WO2023116391A1 - 一种含b酸的加氢催化剂载体及其制备与应用 - Google Patents

一种含b酸的加氢催化剂载体及其制备与应用 Download PDF

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Publication number
WO2023116391A1
WO2023116391A1 PCT/CN2022/136126 CN2022136126W WO2023116391A1 WO 2023116391 A1 WO2023116391 A1 WO 2023116391A1 CN 2022136126 W CN2022136126 W CN 2022136126W WO 2023116391 A1 WO2023116391 A1 WO 2023116391A1
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Prior art keywords
acid
hydrogenation catalyst
catalyst carrier
alumina
carrier
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PCT/CN2022/136126
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English (en)
French (fr)
Inventor
王丹
宋金鹤
张文成
温广明
马宝利
徐铁钢
李瑞峰
郭金涛
徐伟池
谭明伟
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中国石油天然气股份有限公司
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Publication of WO2023116391A1 publication Critical patent/WO2023116391A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to a hydrogenation catalyst carrier containing B acid and its preparation and application, belonging to the technical field of petroleum refining hydrogenation.
  • the catalyst carrier for diesel hydrotreating is generally dominated by alumina, and the unmodified alumina carrier surface only has L acid.
  • researchers added F, B, Zr and other elements to increase the B acid content of the carrier, but the B acid centers formed by these modification methods are random and the acid content is uncontrollable.
  • Diesel hydrorefining catalysts should not have too strong requirements on the strength of the carrier acid, and weak acids should be the main ones to avoid cracking during the hydrogenation process and affect the yield of refined diesel oil.
  • molecular sieves and amorphous silica-alumina are generally added to the carrier to adjust the acidity and acidity of the carrier. Generally, this type of catalyst requires stronger acidity.
  • Chinese patent CN104646073A discloses a hydrogenation catalyst carrier, which is molecular sieve 10-70wt%, alumina 10-40wt%, silicon dioxide 5-30wt% by weight percentage, and the rest is binder; hydrogenation catalyst carrier specific surface area is 380-573m 2 /g, pore volume 0.63-0.94cc/g, infrared acid content 0.10-0.45mmol/g, ratio of B acid to L acid 2.3-0.9:1; molecular sieve is mesoporous amorphous silicon aluminum
  • the multi-level porous composite molecular sieve coated with microporous Beta molecular sieve has a sodium oxide content of ⁇ 0.05 wt%, and an infrared acid content of 0.23-0.58 mmol/g.
  • Chinese patent CN108262066A discloses a hydrogenation catalyst carrier, including a solid acid component and an amorphous heat-resistant oxide, wherein, the specific surface area of the hydrogenation catalyst carrier is 220-430m 2 /g, and the total pore volume is 0.35- 0.70mL/g, the amount of infrared acid is 0.50-1.0mmol/g, the ratio of B acid to L acid is 0.2-1.0, and the radial crush resistance is greater than 130N/cm; based on the total weight of the carrier, the The content of the solid acid component is 10-80%, and the content of the amorphous heat-resistant oxide is 20-90%; wherein, the solid acid component is MCM-22 molecular sieve, and its silicon-aluminum ratio is 10-50, The specific surface area is 400-700m 2 /g, and the pore volume is 0.35-0.75mL/g.
  • Chinese patent CN106311309A discloses a hydrogenation catalyst carrier, including an alumina carrier and a molecular sieve, the weight ratio of the alumina carrier to the molecular sieve is 7:1; the preparation method of the above-mentioned hydrogenation catalyst carrier includes the following steps: a. Aluminum carrier and molecular sieve are dissolved in deionized water to form a mixed slurry; b.
  • the mixed slurry is roasted to obtain a finished catalyst carrier;
  • the pore volume of the alumina carrier is 0.2-0.5mL/g, and the specific surface area is 400-500m 2 /g , the pores with a diameter of 5-8nm account for 90% of the total pore volume, the crushing strength is 300N/cm-500N/cm, the total infrared acid content is 0.30-0.45mmol/g, and the medium-strong acid content/infrared total acid content is 0.56-0.81, L acid content/B acid content is 1.40-2.30.
  • Chinese patent CN108262076A discloses a hydrogenation catalyst carrier, including a solid acid component and an amorphous heat-resistant oxide, wherein: the specific surface area of the hydrogenation catalyst carrier is 220-450m 2 /g, and the total pore volume is 0.35-0.70 mL/g, the amount of infrared acid is 0.50-1.0mmol/g, the ratio of B acid to L acid is 0.2-1.0, and the radial crush resistance is greater than 130N/cm; based on the total weight of the carrier, the solid acid The component content is 10-80%, and the amorphous heat-resistant oxide content is 20-90; wherein, the solid acid component is a mixture of MCM-22 molecular sieve and ZSM-5 molecular sieve, and the mixing ratio is 1:10-10 : 1; the silicon-aluminum ratio of the MCM-22 molecular sieve is 10-60, the specific surface area is 400-600m 2 /g, and the pore volume is 0.35-0.75mL/g;
  • Chinese patent CN108262074A discloses a hydrogenation catalyst carrier, including a solid acid component and an amorphous heat-resistant oxide, wherein: the specific surface area of the hydrogenation catalyst carrier is 220-450m 2 /g, and the total pore volume is 0.35- 0.70mL/g, the amount of infrared acid is 0.50-1.0mmol/g, the ratio of B acid to L acid is 0.2-1.0, and the radial crush resistance is greater than 130N/cm; based on the total weight of the carrier, solid The acid component content is 10-80%, and the amorphous heat-resistant oxide content is 20-90%; wherein, the solid acid component is a mixture of MCM-22 molecular sieve and Y molecular sieve, and the mixing ratio is 1:10-10 : 1; the silicon-aluminum ratio of the MCM-22 molecular sieve is 10-60, the specific surface area is 400-600m 2 /g, and the pore volume is 0.35-0.75mL/g; the silicon-
  • Chinese patent CN105983445A discloses a hydrogenation catalyst carrier, wherein: aluminum oxide containing silicon and phosphorus is used as the hydrogenation catalyst carrier, the pore volume of the carrier is 0.7-1.5mL/g, the specific surface area is 250-450m 2 /g, the catalyst The 20-30nm pore ratio of the carrier reaches more than 20%.
  • the acid properties of the carrier surface are: the acid content is 0.2-0.7mmol/g, and the B acid is 0.1-0.3mmol/g.
  • Chinese patent CN103896318A discloses a B-rich acid-rich mesoporous alumina support material for catalytic cracking catalysts, which is prepared by modifying pseudo-boehmite with NH 4 BF 4 and adding P123 template agent.
  • the material has mesoporous structure, the pore volume is 0.32-0.41mL/g, and the specific surface area is 200-237m 2 /g; the defect of this technology or the deficiency relative to the present invention: the pore volume specific surface area of the material disclosed in the present invention has limitations, and the oxidation Aluminum material is used in catalytic cracking.
  • Chinese patent CN112619632A discloses a boron, phosphorus, fluorine, magnesium and other element-modified alumina carrier prepared by co-precipitation method.
  • the amount of acid is 0.08-0.150mmol/g
  • the amount of L acid is 0.10-0.40mmol/g.
  • B acid is introduced into the catalyst carrier in this field, and most of them are added various molecular sieves containing B acid in the carrier, but the catalyst carrier containing molecular sieve has strong acidity and is suitable for preparing cracking catalyst; Introducing elements such as F, B, Zr, etc., the acid centers of the carrier prepared by this method are randomly formed, and the amount of acid is uncontrollable.
  • the amount of carrier B acid the total acid amount of the carrier is too large, or the ratio of B acid amount is increased but the amount of B acid is not significantly increased.
  • the specific surface area of the carrier is increased while the carrier pore size is increased. The loss is too great.
  • an object of the present invention is to provide a hydrogenation catalyst carrier containing B acid.
  • Another object of the present invention is to provide a method for preparing the above-mentioned hydrogenation catalyst carrier containing B acid.
  • Another object of the present invention is to provide a hydrorefining catalyst whose carrier is the above-mentioned B acid-containing hydrogenation catalyst carrier.
  • Another object of the present invention is to provide the application of the above-mentioned hydrorefining catalyst in the hydrorefining process in the field of petroleum refining.
  • the present invention provides a hydrogenation catalyst carrier containing B acid, wherein, the hydrogenation catalyst carrier containing B acid is based on a commercial alumina carrier and an alumina material containing B acid
  • the raw material is prepared, wherein, based on the total weight of the raw material being 100%, it includes 50-95% of commercial alumina carrier and 5-50% of alumina material containing B acid.
  • the B-acid-containing hydrogenation catalyst carrier of the present invention includes 60-75% of commercial oxidation Aluminum support and 25-40% alumina material containing B acid.
  • the B/L acid value of the B-acid-containing alumina material is 0.3-2.5, and the specific surface area is 200-300m 2 / g, the pore volume is 0.55-0.90mL/g.
  • the B/L acid value of the B-acid-containing alumina material is 0.8-1.6.
  • the alumina material containing B acid is made of common pseudo-boehmite as a raw material and passed through NH4 by sol-gel method Modified BF 4 , including:
  • the pseudo-boehmite is prepared into a uniform aluminum sol slurry with an acid solution at a temperature of 70-80°C.
  • the acid solution includes an inorganic acid solution or an organic acid solution.
  • the inorganic acid solution may be, for example, concentrated nitric acid.
  • the specific surface area of the pseudo-boehmite is 300-600m 2 /g, and the pore volume is 0.40-0.70mL/g.
  • the dropping rate of the NH 4 BF 4 saturated solution is 3-5 mL/min.
  • the calcination temperature is 350-450°C, preferably 400-450°C.
  • the present invention controls the calcination temperature in the preparation process of the B-acid-containing alumina material within the above-mentioned range, which can ensure that the B-acid content on the surface of the B-acid-containing alumina material is not destroyed.
  • the specific surface area of the commercial alumina carrier is 380-600m 2 /g, and the pore volume is 0.40-0.60mL/g.
  • the specific surface area of the hydrogenation catalyst carrier containing B acid is 220-450m 2 /g, and the pore volume is 0.45-0.70mL /g;
  • the specific surface area is 300-400m 2 /g, and the pore volume is 0.50-0.60mL/g.
  • the B/L acid value of the B-acid-containing hydrogenation catalyst carrier is between 0.01-0.8, and the infrared acid content at 150°C is It accounts for 60-70% of the total acid content, of which B acid accounts for 5-40% of the infrared acid content; 250°C infrared acid accounts for 20-30% of the total acid content, of which B acid accounts for 4-4% of the infrared acid content 40%; 350 °C infrared acid accounts for 5-15% of the total acid, of which B acid accounts for 2-35% of the infrared acid;
  • the B/L acid value of the hydrogenation catalyst carrier containing B acid is between 0.3-0.59, and the amount of infrared acid at 150°C accounts for 63-68% of the total acid amount, wherein the amount of B acid accounts for 10% of the amount of infrared acid 20-40%; 250°C infrared acid accounts for 23-28% of the total acid amount, of which B acid accounts for 20-40% of the infrared acid amount; 350°C infrared acid amount accounts for 8-12% of the total acid amount, of which The amount of B acid accounts for 12-34% of the amount of infrared acid.
  • the "infrared acid content” in the present invention is the sum of "B acid content” and “L acid content”
  • total acid content refers to the sum of infrared acid content at different temperature points
  • the ratio to the total acid refers to the ratio of the infrared acid corresponding to the temperature point to the total acid.
  • the present invention also provides the preparation method of the hydrogenation catalyst carrier containing B acid mentioned above, wherein, the preparation method comprises:
  • the nitric acid solution is added to the dry mixed sample for wet mixing to obtain a wet mixed sample;
  • the wet-mixed sample is molded, and then the molded product is dried and roasted to obtain the hydrogenation catalyst carrier containing B acid.
  • the commercial alumina carrier and the alumina material containing B acid are mixed in a certain proportion to prepare the hydrogenation catalyst carrier containing B acid, and the alumina material containing B acid can be introduced into the carrier of the catalyst, thereby realizing B on the catalyst carrier. Controllable preparation of acidity.
  • the present invention does not make any adjustments to the amount of scallop powder used in the preparation process of the hydrogenation catalyst carrier containing B acid, the concentration and amount of nitric acid solution, the dry mixing time, the wet mixing time, the molding method, drying and roasting conditions, etc.
  • those skilled in the art can reasonably set these parameters according to actual operation needs, as long as the purpose of preparing the hydrogenation catalyst carrier containing B acid can be realized.
  • the present invention also provides a hydrofinishing catalyst, wherein the carrier of the hydrofinishing catalyst is the above-mentioned B acid-containing hydrogenation catalyst carrier.
  • the strength of the hydrotreating catalyst is >130 N/cm. In some preferred embodiments of the present invention, the strength of the hydrofining catalyst is ⁇ 160 N/cm.
  • the present invention also provides the application of the above-mentioned hydrorefining catalyst in the hydrorefining process in the field of petroleum refining.
  • the hydrofinishing process in the field of petroleum refining comprises gasoline and diesel hydrofinishing.
  • the present invention firstly synthesizes an alumina material containing a high amount of B acid by a sol-gel method, and then mixes an appropriate proportion of the alumina material containing B acid with a commercial alumina carrier to prepare the hydrogenation catalyst carrier containing B acid.
  • a method of introducing B acid into the hydrogenation catalyst carrier makes the acid strength and acid amount of B acid on the carrier all within a controllable range, and the appropriate acid strength and acid amount on the carrier can promote the distillate oil with steric hindrance.
  • the difficult-to-remove sulfides are removed through the direct desulfurization reaction path, thereby increasing the hydrodesulfurization reaction rate, reducing the reaction temperature, and simultaneously promoting the simultaneous removal of sulfur, nitrides, and aromatics.
  • the alumina material containing B acid into the catalyst carrier, a carrier material rich in B acid centers is prepared, and the carrier material is mainly weak acid and medium strong acid.
  • Ni-W catalyst activity evaluation result that adopts the hydrogenation catalyst carrier preparation that contains B acid provided by the present invention shows that this catalyst hydrodesulfurization activity is high, and has improved the direct desulfurization of 4,6-DMDBT and iso Structure-direct desulfurization reaction path, and did not significantly affect the liquid yield, indicating that no obvious cracking reaction occurred during the hydrogenation reaction.
  • the reason or mechanism for this beneficial effect is: 4,6-DMDBT has a large steric hindrance, and the hydrogenation active center is difficult to contact with the sulfur atom, resulting in a low reaction rate and desulfurization rate in the direct hydrodesulfurization reaction.
  • the B in the catalyst The existence of the acid center promotes the methyl transfer of 4 and 6 positions of 4,6-DMDBT and improves the direct desulfurization and isomerization-direct desulfurization reaction pathways, greatly improving the desulfurization efficiency and desulfurization activity.
  • ranges are given in terms of lower limits and upper limits. There can be one or more lower bounds, and one or more upper bounds, respectively.
  • a given range is defined by selecting a lower limit and an upper limit. Selected lower and upper limits define the boundaries of a particular range. All ranges defined in this manner are combinable, ie, any lower limit can be combined with any upper limit to form a range. For example, ranges of 60-120 and 80-110 are listed for a particular parameter, with the understanding that ranges of 60-110 and 80-120 are also contemplated. Additionally, if the minimum range values listed are 1 and 2, and the maximum range values listed are 3, 4, and 5, the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
  • the numerical range “a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range “0-5" indicates that all real numbers between "0-5" have been listed in the present invention, and "0-5" is only an abbreviated representation of these numerical combinations.
  • This embodiment provides a series of alumina materials containing B acid, which are prepared by a preparation method comprising the following steps:
  • the F/Al molar ratios obtained by elemental analysis of the alumina material containing B acid are respectively 0.06, 0.09, 0.12, 0.15, and 0.18.
  • the alumina material containing B acid is recorded as CL1-CL5
  • the pseudo-boehmite aluminum blank sample is recorded as CL0
  • the pore structure properties and acidity of CL0 and CL1-CL5 are shown in Table 1.
  • the alumina material containing B acid was successfully prepared in Example 1, the B/L acid value is 0.3-2.5, the specific surface area is 200-300m 2 /g, and the pore volume is 0.55-0.7mL/ g.
  • This example provides a series of alumina materials containing B acid.
  • the physical property data of the pseudo-boehmite (DLO and ELO) used are shown in Table 2 below.
  • the specific surface area of the B acid-containing alumina materials DL1 and EL1 synthesized in this example is in the range of 200-300m 2 /g, and the pore volume is in the range of 0.7-0.9mL/g.
  • a series of alumina hydrogenation catalyst supports containing B acid were prepared by using commercial alumina, wherein the specific surface area of commercial alumina powder was 425 m 2 /g, and the pore volume was 0.52 mL/g.
  • This embodiment provides a series of hydrogenation catalyst supports containing B acid, which are prepared by a preparation method comprising the following steps:
  • the wet-mixed sample was extruded with a twin-screw extruder, and the final extruded sample was a clover strip carrier with an outer diameter of 1.8mm.
  • the program After drying in a blast drying oven at 120°C for 4 hours, the program Raise the temperature to 450°C and roast for 4 hours to obtain hydrogenation catalyst supports containing B acid, which are respectively denoted as ZT2-1, ZT3-1, and ZT4-1.
  • This embodiment provides a series of hydrogenation catalyst supports containing B acid, which are prepared by a preparation method comprising the following steps:
  • the wet-mixed sample was extruded with a twin-screw extruder, and the final extruded sample was a clover strip carrier with an outer diameter of 1.8mm.
  • the program After drying in a blast drying oven at 120°C for 4 hours, the program Raise the temperature to 450°C and roast for 4 hours to obtain hydrogenation catalyst supports containing B acid, which are respectively denoted as ZT2-2, ZT3-2, and ZT4-2.
  • This embodiment provides a series of hydrogenation catalyst supports containing B acid, which are prepared by a preparation method comprising the following steps:
  • the wet-mixed sample was extruded with a twin-screw extruder, and the final extruded sample was a clover strip carrier with an outer diameter of 1.8mm.
  • the program After drying in a blast drying oven at 120°C for 4 hours, the program Raise the temperature to 450°C and roast for 4 hours to obtain hydrogenation catalyst supports containing B acid, which are respectively denoted as ZT2-3, ZT3-3, and ZT4-3.
  • the present embodiment provides a series of B acid-containing hydrogenation catalyst supports, which are prepared by a preparation method comprising the following steps:
  • the wet-mixed sample was extruded with a twin-screw extruder, and the final extruded sample was a clover strip carrier with an outer diameter of 1.8mm.
  • the program After drying in a blast drying oven at 120°C for 4 hours, the program Raise the temperature to 450°C and roast for 4 hours to obtain hydrogenation catalyst supports containing B acid, which are respectively denoted as ZT2-4, ZT3-4, and ZT4-4.
  • This embodiment provides a series of hydrogenation catalyst supports containing B acid, which are prepared by a preparation method comprising the following steps:
  • the wet-mixed sample was extruded with a twin-screw extruder, and the final extruded sample was a clover strip carrier with an outer diameter of 1.8mm.
  • the program After drying in a blast drying oven at 120°C for 4 hours, the program Raise the temperature to 450°C and roast for 4 hours to obtain hydrogenation catalyst supports containing B acid, which are respectively denoted as ZT2-5, ZT3-5, and ZT4-5.
  • This embodiment provides a series of hydrogenation catalyst supports containing B acid, which are prepared by a preparation method comprising the following steps:
  • the wet-mixed sample was extruded with a twin-screw extruder, and the final extruded sample was a clover strip carrier with an outer diameter of 1.8mm.
  • the program After drying in a blast drying oven at 120°C for 4 hours, the program Raise the temperature to 450°C and roast for 4 hours to obtain hydrogenation catalyst supports containing B acid, which are respectively denoted as ZT2-6, ZT3-6, and ZT4-6.
  • This embodiment provides a series of hydrogenation catalyst supports containing B acid, which are prepared by a preparation method comprising the following steps:
  • the wet-mixed sample was extruded with a twin-screw extruder, and the final extruded sample was a clover strip carrier with an outer diameter of 1.8mm.
  • the program After drying in a blast drying oven at 120°C for 4 hours, the program Raise the temperature to 450°C and roast for 4 hours to obtain hydrogenation catalyst supports containing B acid, which are respectively denoted as ZT2-7, ZT3-7, and ZT4-7.
  • This comparative example provides a kind of hydrogenation catalyst carrier, and it is to make by the preparation method comprising the following steps:
  • the wet-mixed sample was extruded with a twin-screw extruder, and the final extruded sample was a clover strip carrier with an outer diameter of 1.8 mm. After drying in a blast drying oven at 120 ° C for 4 hours, the The temperature was raised to 450°C and calcined for 4 hours to obtain a hydrogenation catalyst carrier, which was designated as ZT-0.
  • This comparative example provides a hydrogenation catalyst carrier containing B acid, which is prepared by a preparation method comprising the following steps:
  • the wet-mixed sample was extruded with a twin-screw extruder, and the final extruded sample was a clover strip carrier with an outer diameter of 1.8 mm. After drying in a blast drying oven at 120 ° C for 4 hours, the The temperature was raised to 450°C and calcined for 4 hours to obtain a hydrogenation catalyst support containing B acid, which was designated as ZT-B1.
  • This comparative example provides a hydrogenation catalyst carrier containing B acid, which is prepared by a preparation method comprising the following steps:
  • Example 1-1 Take 100 g of the alumina material DL1 containing B acid prepared in Example 1-1, add 3 g of turnip powder in a large crucible and carry out dry mixing for 20 minutes, so that the powder is evenly mixed, and a dry mixed sample is obtained;
  • the wet-mixed sample was extruded with a twin-screw extruder, and the final extruded sample was a clover strip carrier with an outer diameter of 1.8 mm. After drying in a blast drying oven at 120 ° C for 4 hours, the The temperature was raised to 450°C, and calcined for 4 hours to obtain a hydrogenation catalyst support containing B acid, which was designated as ZT-B2.
  • the specific surface area of the hydrogenation catalyst carrier containing B acid is 220-450m2 /g, the pore volume is 0.45-0.70mL/g, and the B/L acid value is between 0.01- Between 0.8 and 150°C, infrared acid accounts for 60-70% of the total acid, of which B acid accounts for 5-40%; at 250°C, infrared acid accounts for 20-30% of the total acid, of which B acid accounts for 4-40% %; 350 °C infrared acid accounts for 5-15% of the total acid, of which B acid accounts for 2-35%.
  • This comparative example provides a kind of W-Ni catalyst, and it is made with ZT-0 that above-mentioned preparation obtains as carrier, and its preparation method specifically comprises:
  • This comparative example provides a kind of W-Ni catalyst, and it is prepared by using ZT-B1 prepared above as a carrier, and its preparation method specifically includes:
  • This comparative example provides a kind of W-Ni catalyst, and it is prepared with the above-mentioned ZT-B2 that obtains as carrier, and its preparation method specifically comprises:
  • the W-Ni catalysts CAT-1, CAT-2, CAT-3, CAT-4, CAT-5 provided in Example 9 and the W-Ni catalysts CAT-0, CAT-B1, CAT-B1 provided in Comparative Examples 4-6
  • the relevant physical parameters of CAT-B2 are shown in Table 5.
  • the W-Ni catalyst prepared with the hydrogenation catalyst support containing B acid provided by the embodiment of the present invention as a carrier CAT-1, CAT-2, CAT-3, CAT-4, CAT-5 have higher B/L acid value; And along with the increase of the B/L value of the added B acid alumina material, the obtained
  • the strength of the W-Ni catalyst has various degrees of decline, but the strength of the W-Ni catalyst CAT-1-CAT-5 provided by the embodiments of the present invention can all meet the needs of industrial production (wherein, usually, the diesel oil used in industrial installations requires The strength of the hydrogenation catalyst is greater than 140 N/cm).
  • This embodiment provides W-Ni catalyst CAT-1, CAT-2, CAT-3, CAT-4 and the W-Ni catalyst CAT-0, CAT-B1, CAT provided in the comparative example 4-6 that the embodiment of the present invention provides
  • the catalytic performance of -B2 was evaluated, including:
  • the evaluation is a 2mL micro-reaction evaluation, the amount of catalyst used is 1g, and the n-decane solution model compound of 4,6-dibenzothiophene (DBT) and quinoline (Q) (which contains sulfur 1000mg/kg and nitrogen 500mg/kg) as the raw material, the reaction temperature is 340°C, the partial pressure of hydrogen is 6.4MPa, the volume ratio of hydrogen to oil is 500:1, and the volume space velocity is 2.0h -1 .
  • DBT 4,6-dibenzothiophene
  • Q quinoline
  • the Ni-W catalyst activity evaluation result prepared by the hydrogenation catalyst carrier containing B acid provided by the present invention shows that compared with the W-Ni catalyst CAT-0 provided by Comparative Example 4 , the W-Ni catalyst containing B acid provided by the embodiment of the present invention, that is, CAT-1, CAT-2, CAT-3, CAT-4, CAT-5 has high hydrodesulfurization and denitrogenation activities, and can realize sulfur Nitrogen was removed at the same time, and the liquid yield was not significantly affected, indicating that no obvious cracking reaction occurred during the hydrogenation reaction.
  • 4,6-DMDBT has a large steric hindrance, and it is difficult for the hydrogenation active center to contact the sulfur atom, resulting in a low reaction rate and desulfurization rate in the direct hydrodesulfurization reaction.
  • the B in the catalyst The existence of the acid center promotes the 4, 6 methyl transfer of 4,6-DMDBT and improves the direct desulfurization and isomerization-direct desulfurization reaction pathways, greatly improving the desulfurization efficiency and desulfurization activity.
  • Comparative Example 5 and Comparative Example 6 adopt two catalysts prepared by a hydrogenation catalyst carrier containing B acid (made only from alumina materials containing B acid), that is, CAT
  • CAT The desulfurization and denitrification activities of -B1 and CAT-B2 are significantly improved compared with the W-Ni catalyst CAT-0 provided in Comparative Example 4, but because the modification process causes a certain degree of loss in contrast surface and pore structure, resulting in CAT-B1 , CAT-B2 these two catalysts are not strong enough, not suitable for mass production and industrial applications.

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Abstract

一种含B酸的加氢催化剂载体及其制备与应用，含B酸的加氢催化剂载体是以商用氧化铝载体和含B酸的氧化铝材料为原料制得的，其中，以原料的总重量为100％计，其包括50-95％的商用氧化铝载体和5-50％的含B酸的氧化铝材料。通过将含B酸的氧化铝材料引入催化剂载体，制备出含有丰富B酸中心的载体材料，且以弱酸和中强酸为主。采用含B酸的加氢催化剂载体制备的Ni-W催化剂活性评价结果表明，催化剂加氢脱硫活性高，并且提高了4,6-DMDBT的直接脱硫和异构-直接脱硫反应路径，且没有明显影响液体收率，说明加氢反应过程中并未发生明显的裂化反应。

Description

一种含B酸的加氢催化剂载体及其制备与应用 技术领域
本发明涉及一种含B酸的加氢催化剂载体及其制备与应用，属于石油炼制加氢技术领域。
背景技术
随着油品质量的不断升级、环保法规的日益严格以及原油日趋劣质化、重质化，加氢技术在全世界范围内都得到广泛重视和应用。国六柴油标准的实施，柴油加氢装置苛刻度提高，装置运行周期缩短，为了不影响装置的运行周期，对催化剂活性提出更高的要求，在催化剂中引入B酸中心，改变硫化物加氢反应路径，提高加氢反应效率进而降低反应温度是解决这一问题的关键。
目前，柴油加氢精制催化剂载体一般以氧化铝为主，未经改性的氧化铝载体表面只有L酸，为了提高催化剂表面的B酸，研究者们在载体制备过程中加入F、B、Zr等元素来增加载体的B酸含量，但这些改性方法形成的B酸中心随机且酸量不可控。柴油加氢精制催化剂对载体酸强度的要求不能太强，以弱酸为主，避免加氢过程中发生裂化，影响精制柴油的收率。而对于裂化和异构类催化剂一般采用向载体中加入分子筛和无定形硅铝来调节载体的酸性和酸量，一般这类催化剂要求的酸性较强。
中国专利CN104646073A公开了一种加氢催化剂载体，按重量百分比为分子筛10-70wt％、氧化铝10-40wt％、二氧化硅5-30wt％，其余为粘结剂；加氢催化剂载体比表面积为380-573m 2/g，孔体积为0.63-0.94cc/g，红外酸量为0.10-0.45mmol/g，B酸和L酸的比值为2.3-0.9:1；分子筛为介孔无定形硅铝包覆微孔Beta分子筛的多级孔复合分子筛，氧化钠的含量≤0.05wt％，红外酸量为0.23-0.58mmol/g。
中国专利CN108262066A公开了一种加氢催化剂载体，包括固体酸组分和无定型耐热氧化物，其中，所述加氢催化剂载体的比表面积为220-430m 2/g，总孔容为0.35-0.70mL/g，红外酸量为0.50-1.0mmol/g，B酸和L酸的比值为0.2-1.0，径向抗压碎力大于130N/cm；以所述载体的总重量为基准，所述固体酸组分含量为10-80％，所述无定型耐热氧化物含量为20-90％；其中，所述固体酸组分为MCM-22分子筛，其硅铝比为10-50，比表面积为400-700m 2/g，孔容为0.35-0.75mL/g。
中国专利CN106311309A公开了一种加氢催化剂载体，包括氧化铝载体、分子筛， 所述氧化铝载体与分子筛的重量比为7:1；上述加氢催化剂载体的制备方法包括如下步骤：a、将氧化铝载体、分子筛溶于去离子水中形成混合浆料；b、混合浆料焙烧得到催化剂载体成品；所述氧化铝载体的孔容为0.2-0.5mL/g，比表面积为400-500m 2/g，孔直径为5-8nm的孔占总孔容的90％，压碎强度为300N/cm-500N/cm，红外总酸量为0.30-0.45mmol/g，中强酸量/红外总酸量为0.56-0.81，L酸量/B酸量为1.40-2.30。
中国专利CN108262076A公开了一种加氢催化剂载体，包括固体酸组分和无定型耐热氧化物，其中：所述加氢催化剂载体的比表面积220-450m 2/g，总孔容为0.35-0.70mL/g，红外酸量为0.50-1.0mmol/g，B酸和L酸的比值为0.2-1.0，径向抗压碎力大于130N/cm；以所述载体的总重量为基准，固体酸组分含量为10-80％，无定型耐热氧化物含量为20-90；其中，所述固体酸组分为MCM-22分子筛和ZSM-5分子筛的混合物，混合比例为1:10-10:1；所述MCM-22分子筛的硅铝比为10-60，比表面积为400-600m 2/g，孔容为0.35-0.75mL/g；所述ZSM-5分子筛的硅铝比为10-60，比表面积为300-500m 2/g，孔容为0.15-0.65mL/g。
中国专利CN108262074A公开了一种加氢催化剂载体，包括固体酸组分和无定型耐热氧化物，其中：所述加氢催化剂载体的比表面积为220-450m 2/g，总孔容为0.35-0.70mL/g，红外酸量为0.50-1.0mmol/g，B酸和L酸的比值为0.2-1.0，径向抗压碎力大于130N/cm；以所述载体的总重量为基准，固体酸组分含量为10-80％，无定型耐热氧化物含量为20-90％；其中，所述固体酸组分为MCM-22分子筛和Y分子筛的混合物，混合比例为1:10-10:1；所述MCM-22分子筛的硅铝比为10-60，比表面积为400-600m 2/g，孔容为0.35-0.75mL/g；所述Y分子筛的硅铝比为5-60，比表面积为500-800m 2/g，孔容为0.8-1.0mL/g，晶胞参数为2.430-2.450nm。
中国专利CN105983445A公开了一种加氢催化剂载体，其中：以含硅和磷的氧化铝为加氢催化剂载体，载体孔容为0.7-1.5mL/g，比表面积为250-450m 2/g，催化剂载体20-30nm孔比例达到20％以上，载体表面酸性质为：酸量为0.2-0.7mmol/g，B酸为0.1-0.3mmol/g。
中国专利CN103896318A公开了一种用于催化裂化催化剂的富B酸介孔氧化铝载体材料，其是以NH 4BF 4改性拟薄水铝石并添加P123模板剂制得，该材料具有介孔结构，孔容为0.32-0.41mL/g，比表面积为200-237m 2/g；该技术的缺陷或相对本发明的不足之处：该发明公开的材料孔容比表面积存在局限，且该氧化铝材料用于催化裂化。
中国专利CN112619632A公开了一种采用共沉淀法制备的硼、磷、氟、镁等元素改性氧化铝载体，该材料250-450℃红外酸酸量为0.18-0.55mmol/g，其中B酸酸量为 0.08-0.150mmol/g，L酸酸量为0.10-0.40mmol/g。
文献“富B酸氧化铝的制备及以其为载体催化剂的加氢脱硫反应性能”中用氟硼酸铵改性拟薄水铝石制备了富B酸氧化铝载体，通过调整F/Al比制备出B/L比值为0.17-1.06的氧化铝载体，用于4,6-DMDBT加氢，可提高4,6-DMDBT的直接经异构-直接脱硫路径。但该载体改性过程中明显破坏了载体比表面和孔结构，当B/L值为1.06时，比表面损失17.3％，孔容损失7.9％，这样的载体不利于活性金属分散和反应物的扩散。
综上，目前本领域于催化剂载体中引入B酸，大多数以在载体中添加各种含B酸的分子筛，但含分子筛的催化剂载体酸性强，适合制备裂化催化剂；还有在载体制备过程中引入F、B、Zr等元素，这种方法制备的载体酸性中心形成随机，酸量不可控。在提高载体B酸酸量的同时导致了载体的总酸量过大，或者提高了B酸酸量的比例但B酸酸量没有显著提高，另外，在提高载体孔径的同时导致了载体比表面积损失过大。
因此，提供一种新型的含B酸的加氢催化剂载体及其制备与应用已经成为本领域亟需解决的技术问题。
发明内容
为了解决上述的缺点和不足，本发明的一个目的在于提供一种含B酸的加氢催化剂载体。
本发明的另一个目的还在于提供以上所述含B酸的加氢催化剂载体的制备方法。
本发明的又一个目的还在于提供一种加氢精制催化剂，其载体为以上所述含B酸的加氢催化剂载体。
本发明的再一个目的还在于提供以上所述的加氢精制催化剂在石油炼制领域中加氢精制过程的应用。
为了实现以上目的，一方面，本发明提供了一种含B酸的加氢催化剂载体，其中，所述含B酸的加氢催化剂载体是以商用氧化铝载体和含B酸的氧化铝材料为原料制得的，其中，以所述原料的总重量为100％计，其包括50-95％的商用氧化铝载体和5-50％的含B酸的氧化铝材料。
作为本发明以上所述含B酸的加氢催化剂载体的一具体实施方式，其中，以所述含B酸的加氢催化剂载体的总重量为100％计，其包括60-75％的商用氧化铝载体和25-40％的含B酸的氧化铝材料。
作为本发明以上所述含B酸的加氢催化剂载体的一具体实施方式，其中，所述含B 酸的氧化铝材料的B/L酸值为0.3-2.5，比表面积为200-300m 2/g，孔容为0.55-0.90mL/g。
作为本发明以上所述含B酸的加氢催化剂载体的一具体实施方式，其中，所述含B酸的氧化铝材料的B/L酸值为0.8-1.6。
作为本发明以上所述含B酸的加氢催化剂载体的一具体实施方式，其中，所述含B酸的氧化铝材料是以普通的拟薄水铝石为原料采用溶胶凝胶法通过NH 4BF 4改性制得的，包括：
先用酸溶液将拟薄水铝石配制成均匀的铝溶胶浆液，然后于搅拌条件下将室温下NH 4BF 4饱和溶液滴加到铝溶胶浆液中并形成凝胶，再对所述凝胶进行真空干燥后焙烧，得到所述含B酸的氧化铝材料。
作为本发明以上所述含B酸的加氢催化剂载体的一具体实施方式，其中，于70-80℃的温度条件下，用酸溶液将拟薄水铝石配制成均匀的铝溶胶浆液。
作为本发明以上所述含B酸的加氢催化剂载体的一具体实施方式，其中，所述酸溶液包括无机酸溶液或有机酸溶液。在本发明的一些实施例中，所述无机酸溶液例如可以为浓硝酸。
作为本发明以上所述含B酸的加氢催化剂载体的一具体实施方式，其中，所述拟薄水铝石的比表面积为300-600m 2/g，孔容为0.40-0.70mL/g。
作为本发明以上所述含B酸的加氢催化剂载体的一具体实施方式，其中，所述NH 4BF 4饱和溶液的滴加速度为3-5mL/min。
作为本发明以上所述含B酸的加氢催化剂载体的一具体实施方式，其中，控制F/Al摩尔比为0.06-0.18。
作为本发明以上所述含B酸的加氢催化剂载体的一具体实施方式，其中，所述焙烧的温度为350-450℃，优选为400-450℃。
本发明将含B酸的氧化铝材料的制备过程中的焙烧温度控制在上述范围，可以保证含B酸的氧化铝材料表面B酸量不被破坏。
作为本发明以上所述含B酸的加氢催化剂载体的一具体实施方式，其中，所述商用氧化铝载体的比表面积为380-600m 2/g，孔容为0.40-0.60mL/g。
作为本发明以上所述含B酸的加氢催化剂载体的一具体实施方式，其中，所述含B酸的加氢催化剂载体的比表面积为220-450m 2/g，孔容为0.45-0.70mL/g；
优选地，所述比表面积为300-400m 2/g，孔容为0.50-0.60mL/g。
作为本发明以上所述含B酸的加氢催化剂载体的一具体实施方式，其中，所述含B酸的加氢催化剂载体的B/L酸值在0.01-0.8之间，150℃红外酸量占总酸量的60-70％， 其中B酸量占红外酸量的5-40％；250℃红外酸量占总酸量的20-30％，其中B酸量占红外酸量的4-40％；350℃红外酸量占总酸量的5-15％，其中B酸量占红外酸量的2-35％；
优选地，所述含B酸的加氢催化剂载体的B/L酸值在0.3-0.59之间，150℃红外酸量占总酸量的63-68％，其中B酸量占红外酸量的20-40％；250℃红外酸量占总酸量的23-28％，其中B酸量占红外酸量的20-40％；350℃红外酸量占总酸量的8-12％，其中B酸量占红外酸量的12-34％。
其中，本发明所述“红外酸量”为“B酸量”与“L酸量”之和，“总酸量”是指不同温度点的红外酸量之和，而不同温度点红外酸量与总酸量之比是指该温度点所对应的红外酸量与总酸量的比值。
另一方面，本发明还提供了以上所述含B酸的加氢催化剂载体的制备方法，其中，所述制备方法包括：
按比例将商用氧化铝载体和含B酸的氧化铝材料混合，加入田菁粉后进行干混并使粉体混合均匀，得到干混样品；
将硝酸溶液加入干混样品中进行湿混，得到湿混样品；
对所述湿混样品进行成型，再对成型后的产品进行烘干、焙烧，得到所述含B酸的加氢催化剂载体。
本发明按一定比例将商用氧化铝载体和含B酸的氧化铝材料混合制备含B酸的加氢催化剂载体，可将含B酸的氧化铝材料引入催化剂的载体中，从而实现催化剂载体上B酸酸量的可控制备。
本发明对所述含B酸的加氢催化剂载体的制备过程中的田菁粉用量、硝酸溶液的浓度以及用量、干混时间、湿混时间、成型方式、烘干以及焙烧条件等均不做具体要求，本领域技术人员可以根据实际作业需要合理设置该些参数，只要保证可以实现制备含B酸的加氢催化剂载体的目的即可。
又一方面，本发明还提供了一种加氢精制催化剂，其中，所述加氢精制催化剂的载体为以上所述含B酸的加氢催化剂载体。
作为本发明以上所述加氢精制催化剂的一具体实施方式，其中，所述加氢精制催化剂的强度>130N/cm。在本发明一些较为优选的实施例中，所述加氢精制催化剂的强度≥160N/cm。
再一方面，本发明还提供了以上所述的加氢精制催化剂在石油炼制领域中加氢精制过程的应用。
作为本发明以上所述应用的一具体实施方式，其中，所述石油炼制领域中加氢精制 过程包括汽柴油加氢精制。
本发明首先通过溶胶凝胶法合成含高B酸量的氧化铝材料，再将合适比例的含B酸的氧化铝材料与商用氧化铝载体混合制备所述含B酸的加氢催化剂载体，这种在加氢催化剂载体中引入B酸的方式使载体上B酸的酸强度和酸量都在可控范围内，载体上适宜的酸强度和酸量能够促进馏分油中带有空间位阻类难脱除的硫化物通过直接脱硫反应路径脱除，从而提高加氢脱硫反应速率，降低反应温度，同时可以促进硫、氮化物、芳烃的同步脱除。
本发明所能达成的有益技术效果包括：
(1)本发明通过将含B酸的氧化铝材料引入催化剂载体，制备出含有丰富B酸中心的载体材料，且以弱酸和中强酸为主。
(2)采用本发明提供的所述含B酸的加氢催化剂载体制备的Ni-W催化剂活性评价结果表明，该催化剂加氢脱硫活性高，并且提高了4,6-DMDBT的直接脱硫和异构-直接脱硫反应路径，且没有明显影响液体收率，说明加氢反应过程中并未发生明显的裂化反应。产生该有益效果的原因或机理为：4,6-DMDBT具有较大的空间位阻，加氢活性中心难于接触硫原子导致直接加氢脱硫反应时反应速率及脱硫率偏低，该催化剂中B酸中心的存在促进了4,6-DMDBT的4、6位甲基转移而提高了直接脱硫和异构-直接脱硫反应路径，大大提高了脱硫效率和脱硫活性。
具体实施方式
需要说明的是，本发明的说明书和权利要求书中的术语“包括”以及其任何变形，意图在于覆盖不排他的包含，例如，包含了一系列步骤或单元的过程、方法、***、产品或设备不必限于清楚地列出的那些步骤或单元，而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。
本发明所公开的“范围”以下限和上限的形式给出。可以分别为一个或多个下限，和一个或多个上限。给定的范围是通过选定一个下限和一个上限进行限定的。选定的下限和上限限定了特别范围的边界。所有以这种方式进行限定的范围是可组合的，即任何下限可以与任何上限组合形成一个范围。例如，针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是可以预料到的。此外，如果列出的最小范围值为1和2，列出的最大范围值为3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。
在本发明中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的 缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本发明中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。
在本发明中，如果没有特别的说明，本发明所提到的所有实施方式以及优选实施方式可以相互组合形成新的技术方案。
在本发明中，如果没有特别的说明，本发明所提到的所有技术特征以及优选特征可以相互组合形成新的技术方案。
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附表及实施例，对本发明进行进一步详细说明。下列所描述的实施例是本发明一部分实施例，而不是全部的实施例，仅用于说明本发明，而不应视为限制本发明的范围。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
实施例1
本实施例提供了一系列含B酸的氧化铝材料，其是通过包括如下步骤的制备方法制得：
首先将20g拟薄水铝石粉(CL0)加入到285mL去离子水中，在搅拌的同时滴加约10g浓度为68wt％(下同)的浓硝酸；然后加热至80℃，再滴加浓硝酸至完全成胶，得到均匀的铝溶胶浆液，控制铝溶胶浆液的pH值<2。
称取一定质量的NH 4BF 4，室温下配置成NH 4BF 4饱和溶液。
将不同量的NH 4BF 4饱和溶液分别倒入速控进样器中，逐渐滴入剧烈搅拌的铝溶胶浆液中，在滴加的过程中，调节滴加的速度为4mL/min，滴完以后，剧烈搅拌直至铝溶胶浆液形成凝胶，然后将此凝胶在110℃真空干燥10小时(真空度小于80mmHg)，之后在400℃焙烧4个小时，焙烧后所得的产物即为含B酸的氧化铝材料。
其中，通过对含B酸的氧化铝材料进行元素分析获得其中的F/Al摩尔比分别为0.06、0.09、0.12、0.15、0.18，相应地，将所述含B酸的氧化铝材料分别记为CL1-CL5，同时将拟薄水铝石铝空白样品记作CL0，CL0和CL1-CL5的孔结构性质及酸性见表1。
表1含B酸的氧化铝材料物性数据
Figure PCTCN2022136126-appb-000001
Figure PCTCN2022136126-appb-000002
注：表1中的比表面积(S BET)、孔容(V)及B/L酸值均是通过本领域常规方法测得的。
由以上表1可知，实施例1成功地制得了含B酸的氧化铝材料，其B/L酸值为0.3-2.5，比表面积为200-300m 2/g，孔容为0.55-0.7mL/g。
从以上表1中还可以获知，拟薄水铝石粉通过NH 4BF 4改性后B酸增加，但同时对比表面造成了一定的负面影响，随着F/Al摩尔比的增加比表面逐渐降低，孔容不断增大；但B/L比值存在拐点，当F/Al＝0.15时，B/L达到2.45，F/Al继续增加至0.18时，B/L下降至1.54。
实施例1-1
本实施例提供了一系列含B酸的氧化铝材料，其制备方法与实施例1中提供的制备方法的区别在于：本实施例通过控制NH 4BF 4饱和溶液的加入量制备F/Al＝0.15的B酸氧化铝材料；
所用的拟薄水铝石(DL0和EL0)的物性数据如下表2所示。
本实施例中所使用的不同的拟薄水铝石的物性数据以及所制备得到的F/Al＝0.15的B酸氧化铝材料的物性数据如下表2所示。
表2不同的拟薄水铝石及所得含B酸的氧化铝材料物性数据
Figure PCTCN2022136126-appb-000003
从以上表2可知，本实施例所合成的含B酸的氧化铝材料DL1和EL1的比表面积在200-300m 2/g范围内，孔容在0.7-0.9mL/g。
以下实施例中采用商用氧化铝制备了一系列含B酸的氧化铝加氢催化剂载体，其中，商用氧化铝粉的比表面积为425m 2/g，孔容为0.52mL/g。
实施例2
本实施例提供了一系列含B酸的加氢催化剂载体，其是通过包括如下步骤的制备方法制得：
取商业氧化铝95g，CL2(或CL3、CL4)材料5g，加入3g田菁粉于大坩埚中干混20min，使粉体混合均匀，得到干混样品；
将0.15g浓硝酸加入至85g去离子水中，充分溶解后，将其缓慢加入至干混样品中，进行粉体湿混20min，得到湿混样品；
用双螺杆挤条机对湿混样品进行挤出成型，最终挤出样品为外径1.8mm的三叶草条形载体，再于鼓风干燥箱中120℃烘干4h后，于马弗炉中程序升温至450℃，焙烧4h，得到含B酸的加氢催化剂载体，分别记为ZT2-1、ZT3-1、ZT4-1。
实施例3
本实施例提供了一系列含B酸的加氢催化剂载体，其是通过包括如下步骤的制备方法制得：
取商业氧化铝90g，CL2(或CL3、CL4)材料10g，加入3g田菁粉于大坩埚中干混20min，使粉体混合均匀，得到干混样品；
将0.15g浓硝酸加入至85g去离子水中，充分溶解后，将其缓慢加入至干混样品中，进行粉体湿混20min，得到湿混样品；
用双螺杆挤条机对湿混样品进行挤出成型，最终挤出样品为外径1.8mm的三叶草条形载体，再于鼓风干燥箱中120℃烘干4h后，于马弗炉中程序升温至450℃，焙烧4h，得到含B酸的加氢催化剂载体，分别记为ZT2-2、ZT3-2、ZT4-2。
实施例4
本实施例提供了一系列含B酸的加氢催化剂载体，其是通过包括如下步骤的制备方法制得：
取商业氧化铝85g，CL2(或CL3、CL4)材料15g，加入3g田菁粉于大坩埚中干混20min，使粉体混合均匀，得到干混样品；
将0.15g浓硝酸加入至85g去离子水中，充分溶解后，将其缓慢加入至干混样品中，进行粉体湿混20min，得到湿混样品；
用双螺杆挤条机对湿混样品进行挤出成型，最终挤出样品为外径1.8mm的三叶草条形载体，再于鼓风干燥箱中120℃烘干4h后，于马弗炉中程序升温至450℃，焙烧4h，得到含B酸的加氢催化剂载体，分别记为ZT2-3、ZT3-3、ZT4-3。
实施例5
本实施例提供了一系列含B酸的加氢催化剂载体，其是通过包括如下步骤的制备方 法制得：
取商业氧化铝80g，CL2(或CL3、CL4)材料20g，加入3g田菁粉于大坩埚中干混20min，使粉体混合均匀，得到干混样品；
将0.15g浓硝酸加入至85g去离子水中，充分溶解后，将其缓慢加入至干混样品中，进行粉体湿混20min，得到湿混样品；
用双螺杆挤条机对湿混样品进行挤出成型，最终挤出样品为外径1.8mm的三叶草条形载体，再于鼓风干燥箱中120℃烘干4h后，于马弗炉中程序升温至450℃，焙烧4h，得到含B酸的加氢催化剂载体，分别记为ZT2-4、ZT3-4、ZT4-4。
实施例6
本实施例提供了一系列含B酸的加氢催化剂载体，其是通过包括如下步骤的制备方法制得：
取商业氧化铝70g，CL2(或CL3、CL4)材料30g，加入3g田菁粉于大坩埚中干混20min，使粉体混合均匀，得到干混样品；
将0.15g浓硝酸加入至85g去离子水中，充分溶解后，将其缓慢加入至干混样品中，进行粉体湿混20min，得到湿混样品；
用双螺杆挤条机对湿混样品进行挤出成型，最终挤出样品为外径1.8mm的三叶草条形载体，再于鼓风干燥箱中120℃烘干4h后，于马弗炉中程序升温至450℃，焙烧4h，得到含B酸的加氢催化剂载体，分别记为ZT2-5、ZT3-5、ZT4-5。
实施例7
本实施例提供了一系列含B酸的加氢催化剂载体，其是通过包括如下步骤的制备方法制得：
取商业氧化铝60g，CL2(或CL3、CL4)材料40g，加入3g田菁粉于大坩埚中干混20min，使粉体混合均匀，得到干混样品；
将0.15g浓硝酸加入至85g去离子水中，充分溶解后，将其缓慢加入至干混样品中，进行粉体湿混20min，得到湿混样品；
用双螺杆挤条机对湿混样品进行挤出成型，最终挤出样品为外径1.8mm的三叶草条形载体，再于鼓风干燥箱中120℃烘干4h后，于马弗炉中程序升温至450℃，焙烧4h，得到含B酸的加氢催化剂载体，分别记为ZT2-6、ZT3-6、ZT4-6。
实施例8
本实施例提供了一系列含B酸的加氢催化剂载体，其是通过包括如下步骤的制备方法制得：
取商业氧化铝50g，CL2(或CL3、CL4)材料50g，加入3g田菁粉于大坩埚中干混20min，使粉体混合均匀，得到干混样品；
将0.15g浓硝酸加入至85g去离子水中，充分溶解后，将其缓慢加入至干混样品中，进行粉体湿混20min，得到湿混样品；
用双螺杆挤条机对湿混样品进行挤出成型，最终挤出样品为外径1.8mm的三叶草条形载体，再于鼓风干燥箱中120℃烘干4h后，于马弗炉中程序升温至450℃，焙烧4h，得到含B酸的加氢催化剂载体，分别记为ZT2-7、ZT3-7、ZT4-7。
对比例1
本对比例提供了一种加氢催化剂载体，其是通过包括如下步骤的制备方法制得：
取商业氧化铝(比表面积为425m 2/g，孔容为0.52mL/g)100g，加入3g田菁粉于大坩埚中进行干混20min，使粉体混合均匀，得到干混样品；
将0.15g浓硝酸加入至85g去离子水中，充分溶解后，将其缓慢加入至干混样品中，进行粉体湿混20min，得到湿混样品；
用双螺杆挤条机对湿混样品进行挤出成型，最终挤出样品为外径为1.8mm的三叶草条形载体，再于鼓风干燥箱中120℃烘干4h后，在马弗炉中程序升温至450℃，焙烧4h，得到加氢催化剂载体，记为ZT-0。
对比例2
本对比例提供了一种含B酸的加氢催化剂载体，其是通过包括如下步骤的制备方法制得：
取100g实施例1中制得的含B酸的氧化铝材料CL1，加入3g田菁粉于大坩埚中进行干混20min，使粉体混合均匀，得到干混样品；
将0.15g浓硝酸加入至80g去离子水中，充分溶解后，将其缓慢加入至干混样品中，进行粉体湿混20min，得到湿混样品；
用双螺杆挤条机对湿混样品进行挤出成型，最终挤出样品为外径为1.8mm的三叶草条形载体，再于鼓风干燥箱中120℃烘干4h后，在马弗炉中程序升温至450℃，焙烧4h，得到含B酸的加氢催化剂载体，记为ZT-B1。
对比例3
本对比例提供了一种含B酸的加氢催化剂载体，其是通过包括如下步骤的制备方法制得：
取100g的实施例1-1中制得的含B酸的氧化铝材料DL1，加入3g田菁粉于大坩埚中进行干混20min，使粉体混合均匀，得到干混样品；
将0.15g浓硝酸加入至80g去离子水中，充分溶解后，将其缓慢加入至干混样品中，进行粉体湿混20min，得到湿混样品；
用双螺杆挤条机对湿混样品进行挤出成型，最终挤出样品为外径为1.8mm的三叶草条形载体，再于鼓风干燥箱中120℃烘干4h后，在马弗炉中程序升温至450℃，焙烧4h，得到含B酸的加氢催化剂载体，记为ZT-B2。
本发明实施例2-实施例8以及对比例2-对比例3提供的含B酸的加氢催化剂载体以及对比例1提供的加氢催化剂载体的物性参数及酸分布情况见表3和表4。
表3实施例2-实施例8以及对比例2-对比例3提供的含B酸的加氢催化剂载体以及对比例1提供的加氢催化剂载体的物性参数
Figure PCTCN2022136126-appb-000004
Figure PCTCN2022136126-appb-000005
注：表3中的比表面积(S BET)、孔容(V)及B/L酸值均是通过本领域常规方法测得的。
表4实施例2-实施例8以及对比例2-对比例3提供的含B酸的加氢催化剂载体以及对比例1提供的加氢催化剂载体的酸分布情况
Figure PCTCN2022136126-appb-000006
Figure PCTCN2022136126-appb-000007
注：表4中的实验数据均是通过本领域常规方法测得的，并且表4中，某温度点的LAS酸量百分含量数据以及BAS酸量百分含量数据是基于总酸量计算得到的。
从表3和表4中可以看出，所述含B酸的加氢催化剂载体的比表面积为220-450m 2/g，孔容为0.45-0.70mL/g，B/L酸值在0.01-0.8之间，150℃红外酸量占总酸量的60-70％，其中B酸占5-40％；250℃红外酸量占总酸量的20-30％，其中B酸占4-40％；350℃红外酸量占总酸量的5-15％，其中B酸占2-35％。
从表3和表4中还可以看出，本发明实施例通过将含B酸的氧化铝材料引入催化剂载体，制备得到了含有丰富B酸中心的载体材料，且以弱酸和中强酸为主。
实施例9
本实施例提供了一系列的W-Ni催化剂，其是以上述制备得到的ZT2-3(B/L＝0.11)、ZT3-4(B/L＝0.27)、ZT3-6(B/L＝0.50)、ZT3-7(B/L＝0.59)、ZT4-7(B/L＝0.80)为载体制得的，其制备方法具体包括：
(1)取17.1g的硝酸镍和46.0g的偏钨酸铵溶于540.0g的去离子水中，配制成混合浸渍液；
(2)分别称量50g的ZT2-3(B/L＝0.11)、ZT3-4(B/L＝0.27)、ZT3-6(B/L＝0.50)、ZT3-7(B/L＝0.59)、ZT4-7(B/L＝0.80)含B酸的加氢催化剂载体，采用等体积浸渍的方法将步骤(1)配制的浸渍液加入至50g载体中，每次浸渍后所得的催化剂前驱体放入超声波振荡器中超声20分钟，然后在110℃干燥4个小时，之后在480℃，空气气氛中焙烧4个小时，制备得到W-Ni催化剂，分别命名为CAT-1、CAT-2、CAT-3、CAT-4、CAT-5。
对比例4
本对比例提供了一种W-Ni催化剂，其是以上述制备得到的ZT-0为载体制得的，其制备方法具体包括：
(1)取17.1g的硝酸镍和46.0g的偏钨酸铵溶于540.0g的去离子水中，配制成混合浸渍液；
(2)称量50g的ZT-0载体，采用等体积浸渍的方法将步骤(1)配制的浸渍液加入至50g载体中，每次浸渍后所得的催化剂前驱体放入超声波振荡器中超声20分钟，然后在110℃干燥4个小时，之后在480℃，空气气氛中焙烧4个小时，制备得到W-Ni催化剂，命名为CAT-0。
对比例5
本对比例提供了一种W-Ni催化剂，其是以上述制备得到的ZT-B1为载体制得的，其制备方法具体包括：
(1)取17.1g的硝酸镍和46.0g的偏钨酸铵溶于540.0g的去离子水中，配制成混合浸渍液；
(2)称量50g的ZT-B1载体，采用等体积浸渍的方法将步骤(1)配制的浸渍液加入至50g载体中，每次浸渍后所得的催化剂前驱体放入超声波振荡器中超声20分钟，然后在110℃干燥4个小时，之后在480℃，空气气氛中焙烧4个小时，制备得到W-Ni催化剂，命名为CAT-B1。
对比例6
本对比例提供了一种W-Ni催化剂，其是以上述制备得到的ZT-B2为载体制得的，其制备方法具体包括：
(1)取17.1g的硝酸镍和46.0g的偏钨酸铵溶于540.0g的去离子水中，配制成混合浸渍液；
(2)称量50g的ZT-B2载体，采用等体积浸渍的方法将步骤(1)配制的浸渍液加入至50g载体中，每次浸渍后所得的催化剂前驱体放入超声波振荡器中超声20分钟，然后在110℃干燥4个小时，之后在480℃，空气气氛中焙烧4个小时，制备得到W-Ni催化剂，命名为CAT-B2。
实施例9中提供的W-Ni催化剂CAT-1、CAT-2、CAT-3、CAT-4、CAT-5及对比例4-6中提供的W-Ni催化剂CAT-0、CAT-B1、CAT-B2的相关物性参数见表5。
表5W-Ni催化剂相关物性参数
Figure PCTCN2022136126-appb-000008
注：表5中的比表面积(S BET)、孔容(V)及B/L酸值均是通过本领域常规方法测得的。
从以上表5中可以看出，相较于对比例4中提供的W-Ni催化剂CAT-0，以本发明实施例提供的含B酸的加氢催化剂载体为载体制得的W-Ni催化剂CAT-1、CAT-2、CAT-3、CAT-4、CAT-5具有更高的B/L酸值；并且随着所加入的B酸氧化铝材料的B/L值的增大，所得W-Ni催化剂的强度有不同程度的下降，但本发明实施例提供的W-Ni催化剂CAT-1-CAT-5的强度均能满足工业生产需求(其中，通常情况下，工业装置要求所用柴油加氢催化剂的强度大于140N/cm)。
从以上表5中还可以看出，对比例5和对比例6分别提供的CAT-B1和CAT-B2两种催化剂的强度明显低于其他催化剂，这种强度的催化剂不能满足工业生产的需求。
催化剂评价实施例10
本实施例对本发明实施例提供的W-Ni催化剂CAT-1、CAT-2、CAT-3、CAT-4以及对比例4-6中提供的W-Ni催化剂CAT-0、CAT-B1、CAT-B2的催化性能进行评价，包括：
所述评价为2mL微反评价，使用的催化剂量为1g，以4,6-二苯并噻吩(DBT)和喹啉(Q)的正癸烷溶液模型化合物(其中含有硫1000mg/kg和氮500mg/kg)为原料，反应温度为340℃，氢分压为6.4MPa，氢油体积比为500:1，体积空速为2.0h -1。
本实施例中，催化剂的微反评价结果见表6。
表6催化剂的微反评价结果
Figure PCTCN2022136126-appb-000009
Figure PCTCN2022136126-appb-000010
从以上表6中可以看出，采用本发明提供的所述含B酸的加氢催化剂载体制备的Ni-W催化剂活性评价结果表明，与对比例4提供的W-Ni催化剂CAT-0相比，本发明实施例提供的含B酸的W-Ni催化剂，即CAT-1、CAT-2、CAT-3、CAT-4、CAT-5的加氢脱硫及脱氮的活性高，可实现硫氮的同时脱除，且没有明显影响液体收率，说明加氢反应过程中并未发生明显的裂化反应。产生该有益效果的原因或机理为：4,6-DMDBT具有较大的空间位阻，加氢活性中心难于接触硫原子导致直接加氢脱硫反应时反应速率及脱硫率偏低，该催化剂中B酸中心的存在促进了4,6-DMDBT的4、6位甲基转移而提高了直接脱硫和异构-直接脱硫反应路径，大大提高了脱硫效率和脱硫活性。
从以上表5-表6中还可以看出，对比例5和对比例6采用含B酸的加氢催化剂载体(仅以含B酸的氧化铝材料制得)制备的两种催化剂，即CAT-B1、CAT-B2的脱硫脱氮活性较对比例4所提供的W-Ni催化剂CAT-0有明显提高，但因为改性过程对比表面和孔结构造成了一定程度的损失，导致CAT-B1、CAT-B2这两种催化剂的强度不够，并不适合批量生产和工业应用。
以上所述，仅为本发明的具体实施例，不能以其限定发明实施的范围，所以其等同组件的置换，或依本发明专利保护范围所作的等同变化与修饰，都应仍属于本专利涵盖的范畴。另外，本发明中的技术特征与技术特征之间、技术特征与技术发明之间、技术发明与技术发明之间均可以自由组合使用。

Claims (12)

  1. 一种含B酸的加氢催化剂载体，其特征在于，所述含B酸的加氢催化剂载体是以商用氧化铝载体和含B酸的氧化铝材料为原料制得的，其中，以所述原料的总重量为100％计，其包括50-95％的商用氧化铝载体和5-50％的含B酸的氧化铝材料。
  2. 根据权利要求1所述的含B酸的加氢催化剂载体，其特征在于，以所述含B酸的加氢催化剂载体的总重量为100％计，其包括60-75％的商用氧化铝载体和25-40％的含B酸的氧化铝材料。
  3. 根据权利要求1所述的含B酸的加氢催化剂载体，其特征在于，所述含B酸的氧化铝材料的B/L酸值为0.3-2.5，比表面积为200-300m 2/g，孔容为0.55-0.90mL/g；
    优选地，所述含B酸的氧化铝材料的B/L酸值为0.8-1.6。
  4. 根据权利要求1-3任一项所述的含B酸的加氢催化剂载体，其特征在于，所述含B酸的氧化铝材料采用溶胶凝胶法制得，包括：
    先用酸溶液将拟薄水铝石配制成均匀的铝溶胶浆液，然后于搅拌条件下将室温下NH 4BF 4饱和溶液滴加到铝溶胶浆液中并形成凝胶，再对所述凝胶进行真空干燥后焙烧，得到所述含B酸的氧化铝材料。
  5. 根据权利要求4所述的含B酸的加氢催化剂载体，其特征在于，于70-80℃的温度条件下，用酸溶液将拟薄水铝石配制成均匀的铝溶胶浆液；
    优选地，所述酸溶液包括无机酸溶液或有机酸溶液；
    还优选地，所述拟薄水铝石的比表面积为300-600m 2/g，孔容为0.40-0.70mL/g；
    还优选地，所述NH 4BF 4饱和溶液的滴加速度为3-5mL/min；
    还优选地，控制F/Al摩尔比为0.06-0.18；
    还优选地，所述焙烧的温度为350-450℃，更优选为400-450℃。
  6. 根据权利要求1或2所述的含B酸的加氢催化剂载体，其特征在于，所述商用氧化铝载体的比表面积为380-600m 2/g，孔容为0.40-0.60mL/g。
  7. 根据权利要求1或2所述的含B酸的加氢催化剂载体，其特征在于，所述含B酸的加氢催化剂载体的比表面积为220-450m 2/g，孔容为0.45-0.70mL/g；
    优选地，所述比表面积为300-400m 2/g，孔容为0.50-0.60mL/g。
  8. 根据权利要求1或2所述的含B酸的加氢催化剂载体，其特征在于，所述含B酸的加氢催化剂载体的B/L酸值在0.01-0.8之间，150℃红外酸量占总酸量的60-70％，其中B酸量占红外酸量的5-40％；250℃红外酸量占总酸量的20-30％，其中B酸量占红外酸量的4-40％；350℃红外酸量占总酸量的5-15％，其中B酸量占红外酸量的2-35％；
    优选地，所述含B酸的加氢催化剂载体的B/L酸值在0.3-0.59之间，150℃红外酸量占总酸量的63-68％，其中B酸量占红外酸量的20-40％；250℃红外酸量占总酸量的23-28％，其中B酸量占红外酸量的20-40％；350℃红外酸量占总酸量的8-12％，其中B酸量占红外酸量的12-34％。
  9. 权利要求1-8任一项所述含B酸的加氢催化剂载体的制备方法，其特征在于，包括：
    按比例将商用氧化铝载体和含B酸的氧化铝材料混合，加入田菁粉后进行干混并使粉体混合均匀，得到干混样品；
    将硝酸溶液加入干混样品中进行湿混，得到湿混样品；
    对所述湿混样品进行成型，再对成型后的产品进行烘干、焙烧，得到所述含B酸的加氢催化剂载体。
  10. 一种加氢精制催化剂，其特征在于，所述加氢精制催化剂的载体为权利要求1-8任一项所述含B酸的加氢催化剂载体。
  11. 权利要求10所述的加氢精制催化剂在石油炼制领域中加氢精制过程的应用。
  12. 根据权利要求11所述的应用，其特征在于，所述石油炼制领域中加氢精制过程包括汽柴油加氢精制。
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