汽条件处理，采用100wt％水蒸汽，水蒸汽按每千克β分子筛原粉50～100L/h通过分子筛原粉。
步骤(2)将步骤(1)所得的产物与氟硅酸铵接触。所述接触的条件包括：温度为40～120℃，优选为70～100℃，时间为0.5～8.0小时，优选为1.0～3.0小时。
优选情况下，步骤(2)采用氟硅酸铵水溶液与步骤(1)所得的β分子筛接触，氟硅酸铵水溶液的浓度是10g～60g/100mL溶液，氟硅酸铵水溶液与β分子筛的液固体积比为3∶1～15∶1。
将步骤(2)接触后的浆液直接过滤，过滤后的滤饼再经过数次水洗。其中所述水洗一般采用去离子水进行洗涤，直到洗涤液pH值接近中性为止。洗涤温度可以为50～100℃，优选为60～90℃，液固体积比一般为5∶1～15∶1，洗涤时间为0.5～1.0小时，以洗涤液pH值接近中性为止。所述干燥优选在100～120℃的条件下干燥3～6小时。
本发明方法改性的β分子筛的收率在85wt％以上。
本发明的β分子筛具有骨架硅铝结构均一、酸性适宜、孔结构合理等特点，适宜作为裂化组分，使催化剂具有更高的催化活性和异构能力。
本发明方法首先采用常压、动态水热处理分子筛原粉，并不需要经过铵交换等预处理过程，在动态高温水蒸汽的作用下可以实现分子筛脱铵(脱模板剂)和选择性降低骨架铝活化能，并避免了对分子筛骨架结构的破坏，保持分子筛骨架结构的均一性，与后续的六氟硅酸铵改性过程相配合，能够有效地将低能量的骨架铝均匀脱出，并在骨架上补充硅原子，使分子筛的骨架结构更加均一和稳定，同时分子筛中的钠离子也一同被带出，可将分子筛中的钠含量脱到0.15wt％以下，从而克服了现有技术中进行多步铵交换(洗钠)和能耗高、污染大等缺点。本发明方法通过六氟硅酸铵能够进一步畅通孔道结 构，能够将产生的非骨架铝从分子筛孔道中脱出，达到了脱出非骨架铝和使分子筛孔道更加通畅的目的。本发明通过优化改性方法，使改性后的分子筛具有骨架硅铝结构均一、孔结构合理、酸性中心强度和酸密度分布更加均匀，有利于提供均匀的裂化中心，提高催化剂的目的产品选择性。
(二)加氢裂化催化剂
根据本发明，本发明的加氢催化剂包含加氢活性金属组分和载体，其中载体包含上述β分子筛、无定形硅铝和/或Y型分子筛、以及氧化铝时，该加氢催化剂具有加氢裂化功能，因而是一种加氢裂化催化剂。优选地，所述加氢裂化催化剂的比表面积是200～400m2/g，孔容是0.35～0.60mL/g。
为区别起见，本发明将载体包含上述β分子筛、无定形硅铝以及氧化铝的加氢催化剂称为第一加氢裂化催化剂，将载体包含上述β分子筛、Y型分子筛、以及氧化铝的加氢催化剂称为第二加氢裂化催化剂。
优选情况下，所述第一加氢裂化催化剂载体中，以载体的重量为基准，β分子筛的含量为3％～20％，无定形硅铝的含量为10％～70％，优选为25％～55％，氧化铝的含量为15％～70％，优选为25％～62％。
优选地，所述无定形硅铝中SiO2的重量含量为5％～40％，无定形硅铝的孔容为0.6～1.1mL/g，比表面积为300～500m2/g。
优选地，所述氧化铝为大孔氧化铝和/或小孔氧化铝，大孔氧化铝的孔容0.7～1.0mL/g，比表面积200～500m2/g，小孔氧化铝的孔容为0.3～0.5mL/g，比表面积为200～400m2/g。
优选地，所述第一加氢裂化催化剂中，以催化剂的总量为基准，第VIB族金属以氧化物计的重量含量为10.0％～30.0％，第VIII族金属以氧化物计的重量含量为4.0％～8.0％。
优选地，所述加氢活性金属组分为第VIB族和/或第VIII族的金属，第VIB族的金属为钼和/或钨，第VIII族的金属为钴和/或镍。
上述第一加氢裂化催化剂以β分子筛为酸性组分，尤其是添加适宜的无定形硅铝为第二裂化组分，既充分发挥了其各自的性能特点，又产生了较好的协同催化作用，使加氢裂化催化剂在活性提高的同时，又具有良好的环烷烃选择性开不、链烷烃异构化、重馏分适度加氢裂化、芳烃饱和及杂原子脱除性能，使加氢裂化催化剂具有活性高，可最大量生产优质低凝柴油，同时可兼产优质的加氢尾油。
上述第一加氢裂化催化剂可以用于以重质馏分油为原料油加氢裂化生产低凝柴油， 同时可兼产优质的加氢尾油。优选地，加氢裂化采用单段工艺流程，反应总压12～20MPa，体积空速0.5～3.0h-1，氢油体积比为800∶1～2000∶1，反应温度365～435℃。
优选情况下，所述第二加氢裂化催化剂载体中，以载体的重量为基准，β分子筛的含量为5％～20％，Y型分子筛的含量为10％～40％，氧化铝的含量为40％～85％。
优选情况下，所述Y型分子筛的比表面积为850m2/g～950m2/g，总孔容为0.43mL/g～0.55mL/g，SiO2/Al2O3摩尔比为20～150，晶胞参数为2.425～2.433nm，红外酸量0.1～0.4mmol/g。
优选情况下，所述氧化铝为大孔氧化铝和/或小孔氧化铝，大孔氧化铝的孔容0.7～1.0mL/g，比表面积200～500m2/g，小孔氧化铝的孔容为0.3～0.5mL/g，比表面积为200～400m2/g。
优选情况下，所述加氢活性金属组分为第VIB族和/或第VIII族的金属，第VIB族的金属为钼和/或钨，第VIII族的金属为钴和/或镍。
优选情况下，所述第二加氢裂化催化剂中，以催化剂的重量为基准，第VIB族金属以氧化物计的含量为10.0％～30.0％，第VIII族金属以氧化物计的含量为4.0％～8.0％。
上述第二加氢裂化催化剂可以用于由重质馏分油加氢裂化生产中间馏分油(航煤+柴油)的方法。优选情况下，所述加氢裂化操作条件包括反应总压为12.0～20.0MPa，体积空速为1.0～3.0h-1，氢油体积比为800∶1～2000∶1，反应温度为365～435℃。
本发明加氢裂化催化剂的制备方法，包括载体的制备和负载加氢活性金属组分，其中载体的制备过程如下：将β分子筛、无定形硅铝或Y型分子筛、氧化铝机械混合，成型，然后干燥和焙烧，制成催化剂载体，其中β分子筛的制备方法如上文所述。
本发明加氢裂化催化剂载体制备方法中，载体的干燥和焙烧可采用常规的条件，一般为在100℃～150℃干燥1～12小时，然后在450℃～550℃焙烧2.5～6.0小时。
本发明加氢裂化催化剂载体通过常规方式负载加氢活性金属组分(第VIB族和第VIII族金属组分如Co、Ni、Mo、W等)，比如混捏法，浸渍法等。本发明中优选采用浸渍法负载加氢活性金属组分，然后经干燥和焙烧得到加氢裂化催化剂。浸渍法可以是饱和浸、过量浸或络合浸，即用含有所需活性组分的溶液浸渍催化剂载体，浸渍后的载体在100℃～150℃干燥1～12小时，然后在450℃～550℃焙烧2.5～6.0小时，制得最终催化剂。
本发明加氢裂化催化剂载体中氧化铝可以采用常规加氢裂化催化剂中所用的氧化铝，如大孔氧化铝和/或小孔氧化铝。所用的大孔氧化铝的孔容0.7～1.0mL/g，比表面积 200～500m2/g。所用的小孔氧化铝的孔容为0.3～0.5mL/g，比表面积为200～400m2/g。
本发明加氢裂化催化剂载体制备过程中还可以加入常规的成型助剂比如胶溶酸、助挤剂等。
本发明的加氢裂化催化剂可用于重质馏分油(VGO、CGO和DAO)的加氢裂化过程，其中也可以加入劣质柴油(焦化柴油和催化柴油等)等原料。
(三)加氢改质催化剂
根据本发明，当载体包含上述β分子筛和氧化铝时，与加氢活性金属组分配合后，该加氢催化剂可以用作加氢改质催化剂。
优选地，所述加氢改质催化剂的比表面积是200～400m2/g，孔容是0.35～0.60mL/g。
优选地，所述加氢改质催化剂载体中，以载体的重量为基准，β分子筛的含量为5％～40％，氧化铝的含量为60％～95％。
优选地，所述氧化铝为大孔氧化铝和/或小孔氧化铝，大孔氧化铝的孔容为0.7～1.0mL/g，比表面积为200～500m2/g，小孔氧化铝的孔容为0.3～0.5mL/g，比表面积为200～400m2/g。
优选地，所述加氢活性金属组分为第VIB族和第VIII族的金属，第VIB族的金属为钼和/或钨，第VIII族的金属为钴和/或镍。
优选地，所述加氢改质催化剂中，以催化剂的重量为基准，第VIB族金属以氧化物计的含量为10.0％～30.0％，第VIII族金属以氧化物计的含量为4.0％～8.0％。
采用上述加氢改质催化剂对柴油加氢改质时，优选地，所述加氢改质操作条件包括反应总压4～12MPa，液时体积空速1～3h-1，氢油体积比为400∶1～2000∶1，反应温度365～435℃。
本发明加氢改质催化剂的制备方法，包括载体的制备和负载加氢活性金属组分，其中载体的制备过程如下：将β分子筛、氧化铝机械混合，成型，然后干燥和焙烧，制成催化剂载体，其中β分子筛的制备方法如上文所述。
本发明加氢改质催化剂载体制备方法中，载体的干燥和焙烧可采用常规的条件，一般为在100℃～150℃干燥1～12小时，然后在450℃～550℃焙烧2.5～6.0小时。
本发明加氢改质催化剂载体通过常规方式负载加氢活性金属组分(第VIB族和第VIII族金属组分如Co、Ni、Mo、W等)，比如混捏法，浸渍法等。本发明中优选采用浸渍法负载加氢活性金属组分，然后经干燥和焙烧得到加氢改质催化剂。浸渍法可以是饱和浸、过量浸或络合浸，即用含有所需活性组分的溶液浸渍催化剂载体， 浸渍后的载体在100℃～150℃干燥1～12小时，然后在450℃～550℃焙烧2.5～6.0小时，制得最终催化剂。
本发明加氢改质催化剂载体中氧化铝可以采用常规加氢改质催化剂中所用的氧化铝，如大孔氧化铝和/或小孔氧化铝。所用的大孔氧化铝的孔容0.7～1.0mL/g，比表面积200～500m2/g。所用的小孔氧化铝的孔容为0.3～0.5mL/g，比表面积为200～400m2/g。
本发明催化剂载体制备过程中还可以加入常规的成型助剂比如胶溶酸，助挤剂等。
本发明加氢改质催化剂选择的β分子筛对长链烷烃和芳烃、环烷烃的长侧链烷基有适宜的裂解作用和很好的异构作用，使催化剂在保持高柴油收率的同时，较大幅度降低柴油馏分的凝点，较大幅度提高改质柴油的十六烷值，柴油产品的密度和硫含量得到有效降低。
本发明加氢改质催化剂用于劣质柴油改质时，特别是在中压条件(4～12MPa)和处理劣质柴油(催化柴油和焦化柴油)具有很高的催化活性和柴油收率，而且柴油馏分的凝点降低幅度大，较大幅度提高改质柴油的十六烷值，柴油产品的密度得到有效降低，能满足炼厂增大操作灵活性、增加装置处理能力、进一步增优质产柴油的需要。
本发明加氢改质催化剂用于劣质柴油改质时的操作条件如下：反应总压4.0～12.0MPa，液时体积空速1.0～3.0h-1，氢油体积比为400∶1～1000∶1，反应温度345～435℃。
下面的实施例用于更详细地说明本发明，但本发明的范围不只限于这些实施例的范围。本发明中，wt％为质量分数。
本发明中所述的比表面积是根据ASTM D3663-2003标准采用低温液氮吸附法测定的。
本发明中所述的孔容是根据ASTM D4222-2003标准采用低温液氮吸附法测定的。
本发明中，NH3-TPD方法是一种常用的测量分子筛酸量的方法，采用的仪器为麦克仪器公司Auto-Chem II 2920型化学吸附仪。采用氨气作为吸脱附介质，氦气(纯度为99.99v％)作为载气，采用程序升温脱附和色谱分析得到不同脱附温度区的酸量即弱酸量、中强酸量和强酸量以及总酸量。具体操作过程如下：取20～40目分子筛样品0.1g，在氦气存在下(氦气流速为30mL/min)，升温至500℃，恒温1小时，然后降至150℃，恒温5分钟。之后，通入氨气直至分子筛吸附饱和，切换成氦气连续吹扫(氦气流速为30mL/min)，升温速度为10℃/分钟，升温250℃，恒温1小时，之后再继续升温至400℃，恒温1小时，再继续升温至500℃，恒温1小时。在氨气脱附过程中，通过色谱仪记录 氨脱附谱图。所得的氨脱附谱图中，按脱附温度分成三个温度区即150℃～250℃、250℃～400℃、400℃～500℃分别对应弱酸、中强酸和强酸的酸量，弱酸、中强酸和强酸的酸量之和为总酸量。酸量单位为：mmol/g，即每克分子筛吸附的氨气量。
本发明红外酸量以吡啶为吸附剂，采用红外光谱法测定，仪器为美国NICOLET公司Nicolet 6700傅立叶红外光谱仪，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)，利用吡啶重量吸附法求得总酸量，并记录上述条件下所得的红外光谱图，其中B酸对应的谱带1545cm-1，L酸对应的谱带1455cm-1，根据各谱带的峰面积比计算B酸量与L酸量的比，由此，得到总酸量、B酸量和L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 PCTCN2014089699-appb-000001
总酸C(单位：毫摩尔/克)：
Figure PCTCN2014089699-appb-000002
注：79.1为吡啶的摩尔质量，单位为克/摩尔。
本发明中，相对结晶度(relative crystallinity)是采用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β分子筛原粉。
本发明中，硅铝摩尔比采用化学法；钠含量采用等离子发射光谱法。
本发明中，采用核磁共振波谱法(NMR法)得到27Al MAS NMR谱图，从而得到 骨架铝及非骨架铝的比例，以Al原子计。采用核磁共振波谱法(NMR法)得到29Si MAS NMR谱图，从而得到硅原子以不同配位状态(Si(4Al)、Si(3Al)、Si(2Al)、Si(1Al)和Si(0Al))形式存在的比例，以Si原子计。核磁共振波谱法(NMR法)是采用Bruker AVANCE III 500型核磁共振谱仪，其中软件采用Topspin 2.0。在测29Si MAS NMR谱图时采用的标准物质为四甲基硅(TMS)，共振频率为99MHz，实验条件：4-6微秒脉冲宽度，60-120秒弛豫延迟。在测27Al MAS NMR谱图时，采用的标准物质为三氯化铝，共振频率为133MHz，实验条件：4-6微秒脉冲宽度，60-120秒弛豫延迟。所得29Si MAS NMR谱图中，Si(4Al)对应的化学位移为-81～-96ppm，Si(3Al)对应的化学位移为-96～-100ppm，Si(2Al)对应的化学位移为-100～-106ppm、Si(1Al)对应的化学位移为-106～-109ppm和Si(0Al)对应的化学位移为-109～-115ppm)。所得27Al MAS NMR谱图中，骨架铝对应的化学位移为40～65ppm，非骨架铝对应的化学位移为-10～10ppm。
实施例1
取β分子筛原粉(以四乙基氢氧化铵为模板剂采用水热法合成的，β分子筛原粉中模板剂的重量含量约为11.8％，由中国石化催化剂抚顺分公司提供)，其化学SiO2/Al2O3摩尔比为25.5，Na2O含量为2.45wt％，其骨架结构中，通过29Si MAS NMR谱图，获得不同配位状态形式存在的硅原子的分布如下：Si(4Al)为7.6％，Si(3Al)为30.6％，Si(2Al)为32.3％，Si(1Al)为21.0％，Si(0Al)为8.5％。取上述β分子筛原粉1000g，装入管式炉中，采用程序升温的方法(升温速率为100℃/小时)，在管式炉温度升到300℃时开始引入100wt％的水蒸汽，水蒸汽的流量为50L/小时，将管式炉加热到550℃，恒温时间为6小时。所得分子筛编号为BS-1。
实施例2
取β分子筛原粉同实施例1。取上述分子筛1000g，装入管式炉中，采用程序升温的方法(升温速率为100℃/小时)，在管式炉温度升到300℃时开始引入100wt％的水蒸汽，水蒸汽的流量为70L/小时，将管式炉加热到600℃，恒温时间为8小时。所得分子筛编号为BS-2。
实施例3
取β分子筛原粉同实施例1。取上述分子筛1000g，装入管式炉中，采用程序升温 的方法(升温速率为100℃/小时)，在管式炉温度升到300℃时开始引入100wt％的水蒸汽，水蒸汽的流量为70L/小时，将管式炉加热到650℃，恒温时间为10小时。所得分子筛编号为BS-3。
实施例4
取β分子筛原粉(以四乙基氢氧化铵为模板剂采用水热法合成的，β分子筛原粉中模板剂的重量含量约为10.6％，由中国石化催化剂抚顺分公司提供)，其化学SiO2/Al2O3摩尔比为22.5，Na2O含量为2.35wt％，其骨架结构中，通过29Si MAS NMR谱图，获得不同配位状态形式存在的硅原子的分布如下：Si(4Al)为7.7％，Si(3Al)为31.5％，Si(2Al)为30.9％，Si(1Al)为21.9％，Si(0Al)为8.0％。取上述β分子筛原粉1000g，装入管式炉中，采用程序升温的方法(升温速率为80℃/小时)，在管式炉温度升到400℃时开始引入100wt％的水蒸汽，水蒸汽的流量为80L/小时，将管式炉加热到600℃，恒温时间为5小时。所得分子筛编号为BS-4。
实施例5
取β分子筛原粉(以四乙基氢氧化铵为模板剂采用水热法合成的，β分子筛原粉中模板剂的重量含量约为13.2％，由中国石化催化剂抚顺分公司提供)，其化学SiO2/Al2O3摩尔比为28.5，Na2O含量为2.75wt％，其骨架结构中，通过29Si MAS NMR谱图，获得不同配位状态形式存在的硅原子的分布如下：Si(4Al)为8.8％，Si(3Al)为28.7％，Si(2Al)为31.3％，Si(1Al）为23.5％，Si(0Al)为7.7％。取上述β分子筛原粉1000g，装入管式炉中，采用程序升温的方法(升温速率为100℃/小时)，在管式炉温度升到280℃时开始引入100wt％的水蒸汽，水蒸汽的流量为100L/小时，将管式炉加热到620℃，恒温时间为10小时。所得分子筛编号为BS-5。
实施例6
取BS-1分子筛200g，与浓度为15g氟硅酸铵/100mL溶液的氟硅酸铵水溶液接触，液固体积比为5∶1，温度为80℃，时间为2小时，恒温结束后，将浆液过滤，得到的滤饼用净水在75℃，液固体积比10∶1，洗涤时间为40分钟，以洗涤液的pH值接近7后停止洗涤。滤饼在烘箱中120℃干燥5小时，得到本发明的β分子筛，编号为BSS-1，物化性质列于表1。
实施例7
取BS-1分子筛200g，与浓度为43g氟硅酸铵/100mL溶液的氟硅酸铵水溶液接触，液固体积比为8∶1，温度为95℃，时间为2小时，恒温结束后，将浆液过滤，得到的滤饼用净水在75℃，液固体积比10∶1，洗涤时间为40分钟，以洗涤液的pH值接近7后停止洗涤。滤饼在烘箱中120℃干燥5小时，得到本发明的β分子筛，编号为BSS-2，物化性质列于表1。
实施例8
取BS-2分子筛200g，与浓度为23.5g氟硅酸铵/100mL溶液的氟硅酸铵水溶液接触，液固体积比为10∶1，温度为95℃，时间为2小时，恒温结束后，将浆液过滤，得到的滤饼用净水在75℃，液固体积比10∶1，洗涤时间为40分钟，以洗涤液的pH值接近7后停止洗涤。滤饼在烘箱中120℃干燥5小时，得到本发明的β分子筛，编号为BSS-3，物化性质列于表1。
实施例9
取BS-2分子筛200g，与浓度为51.3g氟硅酸铵/100mL溶液的氟硅酸铵水溶液接触，液固体积比为6∶1，温度为75℃，时间为1小时，恒温结束后，将浆液过滤，得到的滤饼用净水在75℃，液固体积比10∶1，洗涤时间为40分钟，以洗涤液的pH值接近7后停止洗涤。滤饼在烘箱和120℃干燥5小时，得到本发明的β分子筛，编号为BSS-4，物化性质列于表1。
实施例10
取BS-3分子筛200g，与浓度为27.8g氟硅酸铵/100mL溶液的氟硅酸铵水溶液接触，液固体积比为8∶1，温度为95℃，时间为3小时，恒温结束后，将浆液过滤，得到的滤饼用净水在75℃，液固体积比10∶1，洗涤时间为40分钟，以洗涤液的pH值接近7后停止洗涤。滤饼在烘箱中120℃干燥5小时，得到本发明的β分子筛，编号为BSS-5，物化性质列于表1。
实施例11
取BS-3分子筛200g，与浓度为56.7g氟硅酸铵/100mL溶液的氟硅酸铵水溶液接触，液固体积比为4∶1，温度为95℃，时间为2小时，恒温结束后，将浆液过滤，得到的滤饼用净水在75℃，液固体积比10∶1，洗涤时间为40分钟，以洗涤液的pH值接近7后停止洗涤。滤饼在烘箱中120℃干燥5小时，得到本发明的β分子筛，编号为BSS-6，物化性质列于表1。
实施例12
取BS-4分子筛200g，与浓度为33.5g氟硅酸铵/100mL溶液的氟硅酸铵水溶液接触，液固体积比为4∶1，温度为75℃，时间为3小时，恒温结束后，将浆液过滤，得到的滤饼用水在75℃，液固体积比10∶1，洗涤时间为40分钟，以洗涤液的pH值接近7后停止洗涤。滤饼在烘箱中120℃干燥5小时，得到本发明的β分子筛，编号为BSS-7，物化性质列于表1。
实施例13
取BS-5分子筛200g，与浓度为45.8g氟硅酸铵/100mL溶液的氟硅酸铵水溶液接触，液固体积比为12∶1，温度为95℃，时间为2小时，恒温结束后，将浆液过滤，得到的滤饼用净水在75℃，液固体积比10∶1，洗涤时间为40分钟，以洗涤液的pH值接近7后停止洗涤。滤饼在烘箱中120℃干燥5小时，得到本发明的β分子筛，编号为BSS-8，物化性质列于表1。
比较例1
采用CN 1393522A公开的方法制备改性β分子筛，编号为BD-1，物化性质列于表1，具体过程如下：
取实施例1中的β分子筛原粉400g，用2.0M硝酸铵溶液以液固体积比为10∶1进行交换，升温至90～95℃，恒温搅拌2小时，然后降温至50～60℃过滤，湿滤饼再进行第二次交换，条件同第一次。经两次铵盐交换的β分子筛，洗涤至pH达到5～6，然后放入干燥箱中，110～120℃干燥6小时。干燥后的β分子筛放入马福炉中快速升温至250℃，恒温2小时，然后继续快速升温至400℃，再恒温4小时，最后升温到540℃，恒温10小时，得到高温焙烧脱铵后的β分子筛BD-0。称量400g由上述方法制得的高温焙烧脱铵后的β分子筛BD-0粉碎后加入0.4M HCl 4000mL，搅拌升温至90℃，恒温搅拌2小时，冷却过滤洗涤。经酸处理的β分子筛过滤洗涤，然后在110～120℃干燥6小时(干基＞80wt％)。将上述干 燥的样品上均匀喷洒定量的净水，放入密闭的水热处理炉中，升温至650℃，控制压力450kPa，恒温恒压焙烧2.5小时，然后自然降至室温，即得到β分子筛BD-1。
采用500MHZ的固相核磁对本发明实施例6制得的β分子筛BSS-1和比较例1制得的β分子筛BD-1进行了表征，各自的27Al MAS NMR谱图分别如图1和图2所示。图1和图2中，0ppm附近的峰对应六配位的非骨架铝，而60ppm附近的峰对应四配位的骨架铝，而峰面积可看作两种铝结构的比例。从图1可以看出，本发明分子筛的铝谱中几乎不存在六配位非骨架铝，且四配位骨架铝的峰强度较强，半峰宽较窄，说明分子筛中铝结构基本都是骨架的四配位铝结构；图2分子筛则存在着大量的六配位非骨架铝结构，几乎达到分子筛中铝含量的20％以上。
比较例2
采用CN 1166560C中β分子筛先经过铵交换，再脱去模板剂的方法制备分子筛，具体如下：
(1)取工业合成SiO2/Al2O3摩尔比25.67，Na2O 3.75wt％的Naβ分子筛过程中晶化后的浆液2000mL，含固相400g(以干基计)，用净水将固液体积比稀释到1∶10，加入硝酸铵，使浆液中含硝酸铵为2.0M，搅拌、升温至95℃，恒温搅拌2小时，然后降温至60℃过滤，湿滤饼再进行第二次交换，条件同第一次；
(2)经两次铵盐交换的β分子筛，洗涤至pH达到6，然后放入干燥箱中，110℃干燥6小时；
(3)干燥后的β分子筛放入马福炉中在1小时内升温至250℃，恒温2小时，然后继续在1小时内升温至400℃，再恒温4小时，最后升温到540℃，恒温10小时，物料全部烧白，残炭≤0.2％；
(4)取分子筛200g，采用浓度为23.5g氟硅酸铵/100mL溶液的氟硅酸铵水溶液，液固体积比为10∶1，处理温度为95℃，处理时间为2小时，恒温结束后，将浆液过滤，得到滤饼在75℃，液固体积比10∶1，洗涤时间为40分钟，以洗涤液的pH值接近7后停止洗涤。滤饼在烘箱中120℃干燥5小时，得到β分子筛，编号为BD-2，物化性质列于表1。
比较例3
取β分子筛原粉同实施例1。取上述β分子筛原粉1000g，装入密闭水热处理炉中， 采用程序升温的方法(升温速率为100℃/小时)，水热处理温度600℃，水热处理压力为0.2MPa，处理时间为3小时，再以水热处理后分子筛为原料进行酸化处理，处理条件为取水热处理后分子筛200g，采用浓度为0.4mol/L的盐酸溶液处理，液固体积比为10∶1，处理温度为95℃，处理时间为2小时，恒温结束后，将浆液过滤，得到滤饼在75℃，液固体积比10∶1，洗涤时间为40分钟，以洗涤液的pH值接近7后停止洗涤。滤饼在烘箱中120℃干燥5小时，得到β分子筛，编号为BD-3，物化性质列于表1。
比较例4
采用实施例6的方法制备β分子筛，不同的是，BS-1分子筛由采用下述方法制备的BDS-4分子筛代替，得到β分子筛，编号为BD-4，物化性质列于表1。
BDS-4分子筛的制备：取β分子筛原粉同实施例1。取上述β分子筛原粉1000g，装入密闭水热处理炉中，采用程序升温的方法(升温速率为100℃/小时)，水热处理温度550℃，水热处理压力为0.2MPa，处理时间为6小时，样品编号为BDS-4。
比较例5
对BS-1分子筛进行气相抽铝补硅。在密闭容器内装入BS-1分子筛200g，通入气化后的四氯化硅，反应温度为95℃，反应时间为2小时，通入四氯化硅的量为9.8gSiCl4/100g分子筛。样品编号为BD-5，物化性质列于表1。
比较例6
采用实施例6的方法，不同的是，将氟硅酸铵换成相同量(摩尔计)的正硅酸乙酯，样品编号为BD-6，物化性质列于表1。
比较例7
按照实施例6的方法制备β分子筛，不同的是，β分子筛原粉由相同重量的比较例1制得的高温焙烧脱铵后的β分子筛BD-0代替，得到β分子筛，编号为BD-7，物化性质列于表1。
表1  β分子筛物化性质
Figure PCTCN2014089699-appb-000003
Figure PCTCN2014089699-appb-000004
续表1
Figure PCTCN2014089699-appb-000005
实施例I-1
将15.6克BSS-1分子筛(干基90wt％)、114.3克无定形硅铝(SiO2含量20wt％，孔容0.85mL/g，比表面积370m2/g，干基70wt％)、94.3克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、133.3克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体ZS-1，性质见表2。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂HC-1，载体及相应催化剂性质见表2。
实施例I-2
将33.3克BSS-1分子筛(干基90wt％)、85.7克无定形硅铝(SiO2含量20wt％，孔容0.85mL/g，比表面积370m2/g，干基70wt％)、100.0克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、133.3克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体ZS-2，性质见表2。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂HC-2，载体及相应催化剂性质见表2。
实施例I-3
将22.2克BSS-5分子筛(干基90wt％)、71.4克无定形硅铝(SiO2含量20wt％，孔容0.85mL/g，比表面积370m2/g，干基70wt％)、128.6克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、133.3克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体ZS-3，性质见表2。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂HC-3，载体及相应催化剂性质见表2。
实施例I-4
将44.4克BSS-5分子筛(干基90wt％)、142.9克无定形硅铝(SiO2含量20wt％，孔容0.85mL/g，比表面积370m2/g，干基70wt％)、28.6克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、133.3克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体ZS-4，性质见表2。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂HC-4，载体及相应催化剂性质见表2。
实施例I-5
将33.3克BSS-2分子筛(干基90wt％)、385.5克无定形硅铝(SiO2含量20wt％，孔容0.75mL/g，比表面积350m2/g，干基70wt％)、256.9克大孔氧化铝(孔容1.0mL/g， 比表面积400m2/g，干基70wt％)、399.6克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体ZS-5，性质见表2。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂HC-5，载体及相应催化剂性质见表2。
实施例I-6
将33.3克BSS-3分子筛(干基90wt％)、171.3克无定形硅铝(SiO2含量20wt％，孔容0.85mL/g，比表面积370m2/g，干基70wt％)、128.4克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、199.8克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体ZS-6，性质见表2。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂HC-6，载体及相应催化剂性质见表2。
实施例I-7
将33.3克BSS-7分子筛(干基90wt％)、142.7克无定形硅铝(SiO2含量20wt％，孔容0.85mL/g，比表面积370m2/g，干基70wt％)、42.8克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、133.2克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体ZS-7，性质见表2。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂HC-7，载体及相应催化剂性质见表2。
实施例I-8
将33.3克BSS-8分子筛(干基90wt％)、122.3克无定形硅铝(SiO2含量20wt％，孔容0.85mL/g，比表面积370m2/g，干基70wt％)、324.1克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、285.3克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体ZS-8，性质见表2。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂HC-8，载体及相应催化剂性质见表2。
比较例I-1
按照实施例I-2的方法制备载体，不同的是，BSS-1分子筛由相同重量的β分子筛BD-2代替，得载体ZDS-1，性质见表2。
使用上述载体按照实施例I-2的方法制备催化剂，得催化剂HCD-1，载体及相应催化剂性质见表2。
比较例I-2
按照实施例I-3的方法制备载体，不同的是，BSS-5分子筛由相同重量的β分子筛BD-3代替，得载体ZDS-2，性质见表2。
使用上述载体按照实施例I-3的方法制备催化剂，得催化剂HCD-2，载体及相应催化剂性质见表2。
比较例I-3
按照实施例I-4的方法制备载体，不同的是，BSS-5分子筛由相同重量的β分子筛BD-1代替，得载体ZDS-3，性质见表2。
使用上述载体按照实施例I-4的方法制备催化剂，得催化剂HCD-3，载体及相应催化剂性质见表2。
比较例I-4
按照实施例I-2的方法制备载体，不同的是，BSS-1分子筛由相同重量的β分子筛BD-4代替，得载体ZDS-4，性质见表2。
使用上述载体按照实施例I-2的方法制备催化剂，得催化剂HCD-4，载体及相应催化剂性质见表2。
比较例I-5
按照实施例I-2的方法制备载体，不同的是，BSS-1分子筛由相同重量的β分子筛BD-5代替，得载体ZDS-5，性质见表2。
使用上述载体按照实施例I-2的方法制备催化剂，得催化剂HCD-5，载体及相应催化剂性质见表2。
比较例I-6
按照实施例I-2的方法制备载体，不同的是，BSS-1分子筛由相同重量的β分子筛BD-6代替，得载体ZDS-6，性质见表2。
使用上述载体按照实施例I-2的方法制备催化剂，得催化剂HCD-6，载体及相应催化剂性质见表2。
比较例I-7
按照实施例I-2的方法制备载体，不同的是，BSS-1分子筛由相同重量的β分子筛BD-7代替，得载体ZDS-7，性质见表2。
使用上述载体按照实施例I-2的方法制备催化剂，得催化剂HCD-7，载体及相应催化剂性质见表2。
表2  催化剂载体及催化剂的物化性质
实施例编号 I-1 I-2 I-3 I-4 I-5 I-6 I-7 I-8
载体                
编号 ZS-1 ZS-2 ZS-3 ZS-4 ZS-5 ZS-6 ZS-7 ZS-8
β分子筛，wt％ 7 15 10 20 5 10 15 7
无定形硅铝，wt％ 40 30 25 50 45 40 50 20
氧化铝 余量 余量 余量 余量 余量 余量 余量 余量
孔容，mL/g 0.74 0.73 0.75 0.68 0.76 0.72 0.67 0.78
比表面积，m2/g 415 440 431 456 428 430 416 443
催化剂                
编号 HC-1 HC-2 HC-3 HC-4 HC-5 HC-6 HC-7 HC-8
WO3，wt％ 17.5 21.5 22.9 27.6 21.6 23.5 21.8 27.0
NiO，wt％ 4.3 5.3 5.6 7.5 5.4 5.5 5.4 6.7
孔容，mL/g 0.58 0.55 0.52 0.44 0.53 0.51 0.38 0.49
比表面积，m2/g 329 334 308 299 311 315 301 300
续表2  催化剂载体及催化剂的物化性质
比较例编号 I-1 I-2 I-3 I-4 I-5 I-6 I-7
载体              
编号 ZDS-1 ZDS-2 ZDS-3 ZDS-4 ZDS-5 ZDS-6 ZDS-7
β分子筛，wt％ 15 10 20 15 15 15 15
无定形硅铝，wt％ 30 25 50 30 30 30 30
氧化铝 余量 余量 余量 余量 余量 余量 余量
孔容，mL/g 0.68 0.70 0.57 0.59 0.65 0.65 0.61
比表面积，m2/g 401 369 336 358 347 409 388
催化剂              
编号 HCD-1 HCD-2 HCD-3 HCD-4 HCD-5 HCD-6 HCD-7
WO3，wt％ 21.8 23.8 27.5 21.4 21.6 21.6 21.5
NiO，wt％ 5.5 6.1 7.4 5.4 5.5 5.2 5.3
孔容，mL/g 0.50 0.49 0.32 0.33 0.41 0.36 0.34
比表面积，m2/g 301 263 24l 256 251 278 254
催化性能评价1
在固定床加氢试验装置上进行评价，评价条件为：反应总压15.0MPa，氢油体积比1500，液时体积空速0.9h-1，使用减压馏分油(VGO)作为原料油，原料油性质列于表3。将催化剂HC-1至HC-8以及HCD-1至HCD-7在相同的工艺条件下评价，得到的评价结果列于表4。
表3  原料油性质
原料油 VGO-1 VGO-2
密度(20℃)，g/cm3 0.9054 0.9118
馏程/℃    
IBP/10％ 303/362 316/385
30％/50％ 393/415 417/443
70％/90％ 445/485 475/520
95％/EBP 510/554 543/553
凝点，℃ 35 33
硫，wt％ 2.08 1.76
氮，μg/g 1180 1236
碳，wt％ 85.28 85.35
氢，wt％ 12.52 12.77
BMCI值 44.06 44.40
表4  性能评价条件及结果
Figure PCTCN2014089699-appb-000006
Figure PCTCN2014089699-appb-000007
续表4  性能评价条件及结果
Figure PCTCN2014089699-appb-000008
Figure PCTCN2014089699-appb-000009
由表4的评价结果可以看出，本发明所制备催化剂在相同的工艺条件下，柴油选择性、收率和产品质量均优于参比催化剂。
实施例II-1
将22.22克BSS-1分子筛(干基90wt％)、44.44克Y型分子筛(SiO2/Al2O3＝50，晶胞常数2.431nm，孔容0.45mL/g，比表面积900m2/g，干基90wt％)、157.1克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、100克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体S-1。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂FC-1，载体及相应催化剂性质见表5。
实施例II-2
将33.33克BSS-1分子筛(干基90wt％)、44.44克Y型分子筛(SiO2/Al2O3＝53.5，晶胞常数2.432nm，孔容0.49mL/g，比表面积878m2/g，干基90wt％)、142.86克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、100克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体S-2。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂FC-2，载体及相应催化剂性质见表5。
实施例II-3
将11.11克BSS-3分子筛(干基90wt％)、66.67克Y型分子筛(SiO2/Al2O3＝91，晶胞常数2.4329nm，孔容0.52mLg，比表面积943m2/g，干基90wt％)、142.86克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、100克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体S-3。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂FC-3，载体及相应催化剂性质见表5。
实施例II-4
将44.44克BSS-3分子筛(干基90wt％)、55.56克Y型分子筛(SiO2/Al2O3＝37，晶胞常数2.433nm，孔容0.45mL/g，比表面积887m2/g，干基90wt％)、88.89克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、100克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体S-4。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂FC-4，载体及相应催化剂性质见表5。
实施例II-5
将22.22克BSS-5分子筛(干基90wt％)、44.3克Y型分子筛(SiO2/Al2O3＝91，晶胞常数2.4329nm，孔容0.52mL/g，比表面积943m2/g，干基90wt％)、66.5克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、88.7克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体S-5。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂FC-5，载体及相应催化剂性质见表5。
实施例II-6
将22.22克BSS-7分子筛(干基90wt％)、155.5克Y型分子筛(SiO2/Al2O3＝91，晶胞常数2.4329nm，孔容0.52mL/g，比表面积943m2/g，干基90wt％)、177.8克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、266.7克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体S-6。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂FC-6，载体及相应催化剂性质见表5。
实施例II-7
将33.33克BSS-8分子筛(干基90wt％)、33.33克Y型分子筛(SiO2/Al2O3＝37，晶胞常数2.433nm，孔容0.45mL/g，比表面积887m2/g，干基90wt％)、142.90克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、133.3克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体S-7。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂FC-7，载体及相应催化剂性质见表5。
比较例II-1
将33.33克BD-1分子筛(干基90wt％)、44.44克Y型分子筛(SiO2/Al2O3＝50，晶胞常数2.431nm，孔容0.45mL/g，比表面积900m2/g，干基90wt％)、128.6克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、133.3克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体DS-1。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂FCD-1，载体及相应催化剂性质见表5。
比较例II-2
将11.11克BD-1分子筛(干基90wt％)、66.67克Y型分子筛(SiO2/Al2O3＝53.5，晶胞常数2.432nm，孔容0.49mL/g，比表面积878m2/g，干基90wt％)、128.6克大孔氧 化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、133.3克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体DS-2。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂FCD-2，载体及相应催化剂性质见表5。
比较例II-3
将33.33克BD-3分子筛(干基90wt％)、44.44克Y型分子筛(SiO2/Al2O3＝91，晶胞常数2.4329nm，孔容0.52mL/g，比表面积943m2/g，干基90wt％)、128.6克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、133.3克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体DS-3。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂FDC-3，载体及相应催化剂性质见表5。
比较例II-4
按照实施例II-4的方法制备载体，不同的是，BSS-3分子筛由相同重量的β分子筛BD-2代替，得载体DS-4，性质见表5。
使用上述载体按照实施例II-4的方法制备催化剂，得催化剂FCD-4，载体及相应催化剂性质见表5。
比较例II-5
按照实施例II-2的方法制备载体，不同的是，BSS-1分子筛由相同重量的β分子筛BD-4代替，得载体DS-5，性质见表5。
使用上述载体按照实施例II-2的方法制备催化剂，得催化剂FCD-5，载体及相应催化剂性质见表5。
比较例II-6
按照实施例II-2的方法制备载体，不同的是，BSS-1分子筛由相同重量的β分子筛BD-5代替，得载体DS-6，性质见表5。
使用上述载体按照实施例II-2的方法制备催化剂，得催化剂FCD-6，载体及相应催化剂性质见表5。
比较例II-7
按照实施例II-2的方法制备载体，不同的是，BSS-1分子筛由相同重量的β分子筛BD-6代替，得载体DS-7，性质见表5。
使用上述载体按照实施例II-2的方法制备催化剂，得催化剂FCD-7，载体及相应催化剂性质见表5。
比较例II-8
按照实施例II-2的方法制备载体，不同的是，BSS-1分子筛由相同重量的β分子筛BD-7代替，得载体DS-8，性质见表5。
使用上述载体按照实施例II-2的方法制备催化剂，得催化剂FCD-8，载体及相应催化剂性质见表5。
表5  催化剂载体及催化剂的物化性质
实施例编号 II-1 II-2 II-3 II-4 II-5 II-6 II-7
载体              
编号 S-1 S-2 S-3 S-4 S-5 S-6 S-7
β分子筛，wt％ 10 15 5 20 15 5 15
Y型分子筛，wt％ 20 20 30 25 30 35 15
氧化铝 余量 余量 余量 余量 余量 余量 余量
孔容，mL/g 435 452 463 489 496 486 443
比表面积，m2/g 0.68 0.65 0.66 0.67 0.65 0.64 0.69
催化剂              
编号 FC-1 FC-2 FC-3 FC-4 FC-5 FC-6 FC-7
WO3，wt％ 22.36 21.63 22.06 22.18 24.36 26.78 22.36
NiO，wt％ 5.4 5.5 5.3 5.5 5.9 6.3 5.2
比表面积，m2/g 330 327 332 349 365 357 352
孔容，mL/g 0.47 0.46 0.45 0.48 0.45 0.47 0.49
续表5  催化剂载体及催化剂的物化性质
Figure PCTCN2014089699-appb-000010
催化性能评价2
在固定床加氢试验装置上进行评价，评价条件为：反应总压15.0MPa，氢油体积比1500，体积空速1.5h-1，使用减压馏分油(VGO)作为原料油，原料油性质如上表3。将催化剂FC-1至FC-7以及FCD-1至FCD-8在相同的工艺条件下评价，得到的评价结果列于表6。
表6  性能评价条件及结果
Figure PCTCN2014089699-appb-000011
Figure PCTCN2014089699-appb-000012
续表6  性能评价条件及结果
Figure PCTCN2014089699-appb-000013
Figure PCTCN2014089699-appb-000014
由表6的评价结果可以看出，本发明所制备催化剂在相同的工艺条件下，喷气燃料和柴油选择性、收率和产品质量均优于参比催化剂。
实施例III-1
将33.3克BSS-2分子筛(干基90wt％)、200.0克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、133.3克粘合剂(干基30wt％，硝酸与小孔氧化铝的 摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体CS-1，性质见表7。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂LC-1，载体及相应催化剂性质见表7。
实施例III-2
将44.4克BSS-2分子筛(干基90wt％)、171.4克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、133.3克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体CS-2，性质见表7。
载体用含钨和镍的浸渍液室温浸渍2小时，120(2干燥4小时，程序升温500℃焙烧4小时，得催化剂LC-2，载体及相应催化剂性质见表7。
实施例III-3
将66.6克BSS-6分子筛(干基90wt％)、142.9克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、133.3克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体CS-3，性质见表7。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂LC-3，载体及相应催化剂性质见表7。
实施例III-4
将77.8克BSS-6分子筛(干基90wt％)、128.6克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、133.3克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体CS-4，性质见表7。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂LC-4，载体及相应催化剂性质见表7。
实施例III-5
将66.6克BSS-4分子筛(干基90wt％)、142.9克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、133.3克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体CS-5，性质见表7。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂LC-5，载体及相应催化剂性质见表7。
实施例III-6
将88.9克BSS-7分子筛(干基90wt％)、114.2克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、133.3克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体CS-6，性质见表7。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂LC-6，载体及相应催化剂性质见表7。
实施例III-7
将22.2克BSS-8分子筛(干基90wt％)、200.0克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、133.3克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体CS-7，性质见表7。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂LC-7，载体及相应催化剂性质见表7。
实施例III-8
将33.3克BSS-1分子筛(干基90wt％)、200.0克大孔氧化铝(孔容1.0mL/g，比表面积400m2/g，干基70wt％)、133.3克粘合剂(干基30wt％，硝酸与小孔氧化铝的摩尔比为0.4)放入碾压机中混碾，加水，碾压成糊膏，挤条，挤出条在110℃干燥4小时，然后在550℃焙烧4小时，得载体CS-8，性质见表7。
载体用含钨和镍的浸渍液室温浸渍2小时，120℃干燥4小时，程序升温500℃焙烧4小时，得催化剂LC-8，载体及相应催化剂性质见表7。
比较例III-1
按照实施例III-2的方法制备载体，不同的是，BSS-2分子筛由相同重量的β分子筛BD-2代替，得载体CDS-1，性质见表7。
使用上述载体按照实施例III-2的方法制备催化剂，得催化剂LCD-1，载体及相应催化剂性质见表7。
比较例III-2
按照实施例III-3的方法制备载体，不同的是，BSS-6分子筛由相同重量的β分子筛BD-3代替，得载体CDS-2，性质见表7。
使用上述载体按照实施例III-3的方法制备催化剂，得催化剂LCD-2，载体及相应催化剂性质见表7。
比较例III-3
按照实施例III-7的方法制备载体，不同的是，BSS-8分子筛由相同重量的β分子筛BD-1代替，得载体CDS-3，性质见表7。
使用上述载体按照实施例III-3的方法制备催化剂，得催化剂LCD-3，载体及相应催化剂性质见表7。
比较例III-4
按照实施例III-8的方法制备载体，不同的是，BSS-1分子筛由相同重量的β分子筛BD-4代替，得载体CDS-4，性质见表7。
使用上述载体按照实施例III-8的方法制备催化剂，得催化剂LCD-4，载体及相应催化剂性质见表7。
比较例III-5
按照实施例III-8的方法制备载体，不同的是，BSS-1分子筛由相同重量的β分子筛BD-5代替，得载体CDS-5，性质见表7。
使用上述载体按照实施例III-8的方法制备催化剂，得催化剂LCD-5，载体及相应催化剂性质见表7。
比较例III-6
按照实施例III-8的方法制备载体，不同的是，BSS-1分子筛由相同重量的β分子筛BD-6代替，得载体CDS-6，性质见表7。
使用上述载体按照实施例III-8的方法制备催化剂，得催化剂LCD-6，载体及相应催化剂性质见表7。
比较例III-7
按照实施例III-8的方法制备载体，不同的是，BSS-1分子筛由相同重量的β分子筛BD-7代替，得载体CDS-7，性质见表7。
使用上述载体按照实施例III-8的方法制备催化剂，得催化剂LCD-7，载体及相应催化剂性质见表7。
表7  催化剂载体及催化剂的物化性质
Figure PCTCN2014089699-appb-000015
续表7  催化剂载体及催化剂的物化性质
比较例编号 III-1 III-2 III-3 III-4 III-5 III-6 III-7
载体              
编号 CDS-1 CDS-2 CDS-3 CDS-4 CDS-5 CDS-6 CDS-7
β分子筛，wt％ 20 30 10 15 15 15 15
氧化铝 余量 余量 余量 余量 余量 余量 余量
比表面积，m2/g 385 406 355 421 369 388 369
孔容，mL/g 0.64 0.59 0.68 0.54 0.62 0.58 0.57
催化剂              
编号 LCD-1 LCD-2 LCD-3 LCD-4 LCD-5 LCD-6 LCD-7
WO3，wt％ 25.3 22.9 22.5 23.6 23.8 23.7 23.5
NiO，wt％ 6.5 6.0 6.4 6.2 6.3 6.1 6.2
催化性能评价3
在固定床加氢试验装置上进行评价，评价条件为：反应总压10.0MPa，氢油体积比600，体积空速2.0h-1，使用催化柴油作为原料油，原料油性质列于表8。将催化剂LC-1至LC-8以及LCD-1至LCD-7在相同的工艺条件下评价，得到的评价结果列于表9。
表8  原料油性质
原料油 催化柴油-1 催化柴油-2
密度(20℃)，g/cm3 0.9423 0.9611
馏程/℃    
IBP/10％ 186/255 191/234
30％/50％ 286/310 259/286
70％/90％ 330/349 321/364
95％/EBP 359/369 377/382
凝点，℃ 5 3
硫，μg/g 8568 13603
氮，μg/g 1150 1088
十六烷值 25 15.6
C，wt％ 88.46 88.53
H，wt％ 11.07 9.31
表9  性能评价结果
Figure PCTCN2014089699-appb-000016
Figure PCTCN2014089699-appb-000017
续表9  性能评价结果
Figure PCTCN2014089699-appb-000018
Figure PCTCN2014089699-appb-000019
由表9  评价结果可以看出，本发明所制备催化剂在相同的工艺条件下，柴油收率和产品质量均优于参比催化剂。

Claims (18)

  1. 一种β分子筛，其特征在于，该β分子筛的SiO2/Al2O3摩尔比30～150，优选为40～150，进一步优选为60～120；非骨架铝占总铝的2％以下，优选为1％以下；以Si(0Al)结构配位的硅原子占骨架结构中硅原子的95％以上，优选为96％～99％。
  2. 按照权利要求1所述的β分子筛，其中，该β分子筛的相对结晶度为100％～140％。
  3. 按照权利要求1或2所述的β分子筛，其中，该β分子筛的红外酸量0.1～0.5mmol/g，NH3-TPD方法测得的中强酸的酸量占总酸量的80％以上；优选地，该β分子筛的红外酸量0.15～0.45mmol/g，NH3-TPD方法测得的中强酸的酸量占总酸量的85％～95％。
  4. 按照权利要求1-3中任意一项所述的β分子筛，其中，该β分子筛的Na2O≤0.15wt％，优选Na2O≤0.10wt％。
  5. 按照权利要求1-4中任意一项所述的β分子筛，其中，该β分子筛的比表面积为400m2/g～800m2/g，总孔容为0.30mL/g～0.50mL/g。
  6. 一种β分子筛的制备方法，该方法包括：
    (1)将β分子筛原粉与常压、动态的水蒸汽接触，接触的温度为500～650℃，时间为5～10小时；
    (2)将步骤(1)所得的产物与氟硅酸铵接触，然后过滤、水洗和干燥，得到β分子筛。
  7. 按照权利要求6所述的方法，其中，步骤(1)采用程序升温，升温速率为50～150℃/小时，升至250～450℃时，开始引入水蒸汽，并继续升温至500～650℃，然后在此温度下停留5～10小时。
  8. 按照权利要求6或7所述的方法，其中，步骤(1)中，水蒸汽按每千克β分子筛原粉50～100L/h通过β分子筛原粉。
  9. 按照权利要求6-8中任意一项所述的方法，其中，步骤(1)β分子筛原粉的SiO2/Al2O3摩尔比22.5～28.5，Na2O含量为1.0wt％～3.0wt％。
  10. 按照权利要求6-9中任意一项所述的方法，其中，步骤(2)采用的氟硅酸铵水溶液的浓度是10g～60g/100mL溶液，氟硅酸铵水溶液与β分子筛的液固体积比为3∶1～15∶1。
  11. 按照权利要求6-10中任意一项所述的方法，其中，所述接触的条件包括温度为40～120℃，时间为0.5～8.0小时。
  12. 一种加氢催化剂，该加氢催化剂包含加氢活性金属组分和载体，其中载体包含β分子筛，其特征在于，所述β分子筛为权利要求1-5中任意一项所述的β分子筛。
  13. 按照权利要求12所述的加氢催化剂，其中，所述加氢催化剂载体中还含有氧化铝，以载体的重量为基准，β分子筛的含量为5％～40％，氧化铝的含量为60％～95％。
  14. 按照权利要求12所述的加氢催化剂，其中，所述加氢催化剂载体中还含有无定形硅铝和氧化铝，以载体的重量为基准，β分子筛的含量为3％～20％，无定形硅铝的含量为10％～70％，氧化铝的含量为15％～70％。
  15. 按照权利要求14所述的加氢催化剂，其中，所述无定形硅铝中SiO2的重量含量为5％～40％，无定形硅铝的孔容为0.6～1.1mL/g，比表面积为300～500m2/g。
  16. 按照权利要求12所述的加氢催化剂，其中，所述加氢催化剂载体中还含有Y型分子筛和氧化铝，以载体的重量为基准，β分子筛的含量为5％～20％，Y型分子筛的含量为10％～40％，氧化铝的含量为40％～85％。
  17. 按照权利要求16所述的加氢催化剂，其中，所述Y型分子筛的比表面积为850m2/g～950m2/g，总孔容为0.43mL/g～0.55mL/g，SiO2/Al2O3摩尔比为20～150，晶胞参数为2.425～2.433nm，红外酸量0.1～0.4mmol/g。
  18. 按照权利要求12-17中任意一项所述的加氢催化剂，其中，所述加氢活性金属组分为第VIB族和第VIII族的金属，第VIB族的金属为钼和/或钨，第VIII族的金属为钴和/或镍，且所述加氢催化剂中，以催化剂的总量为基准，第VIB族金属以氧化物计的重量含量为10％～30％，第VIII族金属以氧化物计的重量含量为4％～8％。
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