CN114453011A - Preparation method of hydrocracking catalyst, hydrocracking catalyst and application - Google Patents

Preparation method of hydrocracking catalyst, hydrocracking catalyst and application Download PDF

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CN114453011A
CN114453011A CN202011133043.9A CN202011133043A CN114453011A CN 114453011 A CN114453011 A CN 114453011A CN 202011133043 A CN202011133043 A CN 202011133043A CN 114453011 A CN114453011 A CN 114453011A
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molecular sieve
beta
sba
hydrocracking catalyst
catalyst
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CN114453011B (en
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于政敏
唐兆吉
樊宏飞
刘建锟
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
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    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • 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
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • 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
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
    • 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
    • C10G2300/70—Catalyst aspects
    • 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
    • C10G2400/02—Gasoline
    • 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
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    • 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

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Abstract

The invention discloses a preparation method of a hydrocracking catalyst, the hydrocracking catalyst and application. The preparation method of the hydrocracking catalyst comprises the following steps: (i) preparing a Beta/Al-SBA-15 composite molecular sieve; (ii) kneading and molding the Beta/Al-SBA-15 composite molecular sieve prepared in the step (i), the Y molecular sieve and alumina to obtain a carrier precursor; (iii) soaking the carrier precursor obtained in the step (ii) with a nano-silica dispersion liquid, and then drying to obtain a hydrocracking catalyst carrier; (iv) and (iv) dipping the carrier obtained in the step (iii) by using a solution containing an active metal component, and drying and roasting the carrier to obtain the hydrocracking catalyst. The hydrocracking catalyst prepared by the method is used for coal tar hydrocracking, and the cetane number and the condensation point of diesel oil can be improved to a great extent.

Description

Preparation method of hydrocracking catalyst, hydrocracking catalyst and application
Technical Field
The invention relates to a preparation method of a hydrocracking catalyst, in particular to a preparation method of a hydrocracking catalyst suitable for converting coal tar distillate into clean gasoline and diesel oil.
Background
Coal tar is an important byproduct in the coal pyrolysis and dry distillation process, is a black or blackish brown viscous liquid with pungent odor, is a complex mixture of high-aromatic hydrocarbon, and can be divided into low-temperature coal tar and high-temperature coal tar according to the coal pyrolysis and dry distillation temperature and the process method. The coal tar raw material has the characteristics of high content of heteroatoms such as sulfur, nitrogen and the like, high ash content, high content of polycyclic aromatic hydrocarbon, high content of colloid and asphaltene and the like.
The hydrogenation of coal tar is carried out under the action of catalyst at high temperature and high pressure to modify the molecular structure and remove S, N, O and other hetero atoms, so as to achieve the effects of cleanness and light weight, and obtain fraction fuels such as gasoline, diesel oil, kerosene and the like. The method can not only improve the utilization rate of non-renewable resources such as coal and reduce the waste of resources, but also provide beneficial supplement for petroleum with short supply. Coal tar contains a large amount of aromatic compounds, the nitrogen content (0.45-1.30%) and the sulfur content (0.29-0.40%) of the coal tar are high, and a large amount of SO can be generated by directly combusting the coal tarXAnd NOXAnd does not meet the exhaust emission standard, thereby causing serious environmental pollution.
The main purpose of hydro-upgrading is to further change the molecular structure of each component in the coal tar, and the product performance is fully improved. Compared with distillate oil hydrogenation, the coal tar has four high characteristics: the oxygen content is high; the content of colloid and carbon residue is high; the content of sulfur and nitrogen is high; the aromatic hydrocarbon content is high, and the developed hydrogenation reforming catalyst has the characteristic of meeting the requirement of being suitable for refining coal tar.
CN101885984A discloses a combined process for generating clean fuel oil by coal tar hydrogenation and a catalyst thereof. The active components of the hydro-upgrading catalyst in the patent are metal oxides NiO of VIII group and VIB group,MoO3、CoO、WO3The carrier is acid modified kaolin. Because the acid modified kaolin is used as the carrier, the pore volume is small and the acidity is high, the colloid and the asphaltene cannot enter the pore channel of the catalyst for the coal tar raw material with high colloid and asphaltene content, and more carbon deposit is formed on the surface of the catalyst, so that the catalyst is easy to inactivate, and the running period is short.
CN102029157A discloses a catalyst for coal tar pitch hydrocracking lightening reaction, which is prepared by taking an inorganic porous material as a carrier, selecting one of alumina, silica gel containing alumina, MCM-41 or SBA-15, loading one or two of metal elements Fe, Ni, Co and Mo of an active component on the carrier in the form of metal oxide or metal sulfide by a vacuum impregnation method, drying under normal pressure under the protection of nitrogen, and roasting. The catalyst prepared by the method has poor activity, more reaction coking, shorter service life, low yield of cracked light oil and further improved conversion rate of coal tar pitch.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a hydrocracking catalyst suitable for coal tar and a preparation method thereof. The hydrocracking catalyst prepared by the method is used for coal tar hydrocracking, and the cetane number and the condensation point of diesel oil can be improved to a great extent.
In a first aspect, the present invention provides a method for preparing a hydrocracking catalyst, comprising:
(i) preparing a Beta/Al-SBA-15 composite molecular sieve;
(ii) kneading and molding the Beta/Al-SBA-15 composite molecular sieve prepared in the step (i), the Y molecular sieve and alumina to obtain a carrier precursor;
(iii) (iii) impregnating the carrier precursor obtained in the step (ii) with a nano silicon dioxide dispersion liquid, and drying to obtain a hydrocracking catalyst carrier;
(iv) and (5) dipping the carrier obtained in the step (iii) in a solution containing an active metal component, and drying and roasting to obtain the hydrocracking catalyst.
Further, the acid amount of the medium strong acid of the Beta/Al-SBA-15 composite molecular sieve is 0.6-1.2 mL/g, preferably 0.7-1.0 mL/g; the ratio of the B acid to the L acid is less than 0.80, preferably less than 0.75, more preferably less than 0.50, still more preferably 0.22 or more, and specifically may be 0.25, 0.30, 0.35 or 0.40.
Furthermore, in the Beta/Al-SBA-15 composite molecular sieve, the mass content of alumina is 2-85%, preferably 5-82%, and more preferably 7.3-77.5%. The Beta/Al-SBA-15 composite molecular sieve has the mass content of alumina which can be adjusted within a wide range, such as 10.3%, 15.5%, 16.5%, 18.6%, 20.4%, 25.5%, 30.5%, 32.5%, 35.5%, 40.5%, 45.2%, 50.5%, 55.3%, 60.5%, 73.5%, 77.5% and the like.
In the Beta/Al-SBA-15 composite molecular sieve, the mass content of the Beta molecular sieve is 10-90%, preferably 25-85%.
Further, in the Beta/Al-SBA-15 composite molecular sieve, the mass content of alumina in the Al-SBA-15 molecular sieve is as follows: 5 to 75 percent. The mass content of alumina in the Al-SBA-15 molecular sieve can be adjusted within a wide range, and can be 8%, 10%, 15%, 18.3%, 25.0%, 28.5%, 33.1%, 54.5%, 65.5% and the like.
Further, the Beta/Al-SBA-15 composite molecular sieve has the following properties: SiO 22/Al2O3The molar ratio is 25-150, and the specific surface area is 500-950 m2Preferably 650 to 850 m/g2The total pore volume is 0.4-1.1 mL/g, preferably 0.48-0.85 mL/g.
The Beta/Al-SBA-15 composite molecular sieve has the following pore distribution: the pore volume of pores with a pore diameter of 4 to 15nm is 42 to 72%, preferably 45 to 65%, and more preferably 55 to 65% of the total pore volume.
Further, the preparation method of the Beta/Al-SBA-15 composite molecular sieve comprises the following steps: amorphous silica-alumina dry gel is used as a raw material, P123 triblock copolymer is used as a template agent to carry out first crystallization to synthesize the Al-SBA-15 molecular sieve, and then Beta molecular sieve slurry is added to carry out second crystallization to obtain the Beta/Al-SBA-15 composite molecular sieve.
Further, noneThe shaped silica-alumina dry glue has the following properties: the specific surface area is 400-650 m2Per g, preferably 450 to 600m2The pore volume is 0.52-1.8 ml/g, preferably 0.85-1.5 ml/g; the pore volume with the pore diameter of 4-15 nm accounts for 85% -95% of the total pore volume, and the pore volume larger than 15nm accounts for less than 5% of the total pore volume.
Further, in the amorphous silica-alumina dry gel, the mass content of alumina is 2-85%. The mass content of the alumina can be adjusted within a wide range, and can be, for example, 5%, 10%, 15%, 16%, 18%, 20%, 25%, 30%, 32%, 35%, 40%, 45%, 50%, 55%, 60%, 70%, 75%, and the like.
Further, the specific preparation method of the Beta/Al-SBA-15 composite molecular sieve comprises the following steps:
(1) mixing amorphous silica-alumina and deionized water, and pulping to form slurry;
(2) preparing an acidic aqueous solution containing a P123 triblock copolymer;
(3) and (2) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2), performing first crystallization, then adding Beta molecular sieve slurry, and performing second crystallization to prepare the Beta/Al-SBA-15 composite molecular sieve.
Furthermore, the Beta molecular sieve slurry can be prepared by adding water into a Beta molecular sieve for pulping, or can be crystallized Beta molecular sieve slurry, and the mass content of the Beta molecular sieve in the slurry is 20-40%.
According to the method, the amorphous silica-alumina in the step (1) is prepared by a carbonization method, and can be prepared by the following steps:
a. respectively preparing a sodium aluminate solution and a sodium silicate solution;
b. adding part or all of sodium silicate solution into sodium aluminate solution, and introducing CO2Controlling the reaction temperature of the gas to be 10-40 ℃, preferably 15-35 ℃, and controlling the pH value of the gel to be 8-11; wherein when CO is introduced2When the gas amount accounts for 40-100 percent of the total input amount, preferably 50-80 percent, adding the rest sodium silicate solution;
c. b, ventilating and stabilizing the mixture for 10-30 minutes under the temperature and pH value control of the step b;
d. c, filtering the solid-liquid mixture obtained in the step c, and washing a filter cake;
e. d, pulping the filter cake obtained in the step d, then carrying out hydrothermal cracking, filtering and drying to obtain the amorphous silica-alumina dry gel; the hydrothermal cracking conditions are as follows: cracking for 2-10 hours at 120-150 ℃ and under the steam pressure of 0.5-4.0 MPa.
Further, in the step a, the concentration of the sodium aluminate solution is 15-55 gAl2O3A further optional amount of 15 to 35gAl2O3L, the concentration of the sodium silicate solution is 50-200 gSiO2A further amount of 50 to 150g SiO2/L。
Further, in the step b, part or all of the sodium silicate solution is added, namely 5wt% -100 wt% of the total added sodium silicate solution. The CO is2The concentration of the gas is 30-60 v%. And c, ventilating and stirring in the gelling process in the step b.
Further, the specific process of step b is as follows: (1) adding all sodium silicate into sodium aluminate, and introducing CO2A gas; (2) adding part of sodium silicate into sodium aluminate, and introducing all CO2Gas, then adding the remaining sodium silicate solution to the mixture; (3) after adding part of sodium silicate to sodium aluminate, part of CO is introduced2Gas, then CO is introduced2The gas was added to the remaining sodium silicate solution.
Further, filtering the slurry obtained in the step d, washing the slurry with deionized water at the temperature of 50-95 ℃ until the slurry is nearly neutral,
and further, mixing the filter cake obtained in the step e according to a solid-liquid volume ratio of 8: 1-12: 1, adding water and pulping.
Further, the drying in the step e can be performed by a conventional method, and can be performed for 6-8 hours at 110-130 ℃.
Further, the mass ratio of the amorphous silica-alumina dry gel to water in the step (1) is 10: 90-30: 70, preferably 12: 88-25: 75.
further, the pH value of the acidic aqueous solution in the step (2) is 1-5, preferably 1.2-2.3, and the mass content of the P123 triblock copolymer in the acidic aqueous solution is 0.5-5.0%, preferably 0.8-2.8%.
Further, in step (2), the P123 triblock copolymer is added to a dilute acid (such as dilute hydrochloric acid) at a concentration of H+0.05 to 0.3mol/L, preferably 0.1 to 0.2 mol/L, and more preferably 0.13 to 0.18 mol/L; in order to sufficiently dissolve the P123 triblock copolymer, the temperature system is controlled to 10 to 60 ℃, preferably 20 to 40 ℃, and more preferably 25 to 35 ℃.
Further, in the step (3), the slurry prepared in the step (1) is mixed with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2), and the amounts of the slurry prepared in the step (1) and the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2) are such that the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 0.5:1 to 5:1, preferably 1:1 to 5:1, and more preferably 1:1 to 3: 1.
Further, the conditions of the first crystallization in the step (3) are: the crystallization temperature is 80-120 ℃, and preferably 90-110 ℃; the crystallization time is 10-35 h, preferably 16-24 h; the pH value in the crystallization process is controlled to be 2.0-5.0, preferably 3.2-4.8.
Further, the conditions of the second crystallization in the step (3) are: the crystallization temperature is 80-130 ℃, and preferably 90-120 ℃; the crystallization time is 4-20 h, preferably 10-15 h; the pH value is controlled to be 2.0-5.0, preferably 4.2-5.0 in the crystallization process.
Further, after the crystallization step of step (3), the Beta/Al-SBA-15 composite molecular sieve may be separated from the obtained mixture by any conventionally known means, such as filtration, washing, drying, etc. The filtration can adopt suction filtration. The washing can be performed by using deionized water as a washing solution. The drying can be carried out at 80-150 ℃, preferably 90-130 ℃, and the drying time is 2-12 hours, preferably 3-6 hours. The drying may be carried out at atmospheric pressure.
Further, the composite molecular sieve prepared by the above method may be calcined to remove the template agent and water and the like if necessary. The roasting can be carried out according to any mode conventionally known in the field, the roasting temperature is controlled to be 450-600 ℃, preferably 480-580 ℃, further preferably 500-560 ℃, and the roasting time is 2-10 hours, preferably 3-6 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen.
Further, the properties of the Y-type molecular sieve used in step (ii) are as follows: SiO 22/Al2O3The molar ratio is 25-150, and the specific surface area is 550-1000 m2(iv)/g, the total pore volume is 0.30-0.60 mL/g.
Further, the properties of the alumina in step (ii) are as follows: the specific surface area is 150-450 m2Preferably 230 to 340 m/g2(ii)/g; the pore volume is 0.4-1.4 mL/g, preferably 0.8-1.2 mL/g, and the average pore diameter is 8-14 nm.
Further, the molding in step (ii) can be performed by a conventional method in the art, such as extrusion molding. Conventional forming aids such as at least one of extrusion aids, peptizing acids, binders, and the like may be added during the forming process. The peptizing acid may be at least one of citric acid and nitric acid, preferably citric acid and nitric acid. The binder may be a small pore alumina. The extrusion aid can be sesbania powder and the like. After forming, drying and roasting processes are generally required. The drying and roasting can be carried out by adopting a conventional method, the drying condition can be 80-150 ℃, the drying time can be 2-12 h, the roasting condition can be 450-650 ℃, and the roasting time can be 2-10 h.
Further, in the step (iii), the mass concentration of the nano silica dispersion in the impregnation liquid is 20% to 50%, preferably 25% to 35%.
Furthermore, the dispersion liquid containing the nano silicon dioxide can adopt a commercially available nano silicon dioxide dispersion liquid, and the particle size of the nano silicon dioxide is 10-20 nanometers.
Further, in step (iii), the impregnation may be carried out by conventional impregnation means in the art, such as equal-volume impregnation, excess impregnation, stepwise impregnation, co-impregnation, etc., preferably equal-volume co-impregnation.
Further, in step (iii), the drying conditions are as follows: the drying temperature is 60-150 ℃, preferably 80-120 ℃. The drying may be performed in an oxygen-containing atmosphere, the oxygen concentration is not particularly limited, such as an air atmosphere or the like, and may be performed in an inert atmosphere, such as a nitrogen atmosphere or the like.
Further, in the step (iii), based on the weight of the hydrocracking catalyst carrier, the weight content of the Beta/Al-SBA-15 composite molecular sieve is 2% to 20%, preferably 3% to 18%, the weight content of the Y molecular sieve is 2% to 15%, preferably 5% to 12%, the weight content of the alumina is 65% to 95%, preferably 75% to 90%, and the weight content of the nano silica is 0.1% to 20%, preferably 0.5% to 18.0%, and more preferably 2% to 15%.
In step (iii), the density molar ratio of the hydroxyl on the surface of the hydrocracking catalyst carrier is 1.5-2.5, preferably 1.8-2.2.
Further, the impregnation in step (iv) may be carried out by methods conventional in the art, such as isovolumetric impregnation, supersaturated impregnation, stepwise impregnation, co-impregnation, etc., preferably isovolumetric co-impregnation.
Further, the drying conditions of step (iv) are as follows: the drying temperature is 60-220 ℃, preferably 90-180 ℃, and the drying time is 0.5-10 h, preferably 1-5 h. The roasting conditions were as follows: the roasting temperature is 350-500 ℃, preferably 380-480 ℃, and the roasting time is 0.5-10 h, preferably 1-5 h.
Further, the active metal component in step (iv) is a group VIII metal and a group VIB metal, the group VIII metal is preferably Co and/or Ni, and the group VIB metal is preferably W and/or Mo.
Further, the content of the group VIII metal calculated by oxide is 1wt% -15 wt%, preferably 4wt% -10 wt% based on the weight of the catalyst; the content of the VIB group metal calculated by oxide is 9-30 wt%, preferably 15-28 wt%, and the content of the hydrocracking catalyst carrier is 60-80 wt%, preferably 65-75 wt%.
In a second aspect the present invention provides a hydrocracking catalyst prepared by the process of the first aspect.
The hydrocracking catalyst had the following properties: the specific surface area is 120-350 m2Preferably 150 to 330 m/g2The pore volume is 0.20 to 0.60mL/g, preferably 0.2 to 0.55 mL/g.
In a third aspect, the invention provides the use of a hydrocracking catalyst prepared by the above process.
Further, the application is a hydrocracking method for converting coal tar into clean gasoline and diesel by applying the hydrocracking catalyst to a coal tar distillate oil hydrocracking process.
Further, the reaction conditions of the hydrocracking catalyst applied to hydrocracking of the coal tar distillate are as follows: the total reaction pressure is 3.0-18.0 MPa, and the liquid hourly space velocity is 0.2h-1~4.0h-1The volume ratio of hydrogen to oil is 200: 1-2000: 1, and the reaction temperature is 230-430 ℃.
Further, the properties of the coal tar are as follows: the density (20 ℃) was 1000kg/m3~1200 kg/m3The nitrogen content is 0.8-1.5 wt%, the sulfur content is 0.2-0.8 wt%, and the aromatic component and the colloid content are high.
Compared with the prior art, the hydrocracking catalyst carrier, the hydrocracking catalyst and the preparation method thereof have the following advantages:
(1) in the method, the Beta/Al-SBA-15 composite molecular sieve adopts amorphous silica-alumina dry gel as a raw material, Al is synchronously and directly introduced into a framework in a form of Si-O-Al bond and is uniformly distributed, the agglomeration of Al on the surface of the molecular sieve is avoided, the pore channel is smooth, and the reaction is favorably carried out; the synthesized Beta/Al-SBA-15 composite molecular sieve reacts in a weakly acidic environment, so that the framework structure of the Beta molecular sieve is prevented from being damaged when the Beta molecular sieve is exposed in an acidic solution for a long time, the obtained Beta/Al-SBA-15 composite molecular sieve has proper acid property and pore structure characteristics, and is matched with a specific Y molecular sieve, so that the Beta/Al-SBA-15 composite molecular sieve is particularly suitable for being used in the process of a coal tar distillate hydrocracking process.
(2) The Beta/Al-SBA-15 composite molecular sieve of the invention still shows the regularity of mesoporous structure even under the condition of very high aluminum content, and the regularity can be characterized by the pore distribution of the molecular sieve (especially the pore volume ratio of pores with the pore diameter of less than 4 nm). As a corroboration, according to the Beta/Al-SBA-15 composite molecular sieve, even if the mass percentage of alumina in the chemical composition of the molecular sieve is widely changed from 2% to 85%, the pore volume of pores with the pore diameters of 4-15 is still 42% -72%, the integrity and regularity of a mesoporous structure are maintained, which are not possessed by Beta/Al-SBA-15 composite molecular sieves manufactured in the prior art, and therefore, the pore structure of a catalyst carrier is transferred to the mesoporous direction after the Beta/Al-SBA-15 micro-mesoporous composite molecular sieve is added, and macromolecule reaction in coal tar distillate is facilitated.
(3) In the method, the carrier is modified by using nano silicon dioxide dispersion liquid, and a large number of unsaturated bonds and hydroxyl groups in different bonding states exist on the surface of the nano silicon dioxide and are loaded on a specific position on the surface of the carrier, so that the density of the hydroxyl groups on the surface of the catalyst carrier is obviously increased, and the high dispersion of active components is facilitated; the alkalescent nano silicon dioxide dispersion can adjust the acid amount on the surface of the carrier, so that the acid amount of medium and strong acid of the carrier is increased, the strong acid is reduced, the matching of the hydrogenation function and the acid function is more reasonable, the yield of diesel oil is improved, and the product performance is improved.
(4) When the catalyst prepared by the method is used in the coal tar distillate hydrocracking process, the yield of diesel oil is increased, the quality is obviously improved, and particularly, the cetane number and the condensation point of the diesel oil are improved simultaneously, so that the catalyst can meet the requirements of different conditions.
(5) The invention can also reduce the discharge of ammonia nitrogen wastewater and the consumption of hydrochloric acid in the preparation process of the composite molecular sieve in the current industrial production, shorten the process flow and reduce the production cost.
Drawings
FIG. 1 is an XRD pattern of Al-SBA-15 molecular sieve obtained in comparative example 4 of the present invention.
Detailed Description
In the present invention, the Al-SBA-15 molecular sieve means that aluminum atoms are introduced into the SBA-15 molecular sieve, the existence state of the aluminum atoms in the SBA-15 molecular sieve is not particularly limited, and a part of the aluminum atoms are generally distributed on the framework of the SBA-15 molecular sieve.
In the invention, the L acid or the B acid is measured by adopting an infrared spectroscopy, an instrument adopts an American Nicot Fourier infrared spectrometer-6700, and the measuring method comprises the following steps: weighing 20mg of sample with granularity less than 200 meshes, pressing into sheet with diameter of 20mm, placing on sample rack of absorption cell, placing 200mg of sample in cup of instrument, connecting absorption cell and adsorption tube, vacuumizing and cracking to vacuum degree of 4 × 10-2And Pa, heating to 500 ℃, keeping for 1 hour to remove adsorbates on the surface of the sample, cooling to room temperature, adsorbing pyridine to saturation, continuously heating to 160 ℃, balancing for 1 hour, and desorbing the physically adsorbed pyridine to obtain the acid quantities of infrared total acid, B acid and L acid, wherein the acid quantity unit of the B acid and the L acid is mmol/L.
In the invention, NH is adopted as the medium strong acid3TPD method, the apparatus is Auto-Chem II 2920 chemical adsorption apparatus of Mike instruments. Ammonia gas is used as an adsorption and desorption medium, helium gas is used as carrier gas, and the acid quantities of different desorption temperature areas are obtained by adopting temperature programming desorption and chromatographic analysis, wherein the ammonia gas desorption temperature corresponding to the acid quantity of the medium-strong acid is 250-400 ℃, and the acid quantity unit is as follows: mL/g is the amount of ammonia adsorbed per gram of molecular sieve.
In the invention, the specific surface area, the pore volume and the pore distribution are measured by adopting an ASAP2405 physical adsorption instrument, and the measuring method is as follows: after cracking the sample, liquid N2Used as adsorbate, the adsorption temperature is-196 ℃, and analysis and test are carried out. Wherein the specific surface area is calculated by a BET method, and the pore volume and the pore distribution are calculated by a BJH method.
The method for measuring the surface hydroxyl density of the catalyst carrier comprises the following steps: first, 0.5g of a sample of the catalyst support is weighed and ground to a particle size of less than 1 micron for use. Then weighing 10mg of sample, tabletting, placing the sample in an in-situ cell of an in-situ infrared spectrometer under the vacuum degree of 10-3Heating the sample in the in-situ cell under the condition of Pa, wherein the heating rate is 10 ℃/min, heating to 500 ℃, keeping the temperature for 2h, and then placing the sample in a vacuum stripAnd cooling to room temperature. Collecting a spectrum by using an in-situ infrared spectrometer, wherein the peak position of the surface hydroxyl peak of the sample is 3600-3850 cm-1The catalyst prepared by the invention and SB powder imported from Germany (the pore volume is 0.5 mL/g) are respectively used for measuring the area of the surface hydroxyl peak under the same condition, and the ratio of the peak areas of the two graphs is the surface hydroxyl density molar ratio of the two samples.
In the present invention, XRD was measured using an X-ray diffractometer model D/max2500 manufactured by Japan science, under the following test conditions: the voltage is 40KV, the current is 80mA, a CuK alpha target is selected, and the incident wavelength is 0.15405 nm.
The effects and effects of the technical solutions of the present invention are further described below by way of examples and comparative examples, but the present invention should not be construed as being limited to these specific examples, and the following examples and comparative examples of the present invention are given as mass percentages unless otherwise specified.
Example 1
(i) Preparation of Beta/Al-SBA-15 composite molecular sieve
(1) Preparation of amorphous silica-alumina dry gel powder A1 and slurry: sodium aluminate solution concentration 15gAl2O3Per L, sodium silicate solution concentration 82SiO2Putting 0.85L of sodium aluminate solution into a gelling tank, adding 0.30L of sodium silicate solution, controlling the reaction temperature to be 20 ℃, and introducing 35 v% CO2Gas, introduction of CO2When the gas accounts for 65 percent of the total input amount, 0.30L of sodium silicate solution is added while introducing gas, the pH value of the formed gel is controlled to be 9.5, then the ventilation is stabilized for 20 minutes, the slurry is filtered and washed to be neutral by deionized water at 65 ℃, a filter cake is added with water according to the solid-liquid volume ratio of 10: 1 for pulping, the obtained product is cracked for 3 hours under the water vapor pressure of 130 ℃ and 3.5MPa, and after the obtained product is dried for 6 hours at 120 ℃, the obtained product is crushed and sieved to obtain an amorphous silica-alumina product A1. The properties of the amorphous silica-alumina dry gel powder A1 are shown in Table 1. Mixing the prepared amorphous silica-alumina A1 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica-alumina dry gel to water is 21: 79;
(2) preparing an acidic aqueous solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into dilute hydrochloric acid, wherein the concentration of a dilute hydrochloric acid solution is 0.12mol/L, the pH value of an acidic aqueous solution containing the P123 triblock copolymer is 1.6, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 26 ℃, and the mass content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 1.8 wt%;
(3) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2); the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 1.2:1, the crystallization temperature is 102 ℃, and the crystallization time is 18 hours; the pH value is controlled to be 3.3 in the crystallization process,
(4) slurry containing 36.5Beta molecular sieve (wherein the Beta molecular sieve has the following properties: specific surface area 793 m)2Per g, pore volume 0.52 mL. g-1，SiO2/Al2O3The mole ratio is 65, the Beta molecular sieve slurry is prepared by pulping the Beta molecular sieve and water), pumping the slurry into the mixed system prepared in the step (3) by using a vacuum pump, drying the slurry for 3h at 100 ℃ after the crystallization time is 12h at the pH value of 4.3 and the temperature of 95 ℃, and roasting the slurry for 3h at the temperature of 550 ℃ to obtain the finished product of BetaAS-1. The properties are shown in Table 2.
(ii) Preparation of the support
Weighing alumina dry glue powder (the specific surface area is 308 m)280g of beta-zeolite/g, the pore volume of 0.81mL/g, the average pore diameter of 8.8nm, 15g of BetaAS-1 composite molecular sieve and Y molecular Sieve (SiO)2/Al2O3The molar ratio is 30, the specific surface area is 650m25g of sesbania powder and 4g of sesbania powder, adding 120mL of aqueous solution containing nitric acid and citric acid (the amount of the nitric acid is 12.6g and the amount of the citric acid is 4.5g), kneading, rolling, extruding into strips, drying at 120 ℃ for 3 hours, and roasting at 550 ℃ for 4 hours to obtain a carrier precursor Z0.
Impregnating a carrier precursor with an impregnating solution (product property: transparent liquid, silicon dioxide mass concentration of 30% and particle size of 10nm) containing nano silicon dioxide dispersion, wherein the nano silicon dioxide dispersion is 5% of the carrier weight, the pH value is 8.0, and then drying at 120 ℃ for 2 hours to obtain the hydrocracking catalyst carrier, the number of which is Z1. The molar ratio of the surface hydroxyl group density of the carrier is shown in Table 3.
(iii) Preparation of the catalyst
Soaking the Z1 in W, Ni-containing soaking solution in the same volume, drying at 130 ℃ for 2h, and roasting at 430 ℃ for 3h to finally obtain the catalyst C-1. The catalyst composition and properties are shown in table 3.
The catalyst C-1 is subjected to a catalyst activity evaluation experiment, and specifically comprises the following steps: the catalyst was presulfided prior to evaluation, on a 200mL small scale hydrogenation unit. The properties of the raw oil used are shown in Table 4. The activity evaluation conditions were as follows: the total reaction pressure is 14.5MPa, and the liquid hourly space velocity is 0.5h-1Hydrogen-oil volume ratio 1500: 1, the reaction temperature is 382 ℃. The results of the catalyst activity tests are shown in Table 5.
Example 2
(i) Preparation of Beta/Al-SBA-15 composite molecular sieve
(1) Preparation of amorphous silica-alumina dry gel powder A2 and slurry: sodium aluminate solution concentration 35gAl2O3Per L, sodium silicate solution concentration 125gSiO2Putting 0.85L of sodium aluminate solution into a gelling tank, adding 0.2L of sodium silicate solution, controlling the reaction temperature to be 22 ℃, and introducing 48 v% CO2Gas, introduction of CO2When the gas accounts for 55 percent of the total input amount, 0.25L of sodium silicate solution is added while introducing gas, the pH value of the formed gel is controlled to be 9.8, then the ventilation and the stabilization are carried out for 20 minutes, the slurry is filtered and washed to be neutral by deionized water at 75 ℃, a filter cake is added with water according to the solid-liquid volume ratio of 8:1 for pulping, the obtained product is cracked for 3 hours under the water vapor pressure of 110 ℃ and 3.0MPa, and after the obtained product is dried for 8 hours at 120 ℃, the obtained product is crushed and sieved to obtain an amorphous silica-alumina product A2, and the properties of the amorphous silica-alumina dry gel powder A2 are shown in Table 1. Mixing the prepared amorphous silica-alumina A2 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica-alumina dry gel to water is 23: 77;
(2) preparing an acidic aqueous solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into dilute hydrochloric acid, wherein the concentration of a dilute hydrochloric acid solution is 0.15mol/L, the pH value of an acidic aqueous solution containing the P123 triblock copolymer is 1.2, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 28 ℃, and the mass content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 2.5 wt%;
(3) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2); the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 1.5:1, the crystallization temperature is 95 ℃, and the crystallization time is 18 hours; the pH value is controlled to be 3.6 in the crystallization process,
(4) a slurry containing 31.4g of Beta molecular sieve (wherein the Beta molecular sieve has the following properties: specific surface area 821 m)2Per g, pore volume 0.56 mL. g-1，SiO2/Al2O3The mole ratio is 55, the Beta molecular sieve slurry is prepared by pulping the Beta molecular sieve and water) and is pumped into the mixed system prepared in the step (3) by a vacuum pump, and after the crystallization time is 13h at the pH value of 2.8 and the temperature of 115 ℃, the Beta molecular sieve slurry is dried for 4h at the temperature of 110 ℃ and roasted for 3h at the temperature of 530 ℃ to obtain the finished product of the Beta AS-2. The properties are shown in Table 2.
(ii) Preparation of the support
Weighing alumina dry glue powder (the specific surface area is 328 m)276g of BetaAS-2 composite molecular sieve, 16g of Y molecular Sieve (SiO), wherein the pore volume is 1.2mL/g, the average pore diameter is 8.8nm2/Al2O3The molar ratio is 35, the specific surface area is 660m2And/g, the total pore volume is 0.50 mL/g), 12g of sesbania powder is 4g, 120mL of aqueous solution containing nitric acid and citric acid is added (the amount of the nitric acid is 12.6g, and the amount of the citric acid is 4.5g), and the carrier precursor is obtained by extrusion molding after kneading and rolling, drying at 120 ℃ for 3 hours and roasting at 550 ℃ for 4 hours.
Impregnating a carrier precursor with an impregnating solution (product property: transparent liquid, silicon dioxide mass concentration of 30% and particle size of 15 nm) containing nano silicon dioxide dispersion liquid, wherein the dosage of the nano silicon dioxide dispersion liquid is 8% of the weight of the carrier, the pH value is 8.2, and then drying for 4 hours at 100 ℃ to obtain the hydrocracking catalyst carrier, the number of which is Z2. The molar ratio of the surface hydroxyl density of the carrier is shown in Table 3.
(iii) Preparation of the catalyst
The catalyst was prepared as in example 1 except that the support Z1 was replaced by support Z2 to give a hydrocracking catalyst, numbered C-2. The catalyst composition and properties are shown in table 3.
Catalyst C-2 was subjected to a catalyst activity evaluation test in the same manner as in example 1. The properties of the crude oil used are shown in Table 4. The results of the catalyst activity tests are shown in Table 5.
Example 3
(i) Preparation of Beta/Al-SBA-15 composite molecular sieve
(1) Preparation of amorphous silica-alumina dry gel powder A3 and slurry: sodium aluminate solution concentration 22gAl2O3Per L, sodium silicate working solution concentration 80gSiO2L, putting 1.08L of sodium aluminate solution into a gel forming tank, then adding 0.25L of sodium silicate solution, controlling the reaction temperature to be 32 ℃, and introducing 55 v% CO2Stopping gas when the pH value reaches 9.8, then ventilating and stabilizing for 20 minutes, washing to be neutral, adding water into a filter cake according to the solid-liquid volume ratio of 8:1 for pulping, cracking for 2.5 hours at the temperature of 130 ℃ under the water vapor pressure of 3.9MPa, drying for 8 hours at the temperature of 120 ℃, crushing and sieving to obtain an amorphous silica-alumina product A3. The properties of the amorphous silica-alumina dry gel powder A3 are shown in Table 1. Mixing the prepared amorphous silica-alumina A3 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica-alumina dry gel to water is 18: 82;
(2) preparing an acidic aqueous solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into dilute hydrochloric acid, wherein the concentration of a dilute hydrochloric acid solution is 0.17mol/L, the pH value of an acidic aqueous solution containing the P123 triblock copolymer is 1.8, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 33 ℃, and the mass content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 2.1 wt%;
(3) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2); the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 1.8:1, the crystallization temperature is 98 ℃, and the crystallization time is 12 hours; controlling the pH value to be 3.6 in the crystallization process;
(4) a slurry containing 35.9g of Beta molecular sieve (wherein the Beta molecular sieve has the following properties: specific surface area 778m2Per g, pore volume 0.53 mL. g-1，SiO2/Al2O3The mole ratio is 62, the Beta molecular sieve slurry is prepared by pulping the Beta molecular sieve and water) and pumping into the mixed system prepared in the step (3) by a vacuum pump, drying for 4h at 110 ℃ and roasting for 3h at 540 ℃ after the pH value is 4.5 and the temperature is 95 ℃ and the crystallization time is 10h, thus obtaining the finished product of the Beta AS-3. The properties are shown in Table 2.
(ii) Preparation of the support
Weighing alumina dry glue powder (specific surface area is 338 m)280g of BetaAS-3 composite molecular sieve, 12g of Y molecular Sieve (SiO), wherein the pore volume is 1.1mL/g, the average pore diameter is 10nm2/Al2O3The molar ratio is 40, the specific surface area is 680m28 g/g, the total pore volume is 0.50 mL/g), 4g of sesbania powder, 120mL of aqueous solution containing nitric acid and citric acid (the amount of the nitric acid is 12.6g, and the amount of the citric acid is 4.5g) is added, and the carrier precursor is obtained by extrusion molding after kneading and rolling, drying at 120 ℃ for 3 hours, and roasting at 550 ℃ for 4 hours.
Impregnating a carrier precursor with an impregnating solution (product property: transparent liquid, silicon dioxide mass concentration of 35% and particle size of 10nm) containing nano silicon dioxide dispersion liquid, wherein the dosage of the nano silicon dioxide dispersion liquid is 10% of the weight of the carrier, the pH value is 8.2, and then drying for 4 hours at 90 ℃ to obtain the hydrocracking catalyst carrier, the number of which is Z3. The molar ratio of the surface hydroxyl group density of the carrier is shown in Table 3.
(iii) Preparation of the catalyst
The catalyst was prepared as in example 1 except that the support Z1 was replaced with the support Z3 to give a hydrocracking catalyst, numbered C-3. The catalyst composition and properties are shown in table 3.
Catalyst C-3 was subjected to a catalyst activity evaluation test in the same manner as in example 1. The properties of the raw oil used are shown in Table 4. The results of the catalyst activity tests are shown in Table 5.
Example 4
(i) Preparation of Beta/Al-SBA-15 composite molecular sieve
(1) Preparation of amorphous silica-alumina dry gel powder A4 and slurry: sodium aluminate solution concentration 22gAl2O3Per L, sodium silicate solution concentration 55gSiO2Taking 0.60L of sodium aluminatePlacing the solution in a gel forming tank, adding 0.15L sodium silicate solution, controlling the reaction temperature at 35 ℃, and introducing 52 v% CO2Stopping gas when the pH value reaches 9.5, then ventilating and stabilizing for 20 minutes, washing to be neutral, adding water into a filter cake according to the solid-liquid volume ratio of 8:1 for pulping, cracking for 2.5 hours at 130 ℃ under the water vapor pressure of 3.2MPa, drying for 8 hours at 120 ℃, crushing and sieving to obtain an amorphous silica-alumina product A4. The properties of the amorphous silica-alumina dry gel powder A4 are shown in Table 1. Mixing the prepared amorphous silica-alumina A4 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica-alumina dry gel to water is 24: 76;
(2) preparing an acidic aqueous solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into diluted hydrochloric acid, wherein the concentration of a diluted hydrochloric acid solution is 0.16mol/L, the pH value of an acidic aqueous solution containing the P123 triblock copolymer is 1.8, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 33 ℃, and the mass content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 1.9 wt%;
(3) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2); the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 1.7:1, the crystallization temperature is 98 ℃, and the crystallization time is 13 hours; controlling the pH value to be 3.5 in the crystallization process;
(4) slurry containing 20g of Beta molecular sieve (wherein the Beta molecular sieve has the following properties: specific surface area 769 m2Per g, pore volume 0.55 mL. g-1，SiO2/Al2O3The mole ratio is 68, the Beta molecular sieve slurry is prepared by pulping a Beta molecular sieve and water), the slurry is pumped into the mixed system prepared in the step (3) by a vacuum pump, and after the crystallization time is 13 hours at the pH value of 4.7 and the temperature of 98 ℃, the product is dried for 4 hours at the temperature of 110 ℃ and roasted for 4 hours at the temperature of 550 ℃ to obtain the finished product BetaAS-4. The properties are shown in Table 2.
(ii) Preparation of the support
Weighing alumina dry glue powder (the specific surface area is 328 m)276g of BetaAS-4 composite molecular sieve, 14g of BetaAS-4 composite molecular sieve and (Y) molecular sieveSiO2/Al2O3The molar ratio is 38, the specific surface area is 650m210g of sesbania powder and 4g of sesbania powder, adding 120mL of aqueous solution containing nitric acid and citric acid (the amount of the nitric acid is 12.6g and the amount of the citric acid is 4.5g), kneading, rolling, extruding into strips, drying at 120 ℃ for 3 hours, and roasting at 550 ℃ for 4 hours to obtain the carrier precursor.
Impregnating a carrier precursor with an impregnating solution (product property: transparent liquid, silicon dioxide mass concentration of 30% and particle size of 10nm) containing nano silicon dioxide dispersion, wherein the nano silicon dioxide dispersion is 12% of the carrier weight, the pH value is 8.0, and then drying at 110 ℃ for 5 hours to obtain the hydrocracking catalyst carrier, the number of which is Z4. The molar ratio of the surface hydroxyl group density of the carrier is shown in Table 3.
(iii) Preparation of the catalyst
The catalyst was prepared as in example 1 except that the support Z1 was replaced with the support Z4 to give a hydrocracking catalyst, numbered C-4. The catalyst composition and properties are shown in table 3.
Catalyst C-4 was subjected to a catalyst activity evaluation test in the same manner as in example 1. The properties of the raw oil used are shown in Table 4. The results of the catalyst activity tests are shown in Table 5.
Comparative example 1
(i) Preparation of Beta/Al-SBA-15 composite molecular sieve
Respectively weighing template agent triblock copolymer P123 and silicon source tetraethoxysilane, wherein the mass of the template agent P123 is 5.5g, and the mass of tetraethoxysilane is 10.2 g; adding a template agent and a silicon source into an HCl solution with the pH value of 2.8, and fully stirring for 30 hours at the temperature of 28 ℃; standing and crystallizing the stirred mixture for 20h at 120 ℃, washing with deionized water, and drying to obtain SBA-15. Pulping the obtained SBA-15 molecular sieve with a solid-to-liquid ratio of 1:10, adding the obtained SBA-15 molecular sieve into hydrochloric acid solution containing 23g of aluminum isopropoxide, heating to 100 ℃, stirring for 20 hours, and cooling to room temperature to obtain a mixed system E.
Pumping slurry containing 34.3g of beta molecular sieve (same as example 1) into a mixed system of the mixed solution F by a vacuum pump, drying at 110 ℃ for 4h after crystallization time of 12h at the pH value of 3.5 and the temperature of 110 ℃, and roasting at 550 ℃ for 4h to obtain the finished product BetaAS-5. The properties are shown in Table 2.
(ii) Preparation of the support
The preparation method of the carrier precursor is the same as that of example 1, except that the BetaAS-1 composite molecular sieve is replaced by the BetaAS-5 composite molecular sieve.
Impregnating a carrier precursor with an impregnating solution (same as example 1) containing nano-silica dispersion, wherein the dosage of the nano-silica dispersion is 2% of the weight of the carrier, the pH value is 8.4, and then drying for 4 hours at 100 ℃ to obtain the hydrocracking catalyst carrier, the number of which is Z5. The molar ratio of the surface hydroxyl group density of the carrier is shown in Table 3.
(iii) Preparation of the catalyst
The catalyst was prepared as in example 1 except that the support Z1 was replaced with the support Z5 to give a hydrocracking catalyst, numbered C-5. The catalyst composition and properties are shown in table 3.
Catalyst C-5 was subjected to a catalyst activity evaluation test in the same manner as in example 1. The properties of the raw oil used are shown in Table 4. The results of the catalyst activity tests are shown in Table 5.
Comparative example 2
(i) Preparation of Beta/Al-SBA-15 composite molecular sieve
Adding 5g of P123 into 2mol/L125mL hydrochloric acid solution, and stirring at 40 ℃ until the P123 is completely dissolved; adding 8.5g of tetraethoxysilane into hydrochloric acid solution containing P123, stirring for 4 hours, adding aluminum nitrate to enable the molar ratio of silicon to aluminum to be 35, continuing to stir for 20 hours, adding the solution into a 250mL reaction kettle, stirring for 48 hours at 100 ℃, cooling to room temperature, adjusting the pH value to 7.5 by using 4mol of ammonia water solution, continuously stirring, heating to 100 ℃, stirring for 72 hours, and cooling to 40 ℃ to obtain solution A for later use.
Pumping slurry containing 34.3g of beta molecular sieve (same as example 1) into a mixed system of A by a vacuum pump, drying at 110 ℃ for 4h after crystallization time of 13h at the pH value of 3.4 and the temperature of 100 ℃, and roasting at 550 ℃ for 4h to obtain a finished product of BetaAS-6. The properties are shown in Table 2.
(ii) Preparation of the support
The preparation method of the carrier precursor is the same as that of example 1, except that the BetaAS-1 composite molecular sieve is replaced by the BetaAS-6 composite molecular sieve.
Impregnating a carrier precursor with an impregnation solution (same as example 1) containing nano-silica dispersion liquid, wherein the dosage of the nano-silica dispersion liquid is 3% of the weight of the carrier, the pH value is 8.0, and drying at 100 ℃ for 4 hours to obtain the hydrocracking catalyst carrier, wherein the number of the hydrocracking catalyst carrier is Z6. The molar ratio of the surface hydroxyl group density of the carrier is shown in Table 3.
(iii) Preparation of the catalyst
The catalyst was prepared as in example 1 except that the support Z1 was replaced with the support Z6 to give a hydrocracking catalyst, numbered C-6. The catalyst composition and properties are shown in table 3.
Catalyst C-6 was subjected to a catalyst activity evaluation test in the same manner as in example 1. The properties of the raw oil used are shown in Table 4. The results of the catalyst activity tests are shown in Table 5.
Comparative example 3
(i) Preparation of the support
18 g of Y molecular Sieve (SiO)2/Al2O3The molar ratio is 30, the specific surface area is 650m2Per g, total pore volume of 0.48mL/g), 12g beta molecular Sieve (SiO)2/Al2O3The molar ratio is 45, the specific surface area is 630m2G, total pore volume of 0.50mL/g, 130 g of macroporous alumina (pore volume 0.9mLg, specific surface area 355m2And/g), 4g of microcrystalline cellulose, and a mixed acidic aqueous solution containing 4g of guar gum and dilute nitric acid (wherein the concentration of the nitric acid is 3.0%) are placed into a rolling machine for mixing and rolling, the mixture is rolled into paste, extruded strips are dried for 4 hours at 120 ℃, and then the extruded strips are roasted for 4 hours at 500 ℃, so that the carrier Z7 is obtained. The molar ratio of the surface hydroxyl group density of the carrier is shown in Table 3.
(ii) Preparation of the catalyst
Soaking the Z7 in W, Ni-containing soaking solution in the same volume, drying at 130 ℃ for 2h, and roasting at 450 ℃ for 3h to finally obtain the catalyst C-7. The catalyst composition and properties are shown in table 3.
Catalyst C-7 was subjected to a catalyst activity evaluation test in the same manner as in example 1. The properties of the raw oil used are shown in Table 4. The results of the catalyst activity tests are shown in Table 5.
Comparative example 4
This comparative example illustrates that the composite molecular sieve prepared in example 1 is a Beta/Al-SBA-15 composite molecular sieve, and compared to example 1, the Al-SBA-15 molecular sieve is synthesized directly without adding Beta molecular sieve slurry, specifically as follows:
(1) preparation of amorphous silica-alumina dry gel powder A1 and slurry: sodium aluminate solution concentration 15gAl2O3Per L, sodium silicate solution concentration 82SiO2Putting 0.85L of sodium aluminate solution into a gelling tank, adding 0.30L of sodium silicate solution, controlling the reaction temperature to be 20 ℃, and introducing 35 v% CO2Gas, introduction of CO2When the gas accounts for 65 percent of the total input amount, 0.30L of sodium silicate solution is added while introducing gas, the pH value of the formed gel is controlled to be 9.5, then the ventilation is stabilized for 20 minutes, the slurry is filtered and washed to be neutral by deionized water at 65 ℃, a filter cake is added with water according to the solid-liquid volume ratio of 10: 1 for pulping, the obtained product is cracked for 3 hours under the water vapor pressure of 130 ℃ and 3.5MPa, and after the obtained product is dried for 6 hours at 120 ℃, the obtained product is crushed and sieved to obtain an amorphous silica-alumina product A1. The properties of the amorphous silica-alumina dry gel powder A1 are shown in Table 1. Mixing the prepared amorphous silicon aluminum A1 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica-alumina dry gel to water is 21: 79;
(2) preparing an acidic aqueous solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into dilute hydrochloric acid, wherein the concentration of a dilute hydrochloric acid solution is 0.12mol/L, the pH value of an acidic aqueous solution containing the P123 triblock copolymer is 1.6, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 26 ℃, and the mass content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 1.8 wt%;
(3) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2); the Al-SBA-15 molecular sieve is prepared after crystallization, filtration, drying and roasting, and the serial number is A-S-1. The mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 1.2:1, the crystallization temperature is 102 ℃, and the crystallization time is 18 hours; and controlling the pH value to be 3.3 in the crystallization process, drying at 100 ℃ for 3h, and roasting at 550 ℃ for 3h to obtain the finished product Al-SBA-15 molecular sieve. The XRD pattern of the A-S-1 molecular sieve obtained in comparative example 4 is shown in FIG. 1, which shows the characteristic peak of Al-SBA-15 molecular sieve.
The Beta/Al-SBA-15 composite molecular sieves prepared in the examples 1-4 of the invention all contain XRD patterns similar to those of the comparative example 4, which shows that the composite molecular sieves prepared in the examples 1-4 are the Beta/Al-SBA-15 composite molecular sieves.
TABLE 1 Properties of amorphous silica-alumina
Item A1 A2 A3 A4
Specific surface area, m2/g 485 516 508 520
Pore volume, ml/g 1.31 1.28 1.33 1.30
Hole distribution,%
4～15nm 91 86.5 88.3 91.2
＞15nm 2.5 4.3 2.8 4.1
TABLE 2 Properties of the composite molecular sieve obtained in examples and comparative examples
Item BetaAS-1 BetaAS-2 BetaAS-3 BetaAS-4 BetaAS-5 BetaAS-6
Alumina content, wt% 23.53 37.59 56.97 63.98 19.80 15.55
The alumina content in the Al-SBA-15 molecular sieve is wt% 20.98 34.59 54.30 61.54 17.25 13.0
Specific surface area, m2/g 758 764 775 769 712 719
Pore volume, mL/g 0.58 0.63 0.59 0.65 0.48 0.45
Relative degree of crystallinity after calcination at 900 ℃% 98 98 97 99 88 85
Acid amount of medium strong acid, mL/g 0.71 0.72 0.75 0.76 0.52 0.48
B/L 0.226 0.228 0.234 0.255 1.05 1.25
Hole distribution,%
4～15nm 55.38 56.35 64.88 56.65 30.47 35.32
＞15nm 4.92 4.85 4.33 3.56 11.34 14.03
TABLE 3 composition and physico-chemical Properties of the catalysts
Item C-1 C-2 C-3 C-4 C-5 C-6 C-7
Specific surface area, m2/g 324 325 321 335 232 245 220
Pore volume, mL/g 0.43 0.44 0.42 0.43 0.32 0.33 0.31
WO3，wt% 23.1 23.6 22.9 23.3 22.8 23.2 23.5
NiO，wt% 5.94 5.92 5.91 5.96 5.87 5.83 5.78
Catalyst carrier surface hydroxyl density molar ratio 1.62 1.65 1.68 1.73 1.41 1.43 0.81
W/Al 0.18 0.19 0.18 0.17 0.12 0.11 0.08
Ni/Al 0.07 0.08 0.08 0.09 0.03 0.04 0.03
TABLE 4 Properties of the feed oils
Analysis item Coal tar
Density (20 ℃), kg/m3 1120
Nitrogen, μ g-g 12600
Distillation range/. degree.C
IBP/10%/30%/50% 170/230/305/340
70%/90%/95%/EBP 370/415/435/466
Saturation fraction 0.6
Aromatic component 67
Glue 32.2
Asphaltenes 0.2
Water content% 1.86
Residual carbon content% 0 .83
Flash point (closed mouth), deg.C 98
Ni，μg/g 0.025
V ，μg/g 0
Fe ，μg/g 1.488
Na ，μg/g 0
TABLE 5 catalyst evaluation results
Item C-1 C-2 C-3 C-4 C-5 C-6 C-7
Heavy naphtha
Yield, wt.% 12.2 11.8 13.3 12.5 14.3 15.5 19.2
Sulfur,. mu.g/g 7.5 8.2 7.6 8.3 20 16 14
Diesel oil
Yield, wt.% 73.3 76.5 77.8 75.6 52.5 60.2 60.8
Aromatic hydrocarbons, wt.% 27.5 28.6 28.2 29.3 38.6 33.3 42.3
Cetane number 60 63 65 67 48 47 43
Freezing point, deg.C -31 -30 -29 -32 -14 -16 -13
As is clear from the evaluation results in table 5, the coal tar hydrocracking catalyst of the present invention has better selectivity and better product properties than the catalyst of the comparative example.

Claims (16)

1. A preparation method of a hydrocracking catalyst is characterized by comprising the following steps: the method comprises the following steps:
(i) preparing a Beta/Al-SBA-15 composite molecular sieve;
(ii) kneading and molding the Beta/Al-SBA-15 composite molecular sieve prepared in the step (i), the Y molecular sieve and alumina to obtain a carrier precursor;
(iii) (iii) impregnating the carrier precursor obtained in the step (ii) with a nano silicon dioxide dispersion liquid, and drying to obtain a hydrocracking catalyst carrier;
(iv) and (5) dipping the carrier obtained in the step (iii) in a solution containing an active metal component, and drying and roasting to obtain the hydrocracking catalyst.
2. The method of claim 1, wherein: in the Beta/Al-SBA-15 composite molecular sieve, the mass content of alumina is 2-85%, preferably 5-82%.
3. The method of claim 1, wherein: in the Beta/Al-SBA-15 composite molecular sieve, the mass content of the Beta molecular sieve is 10-90%, preferably 25-85%.
4. The method of claim 1, wherein: in the Beta/Al-SBA-15 composite molecular sieve, the mass content of alumina in the Al-SBA-15 molecular sieve is as follows: 5 to 75 percent.
5. The method of claim 1, wherein: the medium-strong acid amount of the Beta/Al-SBA-15 composite molecular sieve is 0.6-1.2 mL/g, preferably 0.7-1.0 mL/g; the ratio of B acid to L acid is less than 0.80.
6. The method of claim 1, wherein: the preparation method of the Beta/Al-SBA-15 composite molecular sieve comprises the following steps:
(1) mixing amorphous silica-alumina and deionized water, and pulping to form slurry;
(2) preparing an acidic aqueous solution containing a P123 triblock copolymer;
(3) and (2) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2), performing first crystallization, then adding Beta molecular sieve slurry, and performing second crystallization to prepare the Beta/Al-SBA-15 composite molecular sieve.
7. The method of claim 6, wherein: the first crystallization conditions in the step (3) are as follows: the crystallization temperature is 80-120 ℃, the crystallization time is 10-35 h, the pH value in the crystallization process is controlled to be 2.0-5.0, and the second crystallization conditions in the step (3) are as follows: the crystallization temperature is 80-130 ℃, the crystallization time is 4-20 h, and the pH value in the crystallization process is controlled to be 2.0-5.0.
8. The method of claim 1, wherein: the properties of the Y-type molecular sieve used in step (ii) are as follows: SiO 22/Al2O3The molar ratio is 25-150, and the specific surface area is 550-1000 m2(iv)/g, the total pore volume is 0.30-0.60 mL/g.
9. The method of claim 1, wherein: the properties of the alumina in step (ii) are as follows: the specific surface area is 150-450 m2Preferably 230 to 340 m/g2(ii)/g; the pore volume is 0.4-1.4 mL/g, preferably 0.8-1.2 mL/g, and the average pore diameter is 8-14 nm.
10. The method of claim 1, wherein: in the step (iii), the mass concentration of the nano silicon dioxide dispersion liquid in the impregnation liquid is 20-50%; the particle size of the nano silicon dioxide is 10-20 nanometers.
11. The method of claim 1, wherein: the active metal component in the step (iv) is metal of a VIII group and a VIB group, the metal of the VIII group is preferably Co and/or Ni, and the metal of the VIB group is preferably W and/or Mo; based on the weight of the catalyst, the content of the VIII family metal calculated by oxide is 1 to 15 weight percent, preferably 4 to 10 weight percent; the content of the VIB group metal calculated by oxide is 9-30 wt%, preferably 15-28 wt%, and the content of the hydrocracking catalyst carrier is 60-80 wt%, preferably 65-75 wt%.
12. The method of claim 1, wherein: the density molar ratio of the hydroxyl on the surface of the hydrocracking catalyst carrier is 1.5-2.5, and preferably 1.8-2.2.
13. A hydrocracking catalyst prepared by the process as claimed in any one of claims 1 to 12.
14. The catalyst of claim 13, wherein: the properties of the hydrocracking catalyst were as follows: the specific surface area is 120-350 m2Preferably 150 to 330 m/g2The pore volume is 0.20 to 0.60mL/g, preferably 0.2 to 0.55 mL/g.
15. An application of a hydrocracking catalyst in a coal tar hydrocracking process is characterized in that: the catalyst is a hydrocracking catalyst prepared according to the process of any one of claims 1 to 12 or a hydrocracking catalyst according to claim 13 or 14.
16. Use according to claim 15, characterized in that: the properties of the coal tar are as follows: the density is 1000 to 1200kg/m3The nitrogen content is 0.8wt% -1.5 wt%, and the sulfur content is 0.2wt% -0.8 wt%.
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