WO2022148474A1 - 一种包含片层结构的硅铝材料、其制造方法及应用 - Google Patents

一种包含片层结构的硅铝材料、其制造方法及应用 Download PDF

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WO2022148474A1
WO2022148474A1 PCT/CN2022/071289 CN2022071289W WO2022148474A1 WO 2022148474 A1 WO2022148474 A1 WO 2022148474A1 CN 2022071289 W CN2022071289 W CN 2022071289W WO 2022148474 A1 WO2022148474 A1 WO 2022148474A1
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silicon
water
aluminum
acid
soluble
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PCT/CN2022/071289
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English (en)
French (fr)
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朱慧红
刘铁斌
金浩
时一鸣
吕振辉
杨光
刘璐
杨涛
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中国石油化工股份有限公司
中国石油化工股份有限公司大连石油化工研究院
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Priority to CA3204249A priority Critical patent/CA3204249A1/en
Priority to EP22736635.8A priority patent/EP4261189A4/en
Priority to US18/256,941 priority patent/US20240033715A1/en
Priority to KR1020237027025A priority patent/KR20230128377A/ko
Publication of WO2022148474A1 publication Critical patent/WO2022148474A1/zh

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    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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    • C07C2523/85—Chromium, molybdenum or tungsten
    • C07C2523/88—Molybdenum
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Definitions

  • the invention belongs to the technical field of catalytic materials, and relates to a silicon-aluminum material, a manufacturing method and application thereof.
  • Molecular sieves are introduced into the hydrocracking catalyst carrier to improve the cracking performance of the catalyst.
  • the macroporous silica-alumina material has suitable pore structure and acidity, good hydrothermal stability and strong cracking performance, and is especially suitable for the residue hydrocracking process.
  • the manufacturing methods of silicon-alumina materials generally include sol-gel method, kneading method, impregnation method, etc.
  • Macroporous silica-alumina materials are usually produced by a sol-gel method, which generally uses water glass or silica sol as the silicon source.
  • the difficulty in the manufacture of macroporous silicon-alumina materials is that with the increase of silica content, the pore volume of silicon-alumina materials gradually decreases, while the sodium content increases significantly.
  • an impurity of silicon-alumina materials sodium needs to be removed. In general, sodium The content needs to be less than 0.5%.
  • silica sol is used as the silicon source in the industry to reduce the times of subsequent washing and sodium removal, or ion exchange is used to achieve the sodium removal.
  • these sodium removal methods greatly increase the manufacturing cost of silicon-aluminum materials, and the economy is relatively low. poor, which limits its large-scale industrial application.
  • CN201710382457.7 discloses a highly active silicon-alumina material and a manufacturing method thereof.
  • the active silicon-alumina material contains 15-45% silicon and 55-85% aluminum based on the weight of oxides, the total BET specific surface area is 300-500 m 2 /g, and the ratio of the micropore specific surface area to the total BET specific surface area is ⁇ 8%, the average pore diameter is 5-18nm;
  • CN201710630418.4 discloses a medium and macroporous silicon-alumina material and a manufacturing method thereof.
  • the medium and macroporous silicon-alumina material in terms of oxide weight, has an anhydrous chemical expression: (0-0.3) Na 2 O : (2-18) Al 2 O 3 : (82-98) SiO 2 ;
  • the pore volume is 0.8-2mL/g, the specific surface area is 150-350m 2 /g, the most probable pore size is 30-100nm, and the B/L acid ratio is 0.8-2.0.
  • the silicon-alumina material of the present invention has the characteristics of high pore volume, large pore size, and high B/L acid ratio.
  • the ammonium salt used in the exchange is selected from one or more of ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium sulfate, and ammonium bicarbonate.
  • CN201710102634.1 discloses a silicon aluminum material, a manufacturing method and an application thereof.
  • the inventor of the present invention found that the difficulty in the preparation of macroporous silica-alumina materials is that with the increase of silica content, the pore volume of the silica-alumina material gradually decreases, while the sodium content increases significantly. Under the premise, it is very critical to effectively reduce the sodium content.
  • ammonium salt is used for ion exchange, which is complicated in processing process and increases the manufacturing cost of silicon-aluminum material.
  • the inventors of the present invention also found that usually more expensive silica sol is used as a silicon source in industry to reduce the times of subsequent washing and sodium removal, or ion exchange is used to achieve sodium removal, but these sodium removal methods greatly increase the amount of silicon aluminum.
  • the preparation cost of the material and the poor economy limit its large-scale industrial application.
  • the inventors of the present invention believe that how to prepare a macroporous silicon-alumina material while reducing the cost of removing sodium is an effective way to prepare a silicon-alumina material with excellent performance and low price. Therefore, the inventor of the present invention has found a new type of silicon-alumina material through assiduous research. The present invention has been completed based on this finding.
  • the present invention relates to the following aspects.
  • the silicon-alumina material described in any one of the preceding aspects its pore volume is not less than 1.1mL/g (preferably greater than 1.15mL/g, more preferably 1.15-1.5mL/g), and/or, its specific surface area is 260.
  • the pore volume of pores with pore diameter ⁇ 10 nm accounts for ⁇ 5% of the total pore volume (preferably pores with pore diameter ⁇ 10 nm
  • the pore volume accounts for ⁇ 3% of the total pore volume
  • the pore volume of the pores with a pore diameter of 10-50nm accounts for 65%-85% of the total pore volume (preferably, the pore volume of the pores with a pore diameter of 10-50nm accounts for the total pore volume 70%-85% of the total pore volume)
  • the pore volume of the pores with a pore diameter >50nm accounts for 10%-30% of the total pore volume (preferably, the pore volume of the pores with a pore diameter >50nm accounts for 12%-25% of the total pore volume)
  • its average pore diameter is 14-23 nm (preferably 16-21 nm).
  • the silicon-alumina material described in any one of the preceding aspects its B acid content is greater than 0.08mmol/g (preferably 0.1-0.2mmol/g or 0.1-0.15mmol/g), and/or, its B acid and L acid The ratio is 0.2-0.8 (preferably 0.3-0.7), and/or, its Na 2 O content is less than 0.3 wt % (preferably less than 0.2 wt %), and/or, in its NMR silicon spectrum, in chemical shift- There are absorption peaks at 87ppm to -89ppm, and in its aluminum NMR spectrum, there are absorption peaks near the chemical shift 57ppm, and/or, its calcined form has no diffraction peaks in the small-angle XRD pattern.
  • the silicon-alumina material according to any one of the preceding aspects further comprising a non-lamellar structure, wherein based on the total volume of the silicon-aluminum material, the lamellar structure accounts for 3% or more (preferably 5% or more). , more preferably 10-80% or 10-60%).
  • a manufacturing method of a silicon-aluminum material comprising the following steps in turn:
  • step (1) the silicon source is a water-soluble or water-dispersible alkaline silicon-containing compound (preferably a water-soluble or water-dispersible alkaline inorganic containing compound).
  • Silicon compound more preferably one or more selected from water-soluble silicate, water glass, silica sol, preferably water glass), and/or, the silicon source is used in the form of an aqueous solution, and is Based on the total weight of the aqueous solution, the concentration of the silicon source (calculated as SiO 2 ) is 5-30 wt% (preferably 15-30 wt%), and/or the acidic aluminum source is a water-soluble acidic aluminum-containing compound ( Preferably water-soluble acidic inorganic aluminum-containing compounds, especially water-soluble inorganic strong acid aluminum salts, more preferably one or more selected from aluminum sulfate, aluminum nitrate, aluminum chloride, preferably aluminum sulfate), and/ Or, the acidic aluminum source is used in the form of an aqueous solution, and based on the total weight of the aqueous solution, the concentration of the acidic aluminum source (calculated as Al 2 O 3 ) is 30-100 g/L (preferably 30-80 g/L). L),
  • step (1) an acid is also added (preferably, the acidic aluminum source is added to the silicon source, and then the acid is added to obtain the Mixture A), and/or, the acid is a water-soluble acid (preferably a water-soluble inorganic acid, more preferably one or more selected from sulfuric acid, nitric acid, and hydrochloric acid, preferably sulfuric acid), and/or,
  • the acid is used in the form of an aqueous solution, and the concentration of the acid is 2-6 wt% (preferably 2-5 wt%) based on the total weight of the aqueous solution, and/or, the acid is added in an amount such that the The pH of mixture A is 2-4 (preferably 3-4).
  • step (2) the basic aluminum source is a water-soluble basic aluminum-containing compound (preferably a water-soluble basic inorganic aluminum-containing compound, especially Alkali metal metaaluminate, more preferably selected from one or more of sodium metaaluminate and potassium metaaluminate, preferably sodium metaaluminate), and/or, the alkaline aluminum source is in the form of an aqueous solution.
  • the basic aluminum source is a water-soluble basic aluminum-containing compound (preferably a water-soluble basic inorganic aluminum-containing compound, especially Alkali metal metaaluminate, more preferably selected from one or more of sodium metaaluminate and potassium metaaluminate, preferably sodium metaaluminate), and/or, the alkaline aluminum source is in the form of an aqueous solution.
  • the concentration of the basic aluminum source is 130-350 g/L (preferably 150-250 g/L) based on the total weight of the aqueous solution, and/or, so that Based on the total volume of the mixture A, the basic aluminum source and water, the amount of the mixture A is 40-80 vol% (preferably 45-75 vol%), and/or, the mixture A, the alkali Based on the total volume of the alkaline aluminum source and water, the amount of the alkaline aluminum source is 10-30 vol% (preferably 12-25 vol%), and/or, based on the mixture A, the alkaline aluminum source and water Based on the total volume of the water, the amount of the water used is 10-30 vol% (preferably 10-25 vol%), and/or, the mixture A and the basic aluminum source are added to the water sequentially or simultaneously (preferably adding all the The mixture A and the basic aluminum source are added to the water in a co-current manner), and/or, the addition flow rate of the mixture A is 15-50 mL/min (preferably 150-250 g/L)
  • step (2) water-soluble carbonate is also added (preferably, the mixture A and the alkaline aluminum source are added to water, and then the water-soluble carbonate is added. carbonate to obtain the slurry B), and/or, the water-soluble carbonate is selected from one or more carbonates of alkali metals and ammonium (preferably selected from sodium carbonate, One or more of potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate, preferably sodium carbonate), and/or, the water-soluble carbonate is used in solid form, and/or , the water-soluble carbonate is added in an amount such that the pH value of the slurry B is 10.5-12 (preferably 11-12).
  • step (3) the silicon-alumina material is separated from the reaction system of the hydrothermal treatment (such as filtration or centrifugation), washed to neutrality, and then Drying, and/or the drying conditions include: a drying temperature of 100-150° C. and a drying time of 6-10 hours.
  • step (1) the temperature is 25-50° C. (preferably 25-40° C.), the pressure is normal pressure, and/or, in step (2), The temperature is 50-90°C (preferably 50-80°C), the pressure is normal pressure, and/or, in step (3), the temperature is 180-300°C (preferably 180-280°C, more preferably 180-250°C °C), the pressure is 0.1-0.5MPa (preferably 0.1-0.3MPa), and/or, in step (3), the initial moment of the hydrothermal treatment is set to be t 0 , and the reaction system of the hydrothermal treatment reaches the viscosity
  • auxiliary agent preferably one or more selected from phosphorus, boron and titanium
  • the weight of the auxiliary agent is based on oxides
  • the content is 1-8 wt % (preferably 2-6 wt %), based on 100 wt % of the total weight of the silicon-alumina material.
  • a catalytic material comprising an active metal component and the silicon-alumina material according to any one of the preceding aspects or the silicon-alumina material produced by the manufacturing method according to any one of the preceding aspects.
  • the active metal component is a metal component having hydrogenation activity (preferably selected from at least one of metals from Group VIB and Group VIII of the Periodic Table of the Elements, In particular, at least one selected from the group consisting of Mo, W, Ni and Co), and/or, based on the total weight of the catalytic material, the active metal component (calculated as oxides) has a weight percent content of 5 -30wt% (preferably 5-25wt%).
  • a process for hydrogenation comprising the step of subjecting a hydrocarbonaceous material to a hydrogenation reaction in the presence of the catalytic material of any preceding aspect.
  • the hydrocarbon-containing material is selected from at least one of diesel oil, wax oil, heavy oil, coal tar, ethylene tar, and catalytic oil slurry, and/or, the
  • the reaction conditions of the hydrogenation reaction include: the reaction pressure is 5-20MPaG, the reaction temperature is 300-450°C, the liquid hourly volume space velocity is 0.1-1.5h -1 , and the hydrogen-oil volume ratio is 100-1000.
  • the silicon-alumina material provided by the present invention has the characteristics of large pore volume, mesoporous-macroporous two-stage gradient channel, and high content of molecular sieve B acid, and the appearance of the lamellar structure causes the silicon-alumina material to It begins to show the crystal characteristics of molecular sieves, low impurity content (especially low sodium content), suitable for use as a catalyst material carrier, especially suitable for use as a heavy oil hydrogenation catalyst carrier.
  • the silicon source is contacted with the acidic aluminum source, especially in a preferred case, further contacted with an acid, so that the silicon source is encapsulated in the ring or in the cage to polymerize the silicic acid
  • the cations (sodium ions, etc.) in the material are dissociated, and the acidified silica gel group is adsorbed on the aluminum hydroxide colloid, so that the sodium ion and the silica gel group are effectively separated. It is easier to remove sodium ions, which greatly reduces the difficulty of removing sodium in subsequent washing and can reduce the water consumption for washing. More importantly, the cations (sodium ions) can be effectively removed, and the acid sites occupied by Na can be restored, making the silicon-alumina materials more acidic.
  • the acidified silica gel group is adsorbed on the aluminum hydroxide colloid, which provides a crystal nucleus for the subsequent reaction, promotes the increase of the crystal grain of the manufactured silicon-alumina material, and is conducive to the formation of macropores Silicon aluminum material with large capacity and pore size.
  • the pH value of the slurry B is adjusted by adding a water-soluble carbonate, and then during the treatment process at a certain temperature and a certain pressure, the slurry system
  • the morphology will change from the initial fluid state to a gel-like thixotropic state, which is manifested in that the viscosity of the reaction system gradually increases and reaches a peak value.
  • the viscosity of the reaction system gradually decreases, and in the process of transforming into a gel-like thixotropic state, the silica-alumina material and water form a variable silica-alumina-oxygen network structure with each other, which is conducive to the manufacture of a large pore volume of the silica-alumina material.
  • the added carbonate promotes the directional growth of the lamellar structure of Si-Al grains, and the content of lamellar structure increases with the prolongation of treatment time.
  • the formation of the lamellar structure changed the bonding mode of Si and Al, and promoted the increase of B acid content.
  • FIG. 1 is a SEM photograph of the silicon-alumina material produced in Example 1 of the present invention.
  • Example 5 is a small-angle XRD pattern of the silicon-alumina material produced in Example 1 of the present invention.
  • both the silica-alumina material and the catalyst are subjected to a calcination treatment, sometimes referred to as "calcined form", prior to taking measurements.
  • the conditions of the calcination treatment include: in an air atmosphere, the calcination temperature is 600° C., and the calcination time is more than 3 hours.
  • the pore volume, specific surface area, average pore size and pore distribution of the silica-alumina materials and catalysts are measured using the low temperature nitrogen adsorption method.
  • the total acid, B acid and L acid of the silica-alumina material and catalyst are measured using the pyridine infrared adsorption method.
  • the content of sodium oxide, aluminum oxide and silicon dioxide of the silico-alumina material is measured using a fluorometric method.
  • the active metal content of the catalyst is measured spectrophotometrically.
  • the wear index is measured using the air jet method.
  • X-ray diffraction (XRD) characterization adopts D/max2500 X-ray diffraction analyzer produced by RIGAKU, Japan, with a working voltage of 40kV, a working current of 40mA, and a scanning range of 10(°) ⁇ 70(° ), the step size is 0.06(°), and the scan rate is 0.21(°) ⁇ min -1 .
  • the small-angle XRD characterization adopts the D/max2500 X-ray diffraction analyzer produced by RIGAKU in Japan, the working voltage is 40kV, the working current is 40mA, the scanning range is 1.5(°) ⁇ 8(°), the step size is 1.5(°) ⁇ 8(°) 0.01(°), scan rate 0.02(°) ⁇ min -1
  • sample morphology characterization was performed on a JXM-7500F field emission scanning electron microscope produced by Japan Electronics Corporation, with a working voltage of 6.5 eV, an acceleration voltage of 5.0 kV, and a magnification of 30,000 times.
  • solid-state nuclear magnetic 29Si MAS NMR experiments were performed on a Varian Infinity plus-600 solid-state NMR spectrometer.
  • the resonance frequencies of 1 H and 29 Si nuclei are 599.51 and 120.35 MHz, respectively.
  • the 29 Si MAS NMR was acquired on a 7.5mm dual-resonance probe using a single-pulse high-power decoupling technique with a ⁇ /2 pulse width of 6.1 ⁇ s, a pulse delay time of 80 s, and a rotational speed of 5 kHz.
  • 29Si spectral chemical shifts were calibrated by kaolin ( -91.5 ppm).
  • the average particle size of the silicon-alumina material is magnified to 30,000 times by SEM, and is obtained by averaging 20 different pictures.
  • the average particle size of the primary particles of the silicon-alumina material is magnified to 30,000 times by SEM, and 20 different pictures are counted and averaged.
  • the average length and average thickness of the lamellar structure are magnified to 30,000 times using SEM, and are averaged from 20 different images.
  • the viscosity of the reaction system can be measured by any method, as long as an effective comparison can be made with the prolongation of the reaction time, and there is no particular limitation.
  • any two or more embodiments of the present invention can be combined arbitrarily, and the technical solutions formed thereby belong to a part of the original disclosure content of this specification, and also fall within the protection scope of the present invention.
  • a silicon-aluminum material whose SiO 2 /Al 2 O 3 molar ratio is 0.8-1.5 (preferably 1.0-1.4).
  • the silicon-alumina material comprises a lamellar structure with an average length of 0.5-2 ⁇ m (preferably 0.5-1.5 ⁇ m) and an average thickness of 30-80 nm (preferably 30-75 nm). This can be confirmed by SEM photographs.
  • the calcined form of the silicon-alumina material has an XRD pattern substantially as shown in Table I below.
  • the calcined form of the silicon-alumina material preferably has an XRD pattern substantially as shown in Table II below.
  • the fired form of the silicon-alumina material has an XRD pattern substantially as shown in FIG. 2 .
  • the pore volume of the silicon-alumina material is not less than 1.1 mL/g (preferably greater than 1.15 mL/g, more preferably 1.15-1.5 mL/g).
  • the specific surface area of the silicon-alumina material is 260-340 m 2 /g (preferably 260-310 m 2 /g).
  • the pore distribution of the silicon-alumina material is such that the pore volume of the pores with the pore diameter ⁇ 10 nm accounts for ⁇ 5% of the total pore volume (preferably, the pore volume of the pores with the pore diameter ⁇ 10 nm accounts for the total pore volume ⁇ 3%), the pore volume of the pores with a pore diameter of 10-50nm accounts for 65%-85% of the total pore volume (preferably, the pore volume of the pores with a pore diameter of 10-50nm accounts for 70%-85% of the total pore volume ), the pore volume of the pores with pore diameter>50nm accounts for 10%-30% of the total pore volume (preferably, the pore volume of the pores with pore diameter>50nm accounts for 12%-25% of the total pore volume).
  • the average pore size of the silicon-alumina material is 14-23 nm (preferably 16-21 nm).
  • the B acid content of the silicon-alumina material is greater than 0.08 mmol/g (preferably 0.1-0.2 mmol/g or 0.1-0.15 mmol/g).
  • the ratio of B acid to L acid of the silicon-alumina material is 0.2-0.8 (preferably 0.3-0.7).
  • the Na 2 O content of the silicon-alumina material is less than 0.3 wt % (preferably less than 0.2 wt %).
  • the average particle size of the silicon-alumina material is 30-100 nm (preferably 30-80 nm).
  • the silicon-alumina material has absorption peaks at chemical shifts of -87ppm to -89ppm in its nuclear magnetic resonance silicon spectrum, indicating that the silicon-oxygen tetrahedron is directly connected to three aluminum-oxygen tetrahedrons.
  • the silicon-alumina material has an absorption peak near the chemical shift of 57 ppm in its nuclear magnetic resonance aluminum spectrum, indicating that four-coordinated framework aluminum exists in the material.
  • the calcined form of the silicon-alumina material has no diffraction peaks on the small-angle XRD pattern, indicating that there are no molecular sieve characteristic peaks.
  • the silicon-alumina material further comprises a non-lamellar structure.
  • the non-lamellar structure is an aggregate of a plurality of primary silicon-alumina particles, showing the characteristics of amorphous silicon-alumina.
  • the average particle size of the silica-alumina primary particles is generally 5-25 nm (preferably 10-25 nm).
  • the proportion of the lamellar structure is more than 3% (preferably more than 5%, more preferably 10-80% or 10-60%) .
  • the present invention also relates to a manufacturing method of a silicon-aluminum material, which can be used to manufacture the silicon-aluminum material as described above in this specification.
  • the manufacturing method includes the following steps in sequence:
  • step (1) the acidic aluminum source is added to the silicon source, instead of adding the silicon source to the acidic aluminum source, otherwise a large amount of precipitation will be formed.
  • the silicon source is a water-soluble or water-dispersible alkaline silicon-containing compound (preferably a water-soluble or water-dispersible alkaline compound) Inorganic silicon-containing compound, more preferably one or more selected from water-soluble silicate, water glass, and silica sol, preferably water glass).
  • a water-soluble or water-dispersible alkaline silicon-containing compound preferably a water-soluble or water-dispersible alkaline compound
  • Inorganic silicon-containing compound more preferably one or more selected from water-soluble silicate, water glass, and silica sol, preferably water glass.
  • the silicon source in the manufacturing method, is used in the form of an aqueous solution.
  • concentration of the silicon source (calculated as SiO 2 ) is 5-30 wt % (preferably 15-30 wt %) based on the total weight of the aqueous solution, and its modulus is generally 2.5-3.2.
  • the acidic aluminum source is a water-soluble acidic aluminum-containing compound (preferably a water-soluble acidic inorganic aluminum-containing compound, especially a water-soluble inorganic strong acid aluminum salt, more It is preferably selected from one or more of aluminum sulfate, aluminum nitrate, and aluminum chloride, preferably aluminum sulfate).
  • a water-soluble acidic aluminum-containing compound preferably a water-soluble acidic inorganic aluminum-containing compound, especially a water-soluble inorganic strong acid aluminum salt, more It is preferably selected from one or more of aluminum sulfate, aluminum nitrate, and aluminum chloride, preferably aluminum sulfate).
  • the acidic aluminum source in the manufacturing method, is used in the form of an aqueous solution, and based on the total weight of the aqueous solution, the acidic aluminum source (as Al 2 O 3 ) has an amount of The concentration is 30-100 g/L (preferably 30-80 g/L).
  • the weight ratio of the silicon source (calculated as SiO 2 ) to the acid aluminum source (calculated as Al 2 O 3 ) is 1:1-9:1 (preferably 1:1-7:1).
  • step (1) in order to achieve more excellent technical effects of the present invention, especially in order to obtain a silicon-aluminum material with a larger pore volume and a lower impurity content, in step (1) , also adding an acid (preferably adding the acidic aluminum source to the silicon source and then adding the acid to give the mixture A).
  • an acid preferably adding the acidic aluminum source to the silicon source and then adding the acid to give the mixture A.
  • the acid is a water-soluble acid (preferably a water-soluble inorganic acid, more preferably one or more selected from sulfuric acid, nitric acid, and hydrochloric acid, preferably sulfuric acid).
  • a water-soluble acid preferably a water-soluble inorganic acid, more preferably one or more selected from sulfuric acid, nitric acid, and hydrochloric acid, preferably sulfuric acid.
  • the acid in the production method, is used in the form of an aqueous solution.
  • concentration of the acid is 2-6 wt% (preferably 2-5 wt%) based on the total weight of the aqueous solution.
  • the acid is added in an amount such that the pH of the mixture A is 2-4 (preferably 3-4).
  • the aluminum content of the mixture A is 5-20 gAl 2 O 3 /L in terms of Al 2 O 3
  • the silicon content is 5-40 gSiO 2 /L in terms of SiO 2 .
  • the basic aluminum source is a water-soluble basic aluminum-containing compound (preferably a water-soluble basic inorganic aluminum-containing compound, In particular, alkali metal metaaluminate, more preferably one or more selected from sodium metaaluminate and potassium metaaluminate, preferably sodium metaaluminate).
  • a water-soluble basic aluminum-containing compound preferably a water-soluble basic inorganic aluminum-containing compound,
  • alkali metal metaaluminate more preferably one or more selected from sodium metaaluminate and potassium metaaluminate, preferably sodium metaaluminate.
  • the alkaline aluminum source in the manufacturing method, is used in the form of an aqueous solution.
  • the concentration of the alkaline aluminum source (calculated as Al 2 O 3 ) is 130-350g/L (preferably 150-250g/L), and its causticity ratio is generally 1.15-1.35, preferably is 1.15-1.30.
  • the amount of the mixture A used is 40-80 vol% (preferably 45-80 vol%). 75vol%).
  • the amount of the basic aluminum source used is 10-30 vol% (preferably 12-25vol%).
  • the amount of the water used is 10-30 vol% (preferably 10-25 vol %). %).
  • the mixture A and the basic aluminum source are added into water sequentially or simultaneously (preferably, the mixture A and the basic aluminum source are in co-current flow). added to the water).
  • the addition flow rate of the mixture A is 15-50 mL/min (preferably 20-40 mL/min).
  • the addition flow rate of the alkaline aluminum source is controlled so that the pH value of the slurry B is maintained at 7.5-10.5 (preferably 8.0-10.5, more preferably 8.5- 10.5).
  • step (2) in order to achieve more excellent technical effects of the present invention, especially in order to obtain a silicon-alumina material with a larger pore volume, in step (2), a water-soluble Carbonate (preferably adding the mixture A and the basic aluminum source to water followed by the water-soluble carbonate to obtain the slurry B).
  • a water-soluble Carbonate preferably adding the mixture A and the basic aluminum source to water followed by the water-soluble carbonate to obtain the slurry B.
  • the water-soluble carbonate is selected from one or more carbonates of alkali metals and ammonium (preferably from sodium carbonate, potassium carbonate, One or more of sodium bicarbonate, potassium bicarbonate, ammonium carbonate and ammonium bicarbonate, preferably sodium carbonate).
  • the water-soluble carbonate is used in the form of a solid.
  • the water-soluble carbonate is added in an amount such that the pH of the slurry B is 10.5-12 (preferably 11-12).
  • the silicon-alumina material is separated from the reaction system of the hydrothermal treatment, washed to neutrality, and then dried.
  • the washing can be carried out by a conventional washing method in the art, preferably with deionized water, and more preferably at 50°C-90°C.
  • the separation can be carried out by any means in the art that can realize the separation of liquid-solid two-phase materials, such as filtration, centrifugal separation, etc.
  • the separation can be carried out by means of filtration and separation, and the solid phase can be obtained after separation. The material and the liquid phase material, the solid phase material is washed and dried to obtain the silicon-alumina material.
  • the drying conditions include: a drying temperature of 100-150° C. and a drying time of 6-10 hours.
  • the temperature is 25-50° C. (preferably 25-40° C.), and the pressure is normal pressure.
  • the temperature is 50-90° C. (preferably 50-80° C.), and the pressure is normal pressure.
  • the temperature is 180-300°C (preferably 180-280°C, more preferably 180-250°C), and the pressure is 0.1-0.5 MPa (preferably 0.1-0.3MPa).
  • the hydrothermal treatment is set.
  • the initial time of the hydrothermal treatment is t 0
  • the time when the reaction system of the hydrothermal treatment reaches the maximum viscosity is t max
  • ⁇ t t max -t 0
  • the time (unit is h) of the hydrothermal treatment is from ⁇ t+1 to ⁇ t+20 (preferably from ⁇ t+2 to ⁇ t+12, in particular from ⁇ t+4 to ⁇ t+8).
  • the time of the hydrothermal treatment may be 6-20h (preferably 8-12h).
  • auxiliary agents such as one or more of P 2 O 5 , B 2 O 3 or TiO 2 , may be added according to actual needs.
  • these precursors may be added in the form of water-soluble inorganic salts during the reaction of step (1).
  • inorganic salt a borate, a sulfate, a nitrate, etc. are mentioned specifically, for example.
  • the addition amount of these additives can be adjusted arbitrarily according to the requirements of subsequent catalysts and the like.
  • the weight content of these additives in terms of oxides is generally 1-8 wt %, preferably 2-6 wt %, relative to the total weight of the silicon-alumina material 100 wt %.
  • a catalytic material comprising an active metal component and the silicon-alumina material as described above in this specification or a silicon-aluminum material manufactured according to the manufacturing method as described above in this specification.
  • the active metal component is a metal component with hydrogenation activity (preferably selected from at least one of metals from Group VIB and Group VIII of the Periodic Table of the Elements, especially from Mo , at least one of W, Ni and Co).
  • the weight percent content of the active metal component (calculated as oxide) is 5-30 wt % (preferably 5-25 wt %).
  • the present invention also relates to a hydrogenation process comprising the step of subjecting a hydrocarbon-containing material to a hydrogenation reaction in the presence of a catalytic material as previously described in this specification.
  • the hydrocarbon-containing material is selected from at least one of diesel oil, wax oil, heavy oil, coal tar, ethylene tar, and catalytic oil slurry.
  • the reaction conditions for the hydrogenation reaction include: the reaction pressure is 5-20MPaG, the reaction temperature is 300-450°C, the liquid hourly volume space velocity is 0.1-1.5h -1 , and the volume ratio of hydrogen to oil is is 100-1000.
  • the aluminum sulfate solution with a concentration of 50gAl 2 O 3 /L and a silica sol solution with a concentration of 50gSiO 2 /L and a modulus of 2.8 were prepared for use, and a dilute sulfuric acid solution with a concentration of 1mol/L was prepared for use.
  • the above slurry was put into the reactor, and under stirring conditions, the treatment temperature was 210° C., the treatment pressure was 0.4 MPa, and the treatment was performed for 8 hours (equivalent to ⁇ t+6 hours).
  • the treated slurry was washed with hot water at 90°C until the liquid was neutral, dried at 120°C for 6 hours to obtain the dried sample PO-1, and calcined at 600°C for 5 hours to obtain the silicon-alumina material P-1, whose properties are shown in Table 1 .
  • the silicon-alumina material includes a lamellar structure and a non-lamellar structure, and its average particle size is 50 nm.
  • the lamella structure has an average length of 1.0 ⁇ m and an average thickness of 50 nm, and accounts for 35% of the total volume of the silicon-alumina material.
  • the SiO 2 /Al 2 O 3 molar ratio of the silicon-alumina material is 1.21.
  • the silicon NMR spectrum of the silicon-alumina material Fig. 3
  • the aluminum NMR spectrum of the silicon-alumina material Fig.
  • Example 2 Other conditions are the same as in Example 1, except that the silica sol is changed to water glass solution, the concentration is adjusted to 58 gSiO 2 /L, the flow rate of the mixed solution A is 15 mL/min, and the deionized water in the reactor is heated to 80 ° C to obtain The dry sample PO-2 of the silicon-alumina material was calcined at 600°C for 5h to obtain the silicon-alumina material P-2, whose properties are shown in Table 1.
  • the SiO 2 /Al 2 O 3 molar ratio of the silicon-aluminum material is 1.44, and the lamellar structure with an average length of 1.5 ⁇ m and an average thickness of 61 nm is included.
  • the lamellar structure accounts for 54% of the total volume of the silicon-alumina material.
  • the carrier Z2 was saturated with the solution L1 solution, dried at 110 °C for 2 h, and calcined at 580 °C for 3 h to obtain the catalyst C2.
  • the specific properties are shown in Table 2.
  • Example 2 Other conditions are the same as in Example 1, the difference is: the pH of controlling the reaction by adjusting the flow rate of sodium metaaluminate is 9.0, adding 53g of sodium carbonate in the reactor under agitation to adjust the pH value to be 11.0, and the treatment temperature is 280 ° C , the processing pressure is 0.4MPa, and the dry sample PO-3 of silicon and aluminum is obtained.
  • the SiO 2 /Al 2 O 3 molar ratio of the silicon-aluminum material is 1.19, and the lamellar structure has an average length of 1.4 ⁇ m and an average thickness of 56 nm.
  • the lamellar structure accounts for 40% of the total volume of the silicon-alumina material.
  • the carrier Z3 was saturated with solution L1 solution, dried at 110 °C for 2 h, and calcined at 480 °C for 4 h to obtain catalyst C3.
  • the specific properties are shown in Table 2.
  • Example 2 The other conditions are the same as those in Example 1, except that: without adding 1 mol/L dilute sulfuric acid solution for acidification, a dry sample of silicon-alumina PO-4 was prepared, and the silicon-alumina material P-4 was obtained by roasting at 600 °C for 5 hours. See Table 1 for properties.
  • the carrier Z4 was saturated with solution L1 solution, dried at 110 °C for 2 h, and calcined at 450 °C for 3 h to obtain catalyst C4.
  • the specific properties are shown in Table 2.
  • the SiO 2 /Al 2 O 3 molar ratio of the silicon-aluminum material is 1.19, and the lamellar structure with an average length of 1.5 ⁇ m and an average thickness of 32 nm is included.
  • the lamellar structure accounts for 15% of the total volume of the silicon-alumina material.
  • Example 2 The other conditions are the same as those in Example 1, except that the caustic ratio of sodium metaaluminate is adjusted to 1.20, the pH value of gel formation is adjusted to 6.0, and the dry sample PFO-5 of silica-alumina is prepared. P-5, whose properties are shown in Table 1.
  • the carrier Z5 was saturated with the solution L1 solution, dried at 110 °C for 2 h, and calcined at 450 °C for 3 h to obtain the catalyst C5.
  • the specific properties are shown in Table 2.
  • the SiO 2 /Al 2 O 3 molar ratio of the silicon-aluminum material is 1.19, and the material includes a lamellar structure with an average length of 1.0 ⁇ m and an average thickness of 20 nm.
  • the lamellar structure accounts for 10% of the total volume of the silicon-alumina material.
  • Example 2 Other conditions are the same as those in Example 1, except that the water-soluble carbonate is changed to sodium hydroxide to prepare a dry sample of silicon-alumina PFO-6, which is calcined at 600°C for 5 hours to obtain a silicon-alumina material P-6. See Table 1.
  • the carrier Z6 was saturated with solution L1 solution, dried at 110 °C for 2 h, and calcined at 450 °C for 3 h to obtain catalyst C6.
  • the specific properties are shown in Table 2.
  • the SiO 2 /Al 2 O 3 molar ratio of the silicon-aluminum material is 1.19, and the lamellar structure with an average length of 0.8 ⁇ m and an average thickness of 15 nm is included.
  • the lamellar structure accounts for 5% of the total volume of the silicon-alumina material.
  • Example 1 The other conditions are the same as those in Example 1, except that no water-soluble carbonate is added to adjust the pH value to prepare a dry sample of silicon-alumina PFO-7, which is calcined at 600°C for 5 hours to obtain a silicon-alumina material P-7. Table 1.
  • the carrier Z7 was saturated with solution L1 solution, dried at 110 °C for 2 h, and calcined at 450 °C for 3 h to obtain catalyst C7.
  • the specific properties are shown in Table 2.
  • the SiO 2 /Al 2 O 3 molar ratio of the silicon-aluminum material is 1.19, which cannot form a lamellar structure.
  • Example 2 Other conditions are the same as those in Example 1, except that: adding ammonium carbonate to adjust the pH value to 9.5 to prepare a dry silicon-alumina sample PFO-8, and calcining at 600°C for 5 hours to obtain a silicon-alumina material P-7, whose properties are shown in Table 1 .
  • the carrier Z8 was saturated with the solution L1, dried at 110 °C for 2 h, and calcined at 450 °C for 3 h to obtain the catalyst C8.
  • the specific properties are shown in Table 2.
  • the SiO 2 /Al 2 O 3 molar ratio of the silicon-aluminum material is 1.20, and the material includes a lamellar structure with an average length of 0.6 ⁇ m and an average thickness of 20 nm.
  • the lamellar structure accounts for 3% of the total volume of the silicon-alumina material.
  • Aluminum sulfate solution with concentration of 60gAl 2 O 3 /L and water glass solution with concentration of 75gSiO 2 /L and modulus of 3.0 were prepared for use, and diluted nitric acid solution with concentration of 2mol/L was prepared for use. It was prepared into a sodium metaaluminate solution with a caustic ratio of 1.30 and a concentration of 130 gAl 2 O 3 /L for use.
  • the above slurry was put into the reactor, and under stirring conditions, the treatment temperature was 230° C., the treatment pressure was 0.5 MPa, and the treatment was carried out for 10 hours.
  • the treated slurry was washed with hot water at 90°C until the liquid was neutral, and dried at 150°C for 4 hours to obtain the dried sample PFO-9, which was calcined at 600°C for 5 hours to obtain the silicon-alumina material P-9. Its properties are shown in Table 1. .
  • the SiO 2 /Al 2 O 3 molar ratio of the silicon-aluminum material is 1.35, and the lamellar structure has an average length of 1.44 ⁇ m and an average thickness of 59 nm.
  • the lamellar structure accounts for 48% of the total volume of the silicon-alumina material.
  • Example 4 Other conditions are the same as in Example 4, except that 600 mL of water is added to the reactor, the gelling temperature is adjusted to 80 °C, and the pH value is adjusted to 10.0.
  • the pressure was 0.4MPa to obtain a dry sample of silicon-alumina PFO-10, which was calcined at 600°C for 5h to obtain a silicon-alumina material PF-10, whose properties are shown in Table 1.
  • the SiO 2 /Al 2 O 3 molar ratio of the silicon-aluminum material is 1.34, and the lamellar structure has an average length of 1.41 ⁇ m and an average thickness of 58 nm.
  • the lamellar structure accounts for 44% of the total volume of the silicon-alumina material.
  • the carrier Z10 was saturated with solution L2 solution, dried at 110 °C for 2 h, and calcined at 550 °C for 3 h to obtain catalyst C10.
  • the specific properties are shown in Table 2.
  • the above slurry was put into the reactor, and under stirring conditions, the treatment temperature was 210° C., the treatment pressure was 0.4 MPa, and the treatment was performed for 8 hours (equivalent to ⁇ t+6 hours).
  • the treated slurry was washed with hot water at 90°C until liquid neutrality, and dried at 120°C for 6 hours to obtain the dried sample PFO-1, which was calcined at 600°C for 5 hours to obtain PF-1, a silicon-alumina material whose properties are shown in Table 1. .
  • the SiO 2 /Al 2 O 3 molar ratio of the silicon-aluminum material is 1.20, and no lamellar structure can be seen from the SEM pictures, all of which are non-lamellar structures.
  • the carrier ZF1 was saturated with solution L1 solution, dried at 110 °C for 2 h, and calcined at 450 °C for 3 h to obtain catalyst CF1.
  • the specific properties are shown in Table 2.
  • the aluminum sulfate solution with a concentration of 50gAl 2 O 3 /L and a silica sol solution with a concentration of 50gSiO 2 /L and a modulus of 2.8 were prepared for use, and a dilute sulfuric acid solution with a concentration of 1mol/L was prepared for use.
  • the above slurry was put into the reactor, and under stirring conditions, the treatment temperature was 210° C., the treatment pressure was 0.4 MPa, and the treatment was performed for 8 hours (equivalent to ⁇ t+6 hours).
  • the treated slurry was washed with hot water at 90°C until the liquid was neutral, and dried at 120°C for 6 hours to obtain the dried sample PFO-2, which was calcined at 600°C for 5 hours to obtain the silicon-alumina material PF-2. Its properties are shown in Table 1. .
  • the carrier ZF2 was saturated with solution L1 solution, dried at 110 °C for 2 h, and calcined at 450 °C for 3 h to obtain catalyst CF2.
  • the specific properties are shown in Table 2.
  • the SiO 2 /Al 2 O 3 molar ratio of the silicon-aluminum material is 1.19, and no lamellar structure can be seen from the SEM photograph, all of which are non-lamellar structures.
  • the aluminum sulfate solution with a concentration of 50gAl 2 O 3 /L and a silica sol solution with a concentration of 50gSiO 2 /L and a modulus of 2.8 were prepared for use, and a dilute sulfuric acid solution with a concentration of 1mol/L was prepared for use.
  • the SiO 2 /Al 2 O 3 molar ratio of the silicon-aluminum material is 1.20, and no lamellar structure can be seen from the SEM pictures, all of which are non-lamellar structures.
  • the carrier ZF3 was saturated with solution L1 solution, dried at 110 °C for 2 h, and calcined at 450 °C for 3 h to obtain catalyst CF3.
  • the specific properties are shown in Table 2.
  • the aluminum sulfate solution with a concentration of 50gAl 2 O 3 /L and a silica sol solution with a concentration of 50gSiO 2 /L and a modulus of 2.8 were prepared for use, and a dilute sulfuric acid solution with a concentration of 1mol/L was prepared for use.
  • the above slurry was put into the reactor, and under stirring conditions, the treatment temperature was 210° C., the treatment pressure was 0.4 MPa, and the treatment was performed for 8 hours (equivalent to ⁇ t+6 hours).
  • the treated slurry was washed with hot water at 90°C until the liquid was neutral, and dried at 120°C for 6 hours to obtain the dried sample PF0-4, which was calcined at 600°C for 5 hours to obtain PF-4, a silicon-alumina material whose properties are shown in Table 1. .
  • the SiO 2 /Al 2 O 3 molar ratio of the silicon-aluminum material is 1.20, and no lamellar structure can be seen from the SEM pictures, all of which are non-lamellar structures.
  • the aluminum sulfate solution with a concentration of 50gAl 2 O 3 /L and a silica sol solution with a concentration of 50gSiO 2 /L and a modulus of 2.8 were prepared for use, and a dilute sulfuric acid solution with a concentration of 1mol/L was prepared for use.
  • the mixed solution A was added to the 5000mL reactor at 28mL/min, and the prepared sodium metaaluminate solution was added in parallel, and the pH of the reaction was controlled to be 8.3 by adjusting the sodium metaaluminate flow rate, and the reactor was maintained by heating in a water bath.
  • the inner slurry temperature was 80°C and pH was constant.
  • the amount of sodium metaaluminate was 325 mL, and 75 g of ammonium carbonate was added to the reactor under stirring to adjust the pH to 10.8.
  • the above slurry was put into the reactor, and under stirring conditions, the treatment temperature was 210° C., the treatment pressure was 0.4 MPa, and the treatment was performed for 8 hours (equivalent to ⁇ t+6 hours).
  • the treated slurry was washed with hot water at 90°C until the liquid was neutral, and dried at 120°C for 6 hours to obtain the dried sample PFO-5, which was calcined at 600°C for 5 hours to obtain PF-5, a silicon-alumina material whose properties are shown in Table 1. .
  • the SiO 2 /Al 2 O 3 molar ratio of the silicon-alumina material is 1.20.
  • the aluminum sulfate solution with a concentration of 50 gAl 2 O 3 /L and a dilute sulfuric acid solution with a concentration of 1 mol/L were prepared for use.
  • a sodium metaaluminate solution with a caustic ratio of 1.25 and a concentration of 160 gAl 2 O 3 /L was prepared for use.
  • the above slurry was put into the reactor, and under stirring conditions, the treatment temperature was 210° C., the treatment pressure was 0.4 MPa, and the treatment was performed for 8 hours (equivalent to ⁇ t+6 hours).
  • the treated slurry was washed with hot water at 90°C until the liquid was neutral, dried at 120°C for 6h to obtain the dried sample PF0-6, and calcined at 600°C for 5h to obtain the silicon-alumina material PF-6, whose properties are shown in Table 1 .
  • the SiO 2 /Al 2 O 3 molar ratio of the silicon-alumina material is 1.20, and the lamellar structure cannot be seen from the SEM photograph.
  • the aluminum sulfate solution with a concentration of 50gAl 2 O 3 /L and a silica sol solution with a concentration of 50gSiO 2 /L and a modulus of 2.8 were prepared for use, and a dilute sulfuric acid solution with a concentration of 1mol/L was prepared for use.
  • the above slurry was put into the reactor, and under stirring conditions, the treatment temperature was 210° C., the treatment pressure was 0.4 MPa, and the treatment was performed for 3 hours (equivalent to ⁇ t+1 hour).
  • the treated slurry was washed with hot water at 90°C until the liquid was neutral, and dried at 120°C for 6 hours to obtain the dried sample PFO-7, which was calcined at 600°C for 5 hours to obtain PF-7, a silicon-alumina material whose properties are shown in Table 1. .
  • the SiO 2 /Al 2 O 3 molar ratio of the silicon-aluminum material is 1.20, and the lamellar structure with an average length of 0.85 ⁇ m and an average thickness of 25 nm is included.
  • the lamellar structure accounts for 2% of the total volume of the silicon-alumina material.
  • the carrier Z7 was saturated with the solution L1 solution, dried at 110 °C for 2 h, and calcined at 450 °C for 3 h to obtain the catalyst CF7.
  • the specific properties are shown in Table 2.
  • the silicon-alumina material manufactured by the present invention has a large pore volume, a small proportion of pores ⁇ 10 nm, a low sodium oxide content, and a high B acid content.
  • the hydrogenation catalyst made of this silicon-alumina material has increased impurity removal rate and residual oil conversion rate, and is especially suitable for use as a heavy oil or residual oil hydrogenation catalyst.

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Abstract

提供了一种硅铝材料、其制造方法及应用。其中，硅铝材料的SiO2/Al2O3摩尔比为0.8-1.5，包含平均长度为0.5-2μm、平均厚度为30-80nm的片层结构，并且其焙烧形式具有特定的XRD图谱。硅铝材料具有大孔容、介孔-大孔两级梯度孔道、兼具分子筛B酸含量高的特点，显示分子筛的晶体特性，杂质含量低，适于用作催化材料载体，特别是适宜于用作重油加氢催化剂的载体。

Description

一种包含片层结构的硅铝材料、其制造方法及应用 技术领域
本发明属于催化材料技术领域，涉及一种硅铝材料、其制造方法及应用。
背景技术
加氢裂化催化剂载体中通过引入分子筛以提高催化剂的裂化性能。但由于渣油原料具有分子大、氮含量高等特点，使用分子筛类催化剂时易发生快速失活等问题，限制了其在渣油加氢裂化工艺上的应用。大孔硅铝材料具有适宜的孔道结构和酸性、良好的水热稳定性和较强的裂化性能，特别适合用于渣油加氢裂化工艺。
硅铝材料制造方法一般包括溶胶-凝胶法、混捏法、浸渍法等。而大孔硅铝材料通常采用溶胶-凝胶法来制造，该方法一般以水玻璃或硅溶胶作为硅源。大孔硅铝材料制造的难点在于随着二氧化硅含量的增加，硅铝材料的孔容逐渐减小，而钠含量却显著增加，钠作为硅铝材料的杂质，需要去除，一般情况下钠含量需要小于0.5％。通常工业上采用价格更贵的硅溶胶作为硅源来减少后续洗涤除钠的次数，或者采用离子交换来实现除钠，但这些除钠方法都大大增加了硅铝材料的制造成本，经济性较差，限制了其大规模工业推广应用。
CN201710382457.7公开了一种高活性硅铝材料及其制造方法。该活性硅铝材料含有以氧化物重量计、15-45％的硅和55-85％的铝，BET总比表面积为300-500m 2/g，微孔比表面积占BET总比表面积的比例为≯8％，平均孔径5-18nm；c表示由XPS方法测得的材料表面Al/Si原子比，所述的d表示由XRF方法测得的材料体相Al/Si原子比时，c/d＝1.2-1.9。
CN201710630418.4公开了一种中大孔硅铝材料及其制造方法。所述中大孔硅铝材料以氧化物重量计，其无水化学表达式为：(0-0.3)Na 2O:(2-18)Al 2O 3:(82-98)SiO 2；其孔体积为0.8-2mL/g，比表面积为150-350m 2/g，最可几孔径在30-100nm，B/L酸比值为0.8-2.0。本发明硅铝材料具有高孔容，大孔径，高B/L酸比值的特征，同时，本发明制造方法采用廉价硅铝源，无需添加有机模板剂，具有低成本，操作简单的特点。本发明提供方法中所采 用的铵盐交换，是将过滤所得的固体沉淀物按沉淀物(干基)：铵盐：H20＝1：(0.1-1)：(5-10)的重量比在室温至100℃下交换1-3次，每次交换0.3-1小时，直至固体沉淀物中钠含量质量百分比低于0.3wt％。交换所用的铵盐选自氯化铵、硝酸铵、碳酸铵、硫酸铵、碳酸氢铵中的一种或多种。
CN201710102634.1公开一种硅铝材料、制造方法及其应用。一种硅铝材料，XRF方法测得的化学组成按氧化物重量计为：(0-0.3)Na 2O·(50-80)SiO2·(20-50)Al 2O 3，其特征在于，该硅铝材料的XRD谱图中仅在25°-27°出现一个弥散的衍射峰，可几孔径介于20-50nm，x/y＝0.55-0.75，其中x表示由XPS方法测得的Si/Al原子比值，y表示由XRF方法测得的Si/Al原子比值。
发明内容
本发明的发明人发现，大孔硅铝材料制备的难点在于随着二氧化硅含量的增加，硅铝材料的孔容逐渐减小，而钠含量却显著增加，如何在保证较大孔容的前提下，有效降低钠含量是非常关键的。但是，在现有技术的硅铝材料制造方法中，为了降低硅铝材料的杂质含量，特别是钠含量都采用铵盐进行离子交换的方法，处理过程繁琐，增加了硅铝材料的制造成本。本发明的发明人还发现，通常工业上采用价格更贵的硅溶胶作为硅源来减少后续洗涤除钠的次数，或者采用离子交换来实现除钠，但这些除钠方法都大大增加了硅铝材料的制备成本，经济性较差，限制了其大规模工业推广应用。为此，本发明的发明人认为，如何制备大孔硅铝材料，同时降低除钠的成本是制备性能优异且价格低廉的硅铝材料的有效途径。为此，本发明的发明人经过刻苦的研究，发现了一种新型的硅铝材料。本发明基于该发现而完成。
具体而言，本发明涉及以下方面的内容。
1.一种硅铝材料，其SiO 2/Al 2O 3摩尔比为0.8-1.5(优选为1.0-1.4)，包含平均长度为0.5-2μm(优选0.5-1.5μm)、平均厚度为30-80nm(优选30-75nm)的片层结构，并且其焙烧形式具有基本上如下表I或表II所示的XRD图谱，优选其焙烧形式具有基本上如图2所示的XRD图谱，
表I
2θ d-间距(nm) 相对强度
14.0 0.12-0.13 VS
24.3 0.18-0.19 VS
34.3 0.07-0.08 S
42.6 0.11-0.13 M
51.9 0.10-0.13 M
66.4 0.06-0.08 M
表II
2θ d-间距(nm) 相对强度
13.9 0.12-0.13 VS
24.2 0.17-0.18 VS
31 0.36-0.38 M
34.4 0.08-0.10 S
39.9 0.08-0.10 M
42.5 0.11-0.12 M
51.6 0.12-0.13 W
57.8 0.14-0.16 W
66.4 0.07-0.09 W
其中设所述XRD图谱中最强衍射峰的强度值为100，则W＝弱，即相对强度>0至≤20，M＝中等，即相对强度>20至≤40，S＝强，即相对强度>40至≤60，VS＝非常强，即相对强度>60至≤100。
2.前述任一方面所述的硅铝材料，其孔容不小于1.1mL/g(优选大于1.15mL/g，进一步优选为1.15-1.5mL/g)，和/或，其比表面积为260-340m 2/g(优选为260-310m 2/g)，和/或，其孔分布为：孔直径＜10nm的孔的孔容占总孔容的≤5％(优选孔直径＜10nm的孔的孔容占总孔容的≤3％)，孔直径为10-50nm的孔的孔容占总孔容的65％-85％(优选孔直径为10-50nm的孔的孔容占总孔容的70％-85％)，孔直径＞50nm的孔的孔容占总孔容的10％-30％(优选孔直径＞50nm的孔的孔容占总孔容的12％-25％)，和/或，其平均孔径为14-23nm(优选为16-21nm)。
3.前述任一方面所述的硅铝材料，其B酸含量大于0.08mmol/g(优选为0.1-0.2mmol/g或0.1-0.15mmol/g)，和/或，其B酸与L酸比值为0.2-0.8(优选为0.3-0.7)，和/或，其Na 2O含量小于0.3wt％(优选小于0.2wt％)， 和/或，在其核磁共振硅谱中，在化学位移-87ppm至-89ppm有吸收峰，并且在其核磁共振铝谱中，在化学位移57ppm附近有吸收峰，和/或，其焙烧形式在小角度XRD图谱上没有衍射峰。
4.前述任一方面所述的硅铝材料，还包含非片层结构，其中以所述硅铝材料的总体积计，所述片层结构所占的比例为3％以上(优选5％以上，更优选10-80％或10-60％)。
5.一种硅铝材料的制造方法，顺次包括以下步骤：
(1)将酸性铝源加入到硅源中而得到混合物A，
(2)将所述混合物A与碱性铝源在水的存在下进行接触而得到浆液B，和
(3)将所述浆液B进行水热处理而得到所述硅铝材料。
6.前述任一方面所述的制造方法，其中在步骤(1)中，所述硅源为水溶性或水分散性的碱性含硅化合物(优选水溶性或水分散性的碱性无机含硅化合物，更优选选自于水溶性硅酸盐、水玻璃、硅溶胶中的一种或几种，优选为水玻璃)，和/或，所述硅源以水溶液的形式使用，并且以所述水溶液的总重量计，所述硅源(以SiO 2计)的浓度为5-30wt％(优选15-30wt％)，和/或，所述酸性铝源为水溶性的酸性含铝化合物(优选水溶性的酸性无机含铝化合物，特别是水溶性的无机强酸铝盐，更优选选自于硫酸铝、硝酸铝、氯化铝中的一种或几种，优选为硫酸铝)，和/或，所述酸性铝源以水溶液的形式使用，并且以所述水溶液的总重量计，所述酸性铝源(以Al 2O 3计)的浓度为30-100g/L(优选30-80g/L)，和/或，所述硅源(以SiO 2计)与所述酸性铝源(以Al 2O 3计)的重量比为1:1-9:1(优选为1:1-7:1)。
7.前述任一方面所述的制造方法，其中在步骤(1)中，还加入酸(优选将所述酸性铝源加入到所述硅源中，然后再加入所述酸，以得到所述混合物A)，和/或，所述酸为水溶性酸(优选水溶性的无机酸，更优选选自于硫酸、硝酸、盐酸中的一种或几种，优选为硫酸)，和/或，所述酸以水溶液的形式使用，并且以所述水溶液的总重量计，所述酸的浓度为2-6wt％(优选2-5wt％)，和/或，所述酸的加入量使得所述混合物A的pH值为2-4(优选为3-4)。
8.前述任一方面所述的制造方法，其中在步骤(2)中，所述碱性铝源 为水溶性的碱性含铝化合物(优选为水溶性的碱性无机含铝化合物，特别是碱金属偏铝酸盐，更优选选自于偏铝酸钠、偏铝酸钾中的一种或几种，优选为偏铝酸钠)，和/或，所述碱性铝源以水溶液的形式使用，并且以所述水溶液的总重量计，所述碱性铝源(以Al 2O 3计)的浓度为130-350g/L(优选150-250g/L)，和/或，以所述混合物A、所述碱性铝源和水的总体积计，所述混合物A的用量为40-80vol％(优选为45-75vol％)，和/或，以所述混合物A、所述碱性铝源和水的总体积计，所述碱性铝源的用量为10-30vol％(优选为12-25vol％)，和/或，以所述混合物A、所述碱性铝源和水的总体积计，所述水的用量为10-30vol％(优选为10-25vol％)，和/或，将所述混合物A与所述碱性铝源先后或同时加入到水中(优选将所述混合物A与所述碱性铝源以并流方式加入到水中)，和/或，所述混合物A的加入流速为15-50mL/min(优选为20-40mL/min)，和/或，控制所述碱性铝源的加入流速，使得所述浆液B的pH值维持在7.5-10.5(优选8.0-10.5，进一步优选为8.5-10.5)。
9.前述任一方面所述的制造方法，其中在步骤(2)中，还加入水溶性碳酸盐(优选将所述混合物A和所述碱性铝源加入水中，然后再加入所述水溶性碳酸盐，以得到所述浆液B)，和/或，所述水溶性碳酸盐选自于碱金属和铵中的一种或几种的碳酸盐(优选选自于碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、碳酸铵、碳酸氢铵中的一种或几种，优选碳酸钠)，和/或，所述水溶性碳酸盐以固体的形式使用，和/或，所述水溶性碳酸盐的加入量使得所述浆液B的pH值为10.5-12(优选11-12)。
10.前述任一方面所述的制造方法，其中在步骤(3)中，将所述硅铝材料从所述水热处理的反应体系中分离(比如过滤或离心分离)、洗涤至中性、然后干燥，和/或，所述干燥的条件包括：干燥温度为100-150℃，干燥时间为6-10小时。
11.前述任一方面所述的制造方法，其中在步骤(1)中，温度为25-50℃(优选25-40℃)，压力为常压，和/或，在步骤(2)中，温度为50-90℃(优选50-80℃)，压力为常压，和/或，在步骤(3)中，温度为180-300℃(优选为180-280℃，进一步优选为180-250℃)，压力为0.1-0.5MPa(优选为0.1-0.3MPa)，和/或，在步骤(3)中，设所述水热处理的初始时刻为t 0，所述水热处理的反应体系达到粘度最大值的时刻为t max，Δt＝t max-t 0，则所述水 热处理的时间(单位是h)为从Δt+1至Δt+20(优选从Δt+2至Δt+12，特别是从Δt+4至Δt+8)，和/或，在步骤(3)中，所述水热处理的时间为6-20h(优选8-12h)。
12.前述任一方面所述的制造方法，其中还加入助剂(优选选自于磷、硼和钛中的一种或几种)，和/或，所述助剂以氧化物计的重量含量为1-8wt％(优选2-6wt％)，相对于所述硅铝材料的总重量100wt％计。
13.一种催化材料，包括活性金属组分和前述任一方面所述的硅铝材料或按照前述任一方面所述的制造方法制造得到的硅铝材料。
14.前述任一方面所述的催化材料，其中所述活性金属组分是具有加氢活性的金属组分(优选选自元素周期表第VIB族金属和第VIII族金属中的至少一种，特别是选自Mo、W、Ni和Co中的至少一种)，和/或，以所述催化材料的总重量计，所述活性金属组分(以氧化物计)的重量百分比含量为5-30wt％(优选5-25wt％)。
15.一种加氢方法，包括使含烃物料在前述任一方面所述的催化材料的存在下进行加氢反应的步骤。
16.前述任一方面所述的加氢方法，其中所述含烃物料选自于柴油、蜡油、重油、煤焦油、乙烯焦油、催化油浆中的至少一种，和/或，所述加氢反应的反应条件包括：反应压力为5-20MPaG，反应温度为300-450℃，液时体积空速为0.1-1.5h -1，氢油体积比为100-1000。
技术效果
(1)本发明提供的硅铝材料具有大孔容、介孔-大孔两级梯度孔道、兼具分子筛B酸含量高的特点，且所述片层结构的出现，导致所述硅铝材料开始显示分子筛的晶体特性，杂质含量低(尤其钠含量低)，适于用作催化材料载体，特别是适宜于用作重油加氢催化剂的载体。
(2)本发明提供的硅铝材料制造方法中，硅源和酸性铝源接触，特别是在优选的情况下再进一步与酸接触，使硅源中包络在环内或笼内硅酸聚合物中的阳离子(钠离子等)游离出来，酸化的硅胶团吸附在氢氧化铝胶体上，使得钠离子与硅胶团有效分离，加入酸性铝源起到隔离游离的阳离子作用，使得后续对阳离子(钠离子)的脱除更加容易，大幅度降低了后续洗涤除钠 的难度并可以减少洗涤用水量。更重要的是可以有效的去除阳离子(钠离子)，可以恢复Na占据的酸性位，使硅铝材料具有更高的酸性。
(3)本发明提供的硅铝材料制造方法中，酸化的硅胶团吸附在氢氧化铝胶体上，为后续反应提供了晶核，促进制造的硅铝材料晶粒增大，有利于形成大孔容、孔径大的硅铝材料。
(4)本发明提供的硅铝材料制造方法中，在优选的情况下，通过加入水溶性碳酸盐来调节浆液B的pH值，然后在一定温度和一定压力下的处理过程中，浆液体系形态会发生由最开始的呈流动性状态转变为呈类似凝胶状的触变性形态，表现为反应体系的粘度逐渐增大并达到峰值，处理一段时间后又转变为具有流动性状态，表现为反应体系的粘度逐渐降低，在转变为呈类似凝胶状的触变性形态过程中，硅铝材料与水相互形成多变的硅铝氧网络结构，有利于制造得到大孔容的硅铝材料。
(5)在调整SiO 2/Al 2O 3比和水热高温条件下，加入的碳酸盐促进硅铝晶粒片层结构定向生长，随着处理时间延长，片层结构含量增加。片层结构的生成改变了Si和Al的结合方式，促进了B酸含量的增加。
附图说明
图1为本发明实施例1制造得到的硅铝材料的SEM照片。
图2为本发明实施例1制造得到的硅铝材料的XRD图(作为水热处理时间，h1＝8小时，h2＝16小时)。
图3为本发明实施例1制造得到的硅铝材料的核磁共振硅谱(作为水热处理时间，h1＝8小时，h2＝16小时)。
图4为本发明实施例1制造得到的硅铝材料的核磁共振铝谱(作为水热处理时间，h1＝8小时，h2＝16小时)。
图5为本发明实施例1制造得到的硅铝材料的小角度XRD图。
具体实施方式
下面对本发明的具体实施方式进行详细说明，但是需要指出的是，本发明的保护范围并不受这些具体实施方式的限制，而是由附录的权利要求书来确定。
本说明书提到的所有出版物、专利申请、专利和其它参考文献全都引于此供参考。除非另有定义，本说明书所用的所有技术和科学术语都具有本领域技术人员常规理解的含义。在有冲突的情况下，以本说明书的定义为准。
当本说明书以词头“本领域技术人员公知”、“现有技术”或其类似用语来导出材料、物质、方法、步骤、装置或部件等时，该词头导出的对象涵盖本申请提出时本领域常规使用的那些，但也包括目前还不常用，却将变成本领域公认为适用于类似目的的那些。
在本说明书的上下文中，在没有相反明确的情况下，在进行测量之前，硅铝材料和催化剂均经过焙烧处理，有时称为“焙烧形式”。在此，所述焙烧处理的条件包括：在空气气氛中，焙烧温度为600℃，焙烧时间为3h以上。
在本说明书的上下文中，硅铝材料和催化剂的孔容、比表面积、平均孔径和孔分布采用低温氮气吸附法测量。
在本说明书的上下文中，硅铝材料和催化剂的总酸、B酸和L酸采用吡啶红外吸附法测量。
在本说明书的上下文中，硅铝材料的氧化钠、氧化铝和二氧化硅的含量采用荧光分析法测量。
在本说明书的上下文中，催化剂的活性金属含量采用分光光度法测量。
在本说明书的上下文中，磨损指数采用空气喷射法测量。
在本说明书的上下文中，X-射线衍射(XRD)表征采用日本RIGAKU生产的D/max2500型X衍射分析仪，工作电压为40kV，工作电流为40mA，扫面范围10(°)～70(°)，步长0.06(°)，扫描速率0.21(°)·min -1。
在本说明书的上下文中，小角度XRD表征采用日本RIGAKU生产的D/max2500型X衍射分析仪，工作电压为40kV，工作电流为40mA，扫面范围1.5(°)～8(°)，步长0.01(°)，扫描速率0.02(°)·min -1
在本说明书的上下文中，样品形貌表征(SEM)采用日本电子公司生产的JXM-7500F场发射扫描电子显微镜上进行表征，工作电压6.5eV，加速电压5.0kV，放大倍数3万倍。
在本说明书的上下文中，固体核磁 27Al MAS NMR实验在Bruker-Avance III-400固体NMR谱仪上进行，在此谱仪上 1H和 27Al核的共振频率分别为 399.33和104.05MHz。 27Al MAS NMR在4mm双共振探头上采用单脉冲小板转角(<π/12，0.21μs)技术，脉冲延迟时间为1s。27Al谱化学位移采用1M Al(NO 3) 3定标
在本说明书的上下文中，固体核磁 29Si MAS NMR实验在Varian Infinity plus-600固体NMR谱仪上进行。在此谱仪上， 1H和 29Si核的共振频率分别为599.51和120.35MHz。 29Si MAS NMR在7.5mm双共振探头上采用单脉冲高功率去耦技术采集，π/2脉冲宽度为6.1μs，脉冲延迟时间为80s，转速为5kHz。 29Si谱化学位移通过高岭土定标(-91.5ppm)。
在本说明书的上下文中，硅铝材料的平均粒径采用SEM放大到3万倍，统计20张不同图片平均得到。
在本说明书的上下文中，硅铝材料一次颗粒的平均粒径采用SEM放大到3万倍，统计20张不同图片平均得到。
在本说明书的上下文中，片层结构的平均长度和平均厚度采用SEM放大到3万倍，统计20张不同图片平均得到。
在本说明书的上下文中，反应体系的粘度可以采用任何方法进行测量，只要可以随着反应时间的延长而进行有效对比即可，并没有特别的限制。
在没有明确指明的情况下，本说明书内所提到的所有百分数、份数、比率等都是以重量为基准的，而且压力是表压。
在本说明书的上下文中，本发明的任何两个或多个实施方式都可以任意组合，由此而形成的技术方案属于本说明书原始公开内容的一部分，同时也落入本发明的保护范围。
根据本发明的一个实施方式，涉及一种硅铝材料，其SiO 2/Al 2O 3摩尔比为0.8-1.5(优选为1.0-1.4)。
根据本发明的一个实施方式，所述硅铝材料包含平均长度为0.5-2μm(优选0.5-1.5μm)、平均厚度为30-80nm(优选30-75nm)的片层结构。这一点可以通过SEM照片予以确认。
根据本发明的一个实施方式，所述硅铝材料的焙烧形式具有基本上如下表I所示的XRD图谱。
表I
2θ d-间距(nm) 相对强度
14.0 0.12-0.13 VS
24.3 0.18-0.19 VS
34.3 0.07-0.08 S
42.6 0.11-0.13 M
51.9 0.10-0.13 M
66.4 0.06-0.08 M
表I(优选)
2θ d-间距(nm) 相对强度
14.0 0.117 VS
24.3 0.190 VS
34.3 0.078 S
42.6 0.121 M
51.9 0.106 M
66.4 0.079 M
根据本发明的一个实施方式，所述硅铝材料的焙烧形式优选具有基本上如下表II所示的XRD图谱。
表II
2θ d-间距(nm) 相对强度
13.9 0.12-0.13 VS
24.2 0.17-0.18 VS
31 0.36-0.38 M
34.4 0.08-0.10 S
39.9 0.08-0.10 M
42.5 0.11-0.12 M
51.6 0.12-0.13 W
57.8 0.14-0.16 W
66.4 0.07-0.09 W
表II(优选)
2θ d-间距(nm) 相对强度
13.9 0.125 VS
24.2 0.171 VS
31 0.373 M
34.4 0.077 S
39.9 0.086 M
42.5 0.114 M
51.6 0.124 W
57.8 0.142 W
66.4 0.079 W
根据本发明，设所述XRD图谱中最强衍射峰的强度值为100，则W＝弱，即相对强度>0至≤20，M＝中等，即相对强度>20至≤40，S＝强，即相对强度>40至≤60，VS＝非常强，即相对强度>60至≤100。
根据本发明的一个实施方式，所述硅铝材料的焙烧形式具有基本上如图2所示的XRD图谱。
根据本发明的一个实施方式，所述硅铝材料的孔容不小于1.1mL/g(优选大于1.15mL/g，进一步优选为1.15-1.5mL/g)。
根据本发明的一个实施方式，所述硅铝材料的比表面积为260-340m 2/g(优选为260-310m 2/g)。
根据本发明的一个实施方式，所述硅铝材料的孔分布为：孔直径＜10nm的孔的孔容占总孔容的≤5％(优选孔直径＜10nm的孔的孔容占总孔容的≤3％)，孔直径为10-50nm的孔的孔容占总孔容的65％-85％(优选孔直径为10-50nm的孔的孔容占总孔容的70％-85％)，孔直径＞50nm的孔的孔容占总孔容的10％-30％(优选孔直径＞50nm的孔的孔容占总孔容的12％-25％)。
根据本发明的一个实施方式，所述硅铝材料的平均孔径为14-23nm(优选为16-21nm)。
根据本发明的一个实施方式，所述硅铝材料的B酸含量大于0.08mmol/g(优选为0.1-0.2mmol/g或0.1-0.15mmol/g)。
根据本发明的一个实施方式，所述硅铝材料的B酸与L酸比值为0.2-0.8(优选为0.3-0.7)。
根据本发明的一个实施方式，所述硅铝材料的Na 2O含量小于0.3wt％(优 选小于0.2wt％)。
根据本发明的一个实施方式，所述硅铝材料的平均粒度为30-100nm(优选为30-80nm)。
根据本发明的一个实施方式，所述硅铝材料在其核磁共振硅谱中，在化学位移-87ppm至-89ppm有吸收峰，表示硅氧四面体与3个铝氧四面体直接相连。
根据本发明的一个实施方式，所述硅铝材料在其核磁共振铝谱中，在化学位移57ppm附近有吸收峰，表明材料中存在四配位的骨架铝。
根据本发明的一个实施方式，所述硅铝材料的焙烧形式在小角度XRD图谱上没有衍射峰，表明没有分子筛特征峰。
根据本发明的一个实施方式，所述硅铝材料还包含非片层结构。这一点也可以通过SEM照片予以确认。在此，所述非片层结构是多个硅铝一次颗粒的聚集体，显示无定形硅铝的特征。另外，所述硅铝一次颗粒的平均粒度一般为5-25nm(优选为10-25nm)。
根据本发明的一个实施方式，以所述硅铝材料的总体积计，所述片层结构所占的比例为3％以上(优选5％以上，更优选10-80％或10-60％)。
根据本发明的一个实施方式，还涉及一种硅铝材料的制造方法，所述制造方法可以用于制造本说明书如前所述的硅铝材料。
根据本发明的一个实施方式，所述制造方法顺次包括以下步骤：
(1)将酸性铝源加入到硅源中而得到混合物A，
(2)将所述混合物A与碱性铝源在水的存在下进行接触而得到浆液B，和
(3)将所述浆液B进行水热处理而得到所述硅铝材料。
根据本发明，在步骤(1)中，将酸性铝源加入到硅源中，而不是将硅源加入到酸性铝源中，否则就会导致大量沉淀生成。
根据本发明的一个实施方式，在所述制造方法中，在步骤(1)中，所述硅源为水溶性或水分散性的碱性含硅化合物(优选水溶性或水分散性的碱性无机含硅化合物，更优选选自于水溶性硅酸盐、水玻璃、硅溶胶中的一种或几种，优选为水玻璃)。
根据本发明的一个实施方式，在所述制造方法中，所述硅源以水溶液的 形式使用。以所述水溶液的总重量计，所述硅源(以SiO 2计)的浓度为5-30wt％(优选15-30wt％)，其模数一般为2.5-3.2。
根据本发明的一个实施方式，在所述制造方法中，所述酸性铝源为水溶性的酸性含铝化合物(优选水溶性的酸性无机含铝化合物，特别是水溶性的无机强酸铝盐，更优选选自于硫酸铝、硝酸铝、氯化铝中的一种或几种，优选为硫酸铝)。
根据本发明的一个实施方式，在所述制造方法中，所述酸性铝源以水溶液的形式使用，并且以所述水溶液的总重量计，所述酸性铝源(以Al 2O 3计)的浓度为30-100g/L(优选30-80g/L)。
根据本发明的一个实施方式，在所述制造方法中，所述硅源(以SiO 2计)与所述酸性铝源(以Al 2O 3计)的重量比为1:1-9:1(优选为1:1-7:1)。
根据本发明的一个实施方式，在所述制造方法中，为了本发明的技术效果更为优异实现，特别是为了获得更大孔容和杂质含量更低的硅铝材料，在步骤(1)中，还加入酸(优选将所述酸性铝源加入到所述硅源中，然后再加入所述酸，以得到所述混合物A)。
根据本发明的一个实施方式，在所述制造方法中，所述酸为水溶性酸(优选水溶性的无机酸，更优选选自于硫酸、硝酸、盐酸中的一种或几种，优选为硫酸)。
根据本发明的一个实施方式，在所述制造方法中，所述酸以水溶液的形式使用。以所述水溶液的总重量计，所述酸的浓度为2-6wt％(优选2-5wt％)。
根据本发明的一个实施方式，在所述制造方法中，所述酸的加入量使得所述混合物A的pH值为2-4(优选为3-4)。
根据本发明的一个实施方式，在所述制造方法中，在步骤(1)中，一般而言，所述混合物A的铝含量以Al 2O 3计含量为5-20gAl 2O 3/L，硅含量以SiO 2计为5-40gSiO 2/L。
根据本发明的一个实施方式，在所述制造方法中，在步骤(2)中，所述碱性铝源为水溶性的碱性含铝化合物(优选为水溶性的碱性无机含铝化合物，特别是碱金属偏铝酸盐，更优选选自于偏铝酸钠、偏铝酸钾中的一种或几种，优选为偏铝酸钠)。
根据本发明的一个实施方式，在所述制造方法中，所述碱性铝源以水溶 液的形式使用。以所述水溶液的总重量计，所述碱性铝源(以Al 2O 3计)的浓度为130-350g/L(优选150-250g/L)，其苛性比一般为1.15-1.35，优选为1.15-1.30。
根据本发明的一个实施方式，在所述制造方法中，以所述混合物A、所述碱性铝源和水的总体积计，所述混合物A的用量为40-80vol％(优选为45-75vol％)。
根据本发明的一个实施方式，在所述制造方法中，以所述混合物A、所述碱性铝源和水的总体积计，所述碱性铝源的用量为10-30vol％(优选为12-25vol％)。
根据本发明的一个实施方式，在所述制造方法中，以所述混合物A、所述碱性铝源和水的总体积计，所述水的用量为10-30vol％(优选为10-25vol％)。
根据本发明的一个实施方式，在所述制造方法中，将所述混合物A与所述碱性铝源先后或同时加入到水中(优选将所述混合物A与所述碱性铝源以并流方式加入到水中)。
根据本发明的一个实施方式，在所述制造方法中，所述混合物A的加入流速为15-50mL/min(优选为20-40mL/min)。
根据本发明的一个实施方式，在所述制造方法中，控制所述碱性铝源的加入流速，使得所述浆液B的pH值维持在7.5-10.5(优选8.0-10.5，进一步优选为8.5-10.5)。
根据本发明的一个实施方式，在所述制造方法中，为了本发明的技术效果更为优异实现，特别是为了获得更大孔容的硅铝材料，在步骤(2)中，还加入水溶性碳酸盐(优选将所述混合物A和所述碱性铝源加入水中，然后再加入所述水溶性碳酸盐，以得到所述浆液B)。
根据本发明的一个实施方式，在所述制造方法中，所述水溶性碳酸盐选自于碱金属和铵中的一种或几种的碳酸盐(优选自于碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、碳酸铵、碳酸氢铵中的一种或几种，优选碳酸钠)。
根据本发明的一个实施方式，在所述制造方法中，所述水溶性碳酸盐以固体的形式使用。
根据本发明的一个实施方式，在所述制造方法中，所述水溶性碳酸盐的 加入量使得所述浆液B的pH值为10.5-12(优选11-12)。
根据本发明的一个实施方式，在所述制造方法中，在步骤(3)中，将所述硅铝材料从所述水热处理的反应体系中分离、洗涤至中性、然后干燥。在此，所述洗涤可采用本领域常规的洗涤方法，优选采用去离子水进行洗涤，进一步优选在50℃-90℃下进行洗涤。另外，所述分离可以采用本领域任何可以实现液固两相物料分离的手段中的一种，如过滤、离心分离等，具体到本发明中可以采用过滤分离方式进行分离，分离后得到固相物料和液相物料，固相物料经洗涤、干燥而获得所述硅铝材料。
根据本发明的一个实施方式，在所述制造方法中，所述干燥的条件包括：干燥温度为100-150℃，干燥时间为6-10小时。
根据本发明的一个实施方式，在所述制造方法中，在步骤(1)中，温度为25-50℃(优选25-40℃)，压力为常压。
根据本发明的一个实施方式，在所述制造方法中，在步骤(2)中，温度为50-90℃(优选50-80℃)，压力为常压。
根据本发明的一个实施方式，在所述制造方法中，在步骤(3)中，温度为180-300℃(优选为180-280℃，进一步优选为180-250℃)，压力为0.1-0.5MPa(优选为0.1-0.3MPa)。
根据本发明的一个实施方式，在所述制造方法中，为了本发明的技术效果更为优异实现，特别是为了获得更高比例的片层结构，在步骤(3)中，设所述水热处理的初始时刻为t 0，所述水热处理的反应体系达到粘度最大值的时刻为t max，Δt＝t max-t 0，则所述水热处理的时间(单位是h)为从Δt+1至Δt+20(优选从Δt+2至Δt+12，特别是从Δt+4至Δt+8)。或者，从简便制造方法控制的角度出发，在步骤(3)中，所述水热处理的时间可以为6-20h(优选8-12h)。
根据本发明的一个实施方式，在所述制造方法中，可根据实际需要加入助剂，如P 2O 5、B 2O 3或TiO 2中的一种或几种。为此，这些前驱物可以以水溶性无机盐的形式在步骤(1)的反应过程中加入。作为所述无机盐，具体比如可以举出硼酸盐、硫酸盐或硝酸盐等。另外，这些助剂的加入量可根据后续催化剂等要求进行任意调整。一般情况下，这些助剂以氧化物计的重量含量一般为1-8wt％，优选2-6wt％，相对于所述硅铝材料的总重量100wt％计。
根据本发明的一个实施方式，还涉及一种催化材料，包括活性金属组分和本说明书如前所述的硅铝材料或按照本说明书如前所述的制造方法制造得到的硅铝材料。
根据本发明的一个实施方式，所述活性金属组分是具有加氢活性的金属组分(优选选自元素周期表第VIB族金属和第VIII族金属中的至少一种，特别是选自Mo、W、Ni和Co中的至少一种)。
根据本发明的一个实施方式，以所述催化材料的总重量计，所述活性金属组分(以氧化物计)的重量百分比含量为5-30wt％(优选5-25wt％)。
根据本发明的一个实施方式，还涉及一种加氢方法，包括使含烃物料在本说明书如前所述的催化材料的存在下进行加氢反应的步骤。
根据本发明的一个实施方式，所述含烃物料选自于柴油、蜡油、重油、煤焦油、乙烯焦油、催化油浆中的至少一种。
根据本发明的一个实施方式，所述加氢反应的反应条件包括：反应压力为5-20MPaG，反应温度为300-450℃，液时体积空速为0.1-1.5h -1，氢油体积比为100-1000。
实施例
以下采用实施例进一步详细地说明本发明，但本发明并不限于这些实施例。
在以下的实施例和比较例中，所有的药剂和原料既可以商购获得，也可以根据已有知识制造。
实施例1
(1)硅铝材料制造
配制浓度为50gAl 2O 3/L的硫酸铝溶液和浓度为50gSiO 2/L、模数为2.8的硅溶胶溶液待用，配制浓度为1mol/L的稀硫酸溶液待用。配制苛性比1.25、浓度160gAl 2O 3/L的偏铝酸钠溶液待用。
量取1.44L浓度为50gSiO 2/L的硅溶胶溶液加入到容器中，在搅拌的条件下，缓慢加入1L浓度为50gAl 2O 3/L的硫酸铝溶液，这个过程有氢氧化铝胶体生成，但溶液仍是液体形式存在。接着加入1mol/L的稀硫酸溶液，调节 pH为3.5，完成酸化处理，得到混合液A。
向5000mL反应器中加入700mL去离子水作为底水，启动搅拌并加热，去离子水加热到80℃后，将混合液A以28mL/min加入到反应器中，同时将配制好的偏铝酸钠溶液并流加入，通过调节偏铝酸钠流速来控制反应的pH为8.3，并保持反应器内浆液温度和pH值恒定。待反应结束后，偏铝酸钠用量为325mL，在搅拌条件下向反应器内加入75g碳酸铵调节pH值为10.8。将上述浆液放入反应器中，在搅拌的条件下，处理温度为210℃，处理压力0.4MPa，处理8h(相当于Δt+6小时)。处理后的浆料用90℃的热水洗涤至液体中性，在120℃干燥6h，得到干燥后样品PO-1，在600℃下焙烧5h得到硅铝材料P-1，其性质见表1。
根据SEM照片(图1)，所述硅铝材料包含片层结构和非片层结构，其平均粒度为50nm。该片层结构的平均长度为1.0μm、平均厚度为50nm，并且占硅铝材料总体积的35％。根据测量，所述硅铝材料的SiO 2/Al 2O 3摩尔比为1.21。另外，所述硅铝材料的焙烧形式的XRD图谱如图2所示，显示出晶体结构，而且随着水热处理时间(上面是h1＝8小时，下面是h2＝16小时)的延长，各衍射峰均逐渐变强，表明所述片层结构在所述硅铝材料中的占比逐渐增加。在所述硅铝材料的核磁共振硅谱(图3)中，在化学位移-87ppm附近有吸收峰，而且随着水热处理时间(h1＝8小时，h2＝16小时)的延长，该吸收峰逐渐变强。在所述硅铝材料的核磁共振铝谱(图4)中，在化学位移57ppm附近有吸收峰，而且随着水热处理时间(h1＝8小时，h2＝16小时)的延长，该吸收峰逐渐变强。所述硅铝材料的焙烧形式在小角度XRD图谱(图5)上没有衍射峰。
(2)加氢催化剂制造
取500g制造的PO-1硅铝干燥样，加入田菁粉10g和柠檬酸12.15g，水420g，混合均匀后然后成球型，将成球后的样品经过650℃焙烧4h得到粒度为0.3-0.8mm的载体Z1。
称取磷酸28.57g，加入蒸馏水800mL，然后依次加入氧化钼77.58g、碱式碳酸镍35.56g，加热搅拌至完全溶解后，用蒸馏水将溶液定容至1000mL，得溶液L1。将载体Z1用溶液L1溶液饱和浸渍，在110℃干燥2h，450℃焙烧3h得到催化剂C1，具体性质见表2。
实施例2
其他条件同实施例1，不同之处在于：将硅溶胶改为水玻璃溶液，浓度调整58gSiO 2/L，混合液A的流速为15mL/min，反应器中去离子水加热到80℃，得到硅铝材料干燥样PO-2，在600℃下焙烧5h得到硅铝材料P-2，其性质见表1。
所述硅铝材料的SiO 2/Al 2O 3摩尔比为1.44，包含平均长度为1.5μm、平均厚度为61nm的片层结构。该片层结构占所述硅铝材料总体积的54％。
取500g制造的PO-2硅铝干燥样，加入21.4g醋酸(85wt％)和410g水，混合均匀后然后成球型，将成球后的样品经过600℃焙烧5h得到粒度为0.3-0.8mm的载体Z2。
将载体Z2用溶液L1溶液饱和浸渍，在110℃干燥2h，580℃焙烧3h得到催化剂C2，具体性质见表2。
实施例3
其他条件同实施例1，不同之处在于：通过调节偏铝酸钠流速来控制反应的pH为9.0，在搅拌条件下向反应器内加入53g碳酸钠调节pH值为11.0，处理温度为280℃，处理压力0.4MPa，得到硅铝干燥样PO-3，在600℃下焙烧5h得到硅铝材料P-3，其性质见表1。
所述硅铝材料的SiO 2/Al 2O 3摩尔比为1.19，包含平均长度为1.4μm、平均厚度为56nm的片层结构。该片层结构占所述硅铝材料总体积的40％。
取500g制造的PO-3硅铝干燥样，加入甲基纤维素10.0g和450g水，混合均匀后成球型，将成球后的样品经过600℃焙烧5h得到粒度为0.3-0.8mm的载体Z3。
将载体Z3用溶液L1溶液饱和浸渍，在110℃干燥2h，480℃焙烧4h得到催化剂C3，具体性质见表2。
实施例4
其他条件同实施例1，不同之处在于：不加入1mol/L的稀硫酸溶液来酸化处理，制备得到硅铝干燥样PO-4，在600℃下焙烧5h得到硅铝材料P-4， 其性质见表1。
取500g制造的PO-4硅铝干燥样，加入田菁粉10g和柠檬酸12.15g，水420g，混合均匀后然后成球型，将成球后的样品经过650℃焙烧4h得到粒度为0.3-0.8mm的载体Z4。
将载体Z4用溶液L1溶液饱和浸渍，在110℃干燥2h，450℃焙烧3h得到催化剂C4，具体性质见表2。
所述硅铝材料的SiO 2/Al 2O 3摩尔比为1.19，包含平均长度为1.5μm、平均厚度为32nm的片层结构。该片层结构占所述硅铝材料总体积的15％。
实施例5
其他条件同实施例1，不同之处在于：调节偏铝酸钠苛性比为1.20，调节成胶pH值为6.0，制备得到硅铝干燥样PFO-5，在600℃下焙烧5h得到硅铝材料P-5，其性质见表1。
取500g制造的PO-5硅铝干燥样，加入田菁粉10g和柠檬酸12.15g，水420g，混合均匀后然后成球型，将成球后的样品经过650℃焙烧4h得到粒度为0.3-0.8mm的载体Z5。
将载体Z5用溶液L1溶液饱和浸渍，在110℃干燥2h，450℃焙烧3h得到催化剂C5，具体性质见表2。
所述硅铝材料的SiO 2/Al 2O 3摩尔比为1.19，包含平均长度为1.0μm、平均厚度为20nm的片层结构。该片层结构占所述硅铝材料总体积的10％。
实施例6
其他条件同实施例1，不同之处在于：将水溶性碳酸盐改为氢氧化钠，制备得到硅铝干燥样PFO-6，在600℃下焙烧5h得到硅铝材料P-6，其性质见表1。
取500g制造的PO-6硅铝干燥样，加入田菁粉10g和柠檬酸12.15g，水420g，混合均匀后然后成球型，将成球后的样品经过650℃焙烧4h得到粒度为0.3-0.8mm的载体Z6。
将载体Z6用溶液L1溶液饱和浸渍，在110℃干燥2h，450℃焙烧3h得到催化剂C6，具体性质见表2。
所述硅铝材料的SiO 2/Al 2O 3摩尔比为1.19，包含平均长度为0.8μm、平均厚度为15nm的片层结构。该片层结构占所述硅铝材料总体积的5％。
实施例7
其他条件同实施例1，不同之处在于：不加水溶性碳酸盐来调节pH值，制备得到硅铝干燥样PFO-7，在600℃下焙烧5h得到硅铝材料P-7，其性质见表1。
取500g制造的PO-7硅铝干燥样，加入田菁粉10g和柠檬酸12.15g，水420g，混合均匀后然后成球型，将成球后的样品经过650℃焙烧4h得到粒度为0.3-0.8mm的载体Z7。
将载体Z7用溶液L1溶液饱和浸渍，在110℃干燥2h，450℃焙烧3h得到催化剂C7，具体性质见表2。
所述硅铝材料的SiO 2/Al 2O 3摩尔比为1.19，不能形成片层结构。
实施例8
其他条件同实施例1，不同之处在于：加入碳酸铵调节pH值为9.5，制备得到硅铝干燥样PFO-8，在600℃下焙烧5h得到硅铝材料P-7，其性质见表1。
取500g制造的PO-8硅铝干燥样，加入田菁粉10g和柠檬酸12.15g，水420g，混合均匀后然后成球型，将成球后的样品经过650℃焙烧4h得到粒度为0.3-0.8mm的载体Z8。
将载体Z8用溶液L1溶液饱和浸渍，在110℃干燥2h，450℃焙烧3h得到催化剂C8，具体性质见表2。
所述硅铝材料的SiO 2/Al 2O 3摩尔比为1.20，包含平均长度为0.6μm、平均厚度为20nm的片层结构。该片层结构占所述硅铝材料总体积的3％。
实施例9
(1)硅铝材料制造
配制浓度为60gAl 2O 3/L的硫酸铝溶液和浓度为75gSiO 2/L，模数为3.0的水玻璃溶液待用，配制浓度为2mol/L的稀硝酸溶液待用。配制成苛性比1.30， 浓度130gAl 2O 3/L的偏铝酸钠溶液待用。
量取1.4L浓度为80gSiO 2/L的硅溶胶溶液加入到容器中，在搅拌的条件下，缓慢加入1L浓度为60gAl 2O 3/L的硫酸铝溶液，这个过程有氢氧化铝胶体生成，但溶液仍是液体形式存在。接着加入2mol/L的稀硝酸溶液，调节pH为4.0，完成酸化处理，得到混合液A。
向5000mL反应器中加入1000mL去离子水作为底水，启动搅拌并加热，去离子水加热到60℃后，将混合液A以20mL/min加入到反应器中，同时将配制好的偏铝酸钠溶液并流加入，通过调节偏铝酸钠流速来控制反应的pH为9.5，并保持反应器内浆液温度和pH值恒定。待反应结束后，偏铝酸钠用量为620mL，在搅拌条件下向反应器内加入84g碳酸氢铵调节pH值为11.0。将上述浆液放入反应器中，在搅拌的条件下，处理温度为230℃，处理压力0.5MPa，处理10h。处理后的浆料用90℃的热水洗涤至液体中性，在150℃干燥4h，得到干燥后样品PFO-9，在600℃下焙烧5h得到硅铝材料P-9，其性质见表1。
所述硅铝材料的SiO 2/Al 2O 3摩尔比为1.35，包含平均长度为1.44μm、平均厚度为59nm的片层结构。该片层结构占所述硅铝材料总体积的48％。
(2)加氢催化剂制造
取500g制造的PFO-9硅铝干燥样，加入田菁粉7g和硝酸(65wt％)31.3g，水410g，混合均匀后然后成球型，将成球后的样品经过550℃焙烧5h得到粒度为0.3-0.8mm的载体Z9。
称取磷酸78.88g，加入蒸馏水800mL，然后依次加入氧化钼185.68g、碱式碳酸钴50.81g，加热搅拌至完全溶解后，用蒸馏水将溶液定容至2000mL，得溶液L2。将载体Z9用溶液L2溶液饱和浸渍，在110℃干燥4h，500℃焙烧3h得到催化剂C9，具体性质见表2。
实施例10
其他条件同实施例4，只是反应器内加入600mL水，成胶温度调整为80℃，pH值调整为10.0，成胶后浆液加入碳酸钠20g调节pH值为10.5，处理温度为280℃，处理压力0.4MPa，得到硅铝干燥样PFO-10，在600℃下焙烧5h得到硅铝材料PF-10，其性质见表1。
所述硅铝材料的SiO 2/Al 2O 3摩尔比为1.34，包含平均长度为1.41μm、平均厚度为58nm的片层结构。该片层结构占所述硅铝材料总体积的44％。
取500g制造的PFO-10硅铝干燥样，加入田菁粉15g和470g水，混合均匀后成球型，将成球后的样品经过750℃焙烧3h得到粒度为0.3-0.8mm的载体Z10。
将载体Z10用溶液L2溶液饱和浸渍，在110℃干燥2h，550℃焙烧3h得到催化剂C10，具体性质见表2。
比较例1
(1)硅铝材料制造
配制浓度为50gAl 2O 3/L的硫酸铝溶液和浓度为50gSiO 2/L、模数为2.8的硅溶胶溶液待用，配制苛性比1.25、浓度160gAl 2O 3/L的偏铝酸钠溶液待用。
向5000mL反应器中加入700mL去离子水作为底水，启动搅拌并加热，去离子水加热到80℃后，将硫酸铝以25mL/min和硅溶胶28mL/min加入到反应器中，同时将配制好的偏铝酸钠溶液并流加入，通过调节偏铝酸钠流速来控制反应的pH为8.3，并保持反应器内浆液温度和pH值恒定。待反应结束后，偏铝酸钠用量为325mL，在搅拌条件下向反应器内加入75g碳酸铵调节pH值为10.8。将上述浆液放入反应器中，在搅拌的条件下，处理温度为210℃，处理压力0.4MPa，处理8h(相当于Δt+6小时)。处理后的浆料用90℃的热水洗涤至液体中性，在120℃干燥6h，得到干燥后样品PFO-1，在600℃下焙烧5h得到硅铝材料PF-1，其性质见表1。
所述硅铝材料的SiO 2/Al 2O 3摩尔比为1.20，并且从SEM照片上看不到片层结构，全部都是非片层结构。
(2)加氢催化剂制造
取500g制造的PFO-1硅铝干燥样，加入田菁粉10g和柠檬酸12.15g，水420g，混合均匀后然后成球型，将成球后的样品经过650℃焙烧4h得到粒度为0.3-0.8mm的载体ZF1。
将载体ZF1用溶液L1溶液饱和浸渍，在110℃干燥2h，450℃焙烧3h得到催化剂CF1，具体性质见表2。
比较例2
(1)硅铝材料制造
配制浓度为50gAl 2O 3/L的硫酸铝溶液和浓度为50gSiO 2/L、模数为2.8的硅溶胶溶液待用，配制浓度为1mol/L的稀硫酸溶液待用。配制苛性比1.25、浓度160gAl 2O 3/L的偏铝酸钠溶液待用。
量取1L浓度为50gAl 2O 3/L的硫酸铝溶液到容器中，在搅拌的条件下，缓慢加入1.44L浓度为50gSiO 2/L的硅溶胶溶液，过程生成大量氢氧化铝凝胶，流动性较差，接着加入1mol/L的稀硫酸溶液，调节pH为3.5，完成酸化处理，得到混合液A。
向5000mL反应器中加入700mL去离子水作为底水，启动搅拌并加热，去离子水加热到80℃后，将混合液A以28mL/min加入到反应器中，同时将配制好的偏铝酸钠溶液并流加入，通过调节偏铝酸钠流速来控制反应的pH为8.3，并保持反应器内浆液温度和pH值恒定。待反应结束后，偏铝酸钠用量为325mL，在搅拌条件下向反应器内加入75g碳酸铵调节pH值为10.8。将上述浆液放入反应器中，在搅拌的条件下，处理温度为210℃，处理压力0.4MPa，处理8h(相当于Δt+6小时)。处理后的浆料用90℃的热水洗涤至液体中性，在120℃干燥6h，得到干燥后样品PFO-2，在600℃下焙烧5h得到硅铝材料PF-2，其性质见表1。
(2)加氢催化剂制造
取500g制造的PFO-2硅铝干燥样，加入田菁粉10g和柠檬酸12.15g，水420g，混合均匀后然后成球型，将成球后的样品经过650℃焙烧4h得到粒度为0.3-0.8mm的载体ZF2。
将载体ZF2用溶液L1溶液饱和浸渍，在110℃干燥2h，450℃焙烧3h得到催化剂CF2，具体性质见表2。
所述硅铝材料的SiO 2/Al 2O 3摩尔比为1.19，并且从SEM照片上看不到片层结构，全部都是非片层结构。
比较例3
(1)硅铝材料制造
配制浓度为50gAl 2O 3/L的硫酸铝溶液和浓度为50gSiO 2/L、模数为2.8的 硅溶胶溶液待用，配制浓度为1mol/L的稀硫酸溶液待用。配制苛性比1.25、浓度160gAl 2O 3/L的偏铝酸钠溶液待用。
量取1.44L浓度为50gSiO 2/L的硅溶胶溶液加入到容器中，在搅拌的条件下，缓慢加入1L浓度为50gAl 2O 3/L的硫酸铝溶液，这个过程有氢氧化铝胶体生成，但溶液仍是液体形式存在。接着加入1mol/L的稀硫酸溶液，调节pH为3.5，完成酸化处理，得到混合液A。
向5000mL反应器中加入700mL去离子水作为底水，启动搅拌并加热，去离子水加热到80℃后，将混合液A以28mL/min加入到反应器中，同时将配制好的偏铝酸钠溶液并流加入，通过调节偏铝酸钠流速来控制反应的pH为8.3，并保持反应器内浆液温度和pH值恒定。待反应结束后，偏铝酸钠用量为325mL，在搅拌条件下向反应器内加入75g碳酸铵调节pH值为10.8。将上述浆液放入反应器中，用90℃的热水洗涤至液体中性，在120℃干燥6h，得到干燥后样品PFO-1，在600℃下焙烧5h得到硅铝材料PF-3，其性质见表1。
所述硅铝材料的SiO 2/Al 2O 3摩尔比为1.20，并且从SEM照片上看不到片层结构，全部都是非片层结构。
(2)加氢催化剂制造
取500g制造的PFO-3硅铝干燥样，加入田菁粉10g和柠檬酸12.15g，水420g，混合均匀后然后成球型，将成球后的样品经过650℃焙烧4h得到粒度为0.3-0.8mm的载体ZF3。
将载体ZF3用溶液L1溶液饱和浸渍，在110℃干燥2h，450℃焙烧3h得到催化剂CF3，具体性质见表2。
比较例4
(1)硅铝材料制造
配制浓度为50gAl 2O 3/L的硫酸铝溶液和浓度为50gSiO 2/L、模数为2.8的硅溶胶溶液待用，配制浓度为1mol/L的稀硫酸溶液待用。配制苛性比1.25、浓度160gAl 2O 3/L的偏铝酸钠溶液待用。
量取1.44L浓度为50gSiO 2/L的硅溶胶溶液加入到容器中，在搅拌的条件下，缓慢加入325mL偏铝酸钠溶液，接着加入1mol/L的稀硫酸溶液，调节pH为3.5，过程生成大量氢氧化铝凝胶，流动性较差，形成悬浊液A。
1L浓度为50gAl 2O 3/L的硫酸铝溶液，这个过程有氢氧化铝胶体生成，但溶液仍是液体形式存在。接着加入1mol/L的稀硫酸溶液，调节pH为3.5，完成酸化处理，得到混合液A。
向5000mL反应器中加入700mL去离子水作为底水，启动搅拌并加热，去离子水加热到80℃后，将悬浊液A以28mL/min加入到反应器中，同时将配制好1L浓度为50gAl2O3/L的硫酸铝溶液并流加入，通过调节偏铝酸钠流速来控制反应的pH为8.3，并保持反应器内浆液温度和pH值恒定。待反应结束后，在搅拌条件下向反应器内加入75g碳酸铵调节pH值为10.8。将上述浆液放入反应器中，在搅拌的条件下，处理温度为210℃，处理压力0.4MPa，处理8h(相当于Δt+6小时)。处理后的浆料用90℃的热水洗涤至液体中性，在120℃干燥6h，得到干燥后样品PF0-4，在600℃下焙烧5h得到硅铝材料PF-4，其性质见表1。
所述硅铝材料的SiO 2/Al 2O 3摩尔比为1.20，并且从SEM照片上看不到片层结构，全部都是非片层结构。
(2)加氢催化剂制造
取500g制造的PFO-4硅铝干燥样，加入田菁粉10g和柠檬酸12.15g，水420g，混合均匀后然后成球型，将成球后的样品经过650℃焙烧4h得到粒度为0.3-0.8mm的载体ZF4。
称取磷酸28.57g，加入蒸馏水800mL，然后依次加入氧化钼77.58g、碱式碳酸镍35.56g，加热搅拌至完全溶解后，用蒸馏水将溶液定容至1000mL，得溶液L1。将载体ZF4用溶液L1溶液饱和浸渍，在110℃干燥2h，450℃焙烧3h得到催化剂CF4，具体性质见表2。
比较例5
(1)硅铝材料制造
配制浓度为50gAl 2O 3/L的硫酸铝溶液和浓度为50gSiO 2/L、模数为2.8的硅溶胶溶液待用，配制浓度为1mol/L的稀硫酸溶液待用。配制苛性比1.25、浓度160gAl 2O 3/L的偏铝酸钠溶液待用。
量取1.44L浓度为50gSiO 2/L的硅溶胶溶液加入到容器中，在搅拌的条件下，缓慢加入1L浓度为50gAl 2O 3/L的硫酸铝溶液，这个过程有氢氧化铝胶 体生成，但溶液仍是液体形式存在。接着加入1mol/L的稀硫酸溶液，调节pH为3.5，完成酸化处理，得到混合液A。
将混合液A以28mL/min加入到5000mL反应器中，同时将配制好的偏铝酸钠溶液并流加入，通过调节偏铝酸钠流速来控制反应的pH为8.3，并水浴加热保持反应器内浆液温度80℃和pH值恒定。待反应结束后，偏铝酸钠用量为325mL，在搅拌条件下向反应器内加入75g碳酸铵调节pH值为10.8。将上述浆液放入反应器中，在搅拌的条件下，处理温度为210℃，处理压力0.4MPa，处理8h(相当于Δt+6小时)。处理后的浆料用90℃的热水洗涤至液体中性，在120℃干燥6h，得到干燥后样品PFO-5，在600℃下焙烧5h得到硅铝材料PF-5，其性质见表1。
所述硅铝材料的SiO 2/Al 2O 3摩尔比为1.20。
(2)加氢催化剂制造
取500g制造的PF0-5硅铝干燥样，加入田菁粉10g和柠檬酸12.15g，水420g，混合均匀后然后成球型，将成球后的样品经过650℃焙烧4h得到粒度为0.3-0.8mm的载体ZF5。
称取磷酸28.57g，加入蒸馏水800mL，然后依次加入氧化钼77.58g、碱式碳酸镍35.56g，加热搅拌至完全溶解后，用蒸馏水将溶液定容至1000mL，得溶液L1。将载体ZF5用溶液L1溶液饱和浸渍，在110℃干燥2h，450℃焙烧3h得到催化剂CF5，具体性质见表2。
比较例6
(1)硅铝材料制造
配制浓度为50gAl 2O 3/L的硫酸铝溶液和浓度为1mol/L的稀硫酸溶液待用。配制苛性比1.25、浓度160gAl 2O 3/L的偏铝酸钠溶液待用。
称取72g白炭黑加入到容器中，缓慢加入1L浓度为50gAl 2O 3/L的硫酸铝溶液，搅拌形成悬浮液。接着加入1mol/L的稀硫酸溶液，调节pH为3.5，完成酸化处理，得到悬浮液A。
向5000mL反应器中加入700mL去离子水作为底水，启动搅拌并加热，去离子水加热到80℃后，将混合液A以28mL/min加入到反应器中，同时将配制好的偏铝酸钠溶液并流加入，通过调节偏铝酸钠流速来控制反应的pH为 8.3，并保持反应器内浆液温度和pH值恒定。待反应结束后，偏铝酸钠用量为325mL，在搅拌条件下向反应器内加入75g碳酸铵调节pH值为10.8。将上述浆液放入反应器中，在搅拌的条件下，处理温度为210℃，处理压力0.4MPa，处理8h(相当于Δt+6小时)。处理后的浆料用90℃的热水洗涤至液体中性，在120℃干燥6h，得到干燥后样品PF0-6，在600℃下焙烧5h得到硅铝材料PF-6，其性质见表1。
所述硅铝材料的SiO 2/Al 2O 3摩尔比为1.20，并且从SEM照片上看不到片层结构。
比较例7
(1)硅铝材料制造
配制浓度为50gAl 2O 3/L的硫酸铝溶液和浓度为50gSiO 2/L、模数为2.8的硅溶胶溶液待用，配制浓度为1mol/L的稀硫酸溶液待用。配制苛性比1.25、浓度160gAl 2O 3/L的偏铝酸钠溶液待用。
量取1.44L浓度为50gSiO 2/L的硅溶胶溶液加入到容器中，在搅拌的条件下，缓慢加入1L浓度为50gAl 2O 3/L的硫酸铝溶液，这个过程有氢氧化铝胶体生成，但溶液仍是液体形式存在。接着加入1mol/L的稀硫酸溶液，调节pH为3.5，完成酸化处理，得到混合液A。
向5000mL反应器中加入700mL去离子水作为底水，启动搅拌并加热，去离子水加热到80℃后，将混合液A以28mL/min加入到反应器中，同时将配制好的偏铝酸钠溶液并流加入，通过调节偏铝酸钠流速来控制反应的pH为8.3，并保持反应器内浆液温度和pH值恒定。待反应结束后，偏铝酸钠用量为325mL，在搅拌条件下向反应器内加入75g碳酸铵调节pH值为10.8。将上述浆液放入反应器中，在搅拌的条件下，处理温度为210℃，处理压力0.4MPa，处理3h(相当于Δt+1小时)。处理后的浆料用90℃的热水洗涤至液体中性，在120℃干燥6h，得到干燥后样品PFO-7，在600℃下焙烧5h得到硅铝材料PF-7，其性质见表1。
所述硅铝材料的SiO 2/Al 2O 3摩尔比为1.20，包含平均长度为0.85μm、平均厚度为25nm的片层结构。该片层结构占所述硅铝材料总体积的2％。
(2)加氢催化剂制造
取500g制造的PFO-7硅铝干燥样，加入田菁粉10g和柠檬酸12.15g，水420g，混合均匀后然后成球型，将成球后的样品经过650℃焙烧4h得到粒度为0.3-0.8mm的载体Z7。
将载体Z7用溶液L1溶液饱和浸渍，在110℃干燥2h，450℃焙烧3h得到催化剂CF7，具体性质见表2。
表1硅铝材料的性质(实施例)
Figure PCTCN2022071289-appb-000001
表1硅铝材料的性质(比较例)
Figure PCTCN2022071289-appb-000002
表2催化剂的性质(实施例)
Figure PCTCN2022071289-appb-000003
表2催化剂的性质(比较例)
Figure PCTCN2022071289-appb-000004
将上述催化剂在高压釜上进行活性评价，评价原料油性质和评价条件见表3。以对比例1的活性为100，其它与对比例1活性比较后的评价结果见表4。
表3原料油性质及评价条件
项目 数值
原料油性质  
硫，％ 5.76
残炭，％ 24.86
镍+钒/μg·g -1 214.38
>500℃渣油收率，％ 93.2
工艺条件  
反应温度/℃ 420
反应压力/MPa 15
油剂体积比 13:1
反应时间/h 1
表4催化剂评价结果(实施例)
Figure PCTCN2022071289-appb-000005
表5催化剂评价结果(比较例)
Figure PCTCN2022071289-appb-000006
从各表中数据可以看出：采用本发明制造的硅铝材料孔容大、<10nm孔所占比例小，氧化钠含量低，B酸含量高。以此硅铝材料制造的加氢催化剂，与对比例制造催化剂相比，增加了杂质脱除率和渣油转化率，尤其适合用做重油或渣油加氢催化剂。

Claims (16)

  1. 一种硅铝材料，其SiO 2/Al 2O 3摩尔比为0.8-1.5(优选为1.0-1.4)，包含平均长度为0.5-2μm(优选0.5-1.5μm)、平均厚度为30-80nm(优选30-75nm)的片层结构，并且其焙烧形式具有基本上如下表I或表II所示的XRD图谱，优选其焙烧形式具有基本上如图2所示的XRD图谱，
    表I
    2θ d-间距(nm) 相对强度 14.0 0.12-0.13 VS 24.3 0.18-0.19 VS 34.3 0.07-0.08 S 42.6 0.11-0.13 M 51.9 0.10-0.13 M 66.4 0.06-0.08 M
    表II
    2θ d-间距(nm) 相对强度 13.9 0.12-0.13 VS 24.2 0.17-0.18 VS 31 0.36-0.38 M 34.4 0.08-0.10 S 39.9 0.08-0.10 M 42.5 0.11-0.12 M 51.6 0.12-0.13 W 57.8 0.14-0.16 W 66.4 0.07-0.09 W
    其中设所述XRD图谱中最强衍射峰的强度值为100，则W＝弱，即相对强度>0至≤20，M＝中等，即相对强度>20至≤40，S＝强，即相对强度>40至≤60，VS＝非常强，即相对强度>60至≤100。
  2. 权利要求1所述的硅铝材料，其孔容不小于1.1mL/g(优选大于1.15mL/g，进一步优选为1.15-1.5mL/g)，和/或，其比表面积为260-340m 2/g(优选为260-310m 2/g)，和/或，其孔分布为：孔直径＜10nm的孔的孔容占总孔容的≤5％(优选孔直径＜10nm的孔的孔容占总孔容的≤3％)，孔直径为10-50nm的孔的孔容占总孔容的65％-85％(优选孔直径为10-50nm的孔的孔容 占总孔容的70％-85％)，孔直径＞50nm的孔的孔容占总孔容的10％-30％(优选孔直径＞50nm的孔的孔容占总孔容的12％-25％)，和/或，其平均孔径为14-23nm(优选为16-21nm)。
  3. 权利要求1所述的硅铝材料，其B酸含量大于0.08mmol/g(优选为0.1-0.2mmol/g或0.1-0.15mmol/g)，和/或，其B酸与L酸比值为0.2-0.8(优选为0.3-0.7)，和/或，其Na 2O含量小于0.3wt％(优选小于0.2wt％)，和/或，在其核磁共振硅谱中，在化学位移-88ppm至-94ppm有吸收峰，并且在其核磁共振铝谱中，在化学位移57ppm附近有吸收峰，和/或，其焙烧形式在小角度XRD图谱上没有衍射峰。
  4. 权利要求1所述的硅铝材料，还包含非片层结构，其中以所述硅铝材料的总体积计，所述片层结构所占的比例为3％以上(优选5％以上，更优选10-80％或10-60％)。
  5. 一种硅铝材料的制造方法，顺次包括以下步骤：
    (1)将酸性铝源加入到硅源中而得到混合物A，
    (2)将所述混合物A与碱性铝源在水的存在下进行接触而得到浆液B，和
    (3)将所述浆液B进行水热处理而得到所述硅铝材料。
  6. 权利要求5所述的制造方法，其中在步骤(1)中，所述硅源为水溶性或水分散性的碱性含硅化合物(优选水溶性或水分散性的碱性无机含硅化合物，更优选选自于水溶性硅酸盐、水玻璃、硅溶胶中的一种或几种，优选为水玻璃)，和/或，所述硅源以水溶液的形式使用，并且以所述水溶液的总重量计，所述硅源(以SiO 2计)的浓度为5-30wt％(优选15-30wt％)，和/或，所述酸性铝源为水溶性的酸性含铝化合物(优选水溶性的酸性无机含铝化合物，特别是水溶性的无机强酸铝盐，更优选选自于硫酸铝、硝酸铝、氯化铝中的一种或几种，优选为硫酸铝)，和/或，所述酸性铝源以水溶液的形式使用，并且以所述水溶液的总重量计，所述酸性铝源(以Al 2O 3计)的浓度为30-100g/L(优选30-80g/L)，和/或，所述硅源(以SiO 2计)与所述酸性铝源(以Al 2O 3计)的重量比为1:1-9:1(优选为1:1-7:1)。
  7. 权利要求5所述的制造方法，其中在步骤(1)中，还加入酸(优选将所述酸性铝源加入到所述硅源中，然后再加入所述酸，以得到所述混合物 A)，和/或，所述酸为水溶性酸(优选水溶性的无机酸，更优选选自于硫酸、硝酸、盐酸中的一种或几种，优选为硫酸)，和/或，所述酸以水溶液的形式使用，并且以所述水溶液的总重量计，所述酸的浓度为2-6wt％(优选2-5wt％wt％)，和/或，所述酸的加入量使得所述混合物A的pH值为2-4(优选为3-4)。
  8. 权利要求5所述的制造方法，其中在步骤(2)中，所述碱性铝源为水溶性的碱性含铝化合物(优选为水溶性的碱性无机含铝化合物，特别是碱金属偏铝酸盐，更优选选自于偏铝酸钠、偏铝酸钾中的一种或几种，优选为偏铝酸钠)，和/或，所述碱性铝源以水溶液的形式使用，并且以所述水溶液的总重量计，所述碱性铝源(以Al 2O 3计)的浓度为130-350g/L(优选150-250g/L)，和/或，以所述混合物A、所述碱性铝源和水的总体积计，所述混合物A的用量为40-70vol％(优选为40-65vol％)，和/或，以所述混合物A、所述碱性铝源和水的总体积计，所述碱性铝源的用量为20-40vol％(优选为25-40vol％)，和/或，以所述混合物A、所述碱性铝源和水的总体积计，所述水的用量为10-20vol％(优选为13-20vol％)，和/或，将所述混合物A与所述碱性铝源先后或同时加入到水中(优选将所述混合物A与所述碱性铝源以并流方式加入到水中)，和/或，所述混合物A的加入流速为15-50mL/min(优选为20-40mL/min)，和/或，控制所述碱性铝源的加入流速，使得所述浆液B的pH值维持在7.5-10.5(优选8.0-10.5，进一步优选为8.5-10.5)。
  9. 权利要求5所述的制造方法，其中在步骤(2)中，还加入水溶性碳酸盐(优选将所述混合物A和所述碱性铝源加入水中，然后再加入所述水溶性碳酸盐，以得到所述浆液B)，和/或，所述水溶性碳酸盐选自于碱金属和铵中的一种或几种的碳酸盐(优选选自于碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、碳酸铵、碳酸氢铵中的一种或几种，优选碳酸钠)，和/或，所述水溶性碳酸盐以固体的形式使用，和/或，所述水溶性碳酸盐的加入量使得所述浆液B的pH值为10.5-12(优选11-12)。
  10. 权利要求5所述的制造方法，其中在步骤(3)中，将所述硅铝材料从所述水热处理的反应体系中分离(比如过滤或离心分离)、洗涤至中性、然后干燥，和/或，所述干燥的条件包括：干燥温度为100-150℃，干燥时间为6-10小时。
  11. 权利要求5所述的制造方法，其中在步骤(1)中，温度为25-50℃(优选25-40℃)，压力为常压，和/或，在步骤(2)中，温度为50-90℃(优选50-80℃)，压力为常压，和/或，在步骤(3)中，温度为180-300℃(优选为180-280℃，进一步优选为180-250℃)，压力为0.1-0.5MPa(优选为0.1-0.3MPa)，和/或，在步骤(3)中，设所述水热处理的初始时刻为t 0，所述水热处理的反应体系达到粘度最大值的时刻为t max，Δt＝t max-t 0，则所述水热处理的时间(单位是h)为从Δt+1至Δt+20(优选从Δt+2至Δt+12，特别是从Δt+4至Δt+8)，和/或，在步骤(3)中，所述水热处理的时间为6-20h(优选8-12h)。
  12. 权利要求5所述的制造方法，其中还加入助剂(优选选自于磷、硼和钛中的一种或几种)，和/或，所述助剂以氧化物计的重量含量为1-8wt％(优选2-6wt％)，相对于所述硅铝材料的总重量100wt％计。
  13. 一种催化材料，包括活性金属组分和权利要求1所述的硅铝材料或按照权利要求5所述的制造方法制造得到的硅铝材料。
  14. 权利要求13所述的催化材料，其中所述活性金属组分是具有加氢活性的金属组分(优选选自元素周期表第VIB族金属和第VIII族金属中的至少一种，特别是选自Mo、W、Ni和Co中的至少一种)，和/或，以所述催化材料的总重量计，所述活性金属组分(以氧化物计)的重量百分比含量为5-30wt％(优选5-25wt％)。
  15. 一种加氢方法，包括使含烃物料在权利要求13所述的催化材料的存在下进行加氢反应的步骤。
  16. 权利要求15所述的加氢方法，其中所述含烃物料选自于柴油、蜡油、重油、煤焦油、乙烯焦油、催化油浆中的至少一种，和/或，所述加氢反应的反应条件包括：反应压力为5-20MPaG，反应温度为300-450℃，液时体积空速为0.1-1.5h -1，氢油体积比为100-1000。
PCT/CN2022/071289 2021-01-11 2022-01-11 一种包含片层结构的硅铝材料、其制造方法及应用 WO2022148474A1 (zh)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4001144A (en) * 1975-12-19 1977-01-04 Kaiser Aluminum & Chemical Corporation Process for modifying the pore volume distribution of alumina base catalyst supports
US20040092390A1 (en) * 2002-11-08 2004-05-13 Timken Hye Kyung C. Method for preparing a highly homogeneous amorphous silica-alumina composition
CN103191773A (zh) * 2012-01-06 2013-07-10 中国石油化工股份有限公司 一种制备加氢裂化催化剂的方法
CN108786926A (zh) * 2017-04-27 2018-11-13 青岛惠城环保科技股份有限公司 一种孔径可调的催化裂化催化剂基质的制备方法
CN108927128A (zh) * 2017-05-26 2018-12-04 中国石油化工股份有限公司 一种高b酸中心的无定形催化材料及其制备方法
CN109305689A (zh) * 2017-07-28 2019-02-05 中国石油天然气股份有限公司 一种中大孔硅铝材料及其制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105983345B (zh) * 2015-02-03 2021-03-19 中国科学院上海高等研究院 干凝胶法制备的sapo-34分子筛膜渗透汽化与汽相渗透分离气液/液体混合物的方法
CN109833899B (zh) * 2017-11-29 2022-03-11 中国石油化工股份有限公司 一种硅铝复合材料及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4001144A (en) * 1975-12-19 1977-01-04 Kaiser Aluminum & Chemical Corporation Process for modifying the pore volume distribution of alumina base catalyst supports
US20040092390A1 (en) * 2002-11-08 2004-05-13 Timken Hye Kyung C. Method for preparing a highly homogeneous amorphous silica-alumina composition
CN103191773A (zh) * 2012-01-06 2013-07-10 中国石油化工股份有限公司 一种制备加氢裂化催化剂的方法
CN108786926A (zh) * 2017-04-27 2018-11-13 青岛惠城环保科技股份有限公司 一种孔径可调的催化裂化催化剂基质的制备方法
CN108927128A (zh) * 2017-05-26 2018-12-04 中国石油化工股份有限公司 一种高b酸中心的无定形催化材料及其制备方法
CN109305689A (zh) * 2017-07-28 2019-02-05 中国石油天然气股份有限公司 一种中大孔硅铝材料及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4261189A4

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