CN116060093A - Hydrocracking catalyst and preparation method thereof - Google Patents

Hydrocracking catalyst and preparation method thereof Download PDF

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Publication number
CN116060093A
CN116060093A CN202111278936.7A CN202111278936A CN116060093A CN 116060093 A CN116060093 A CN 116060093A CN 202111278936 A CN202111278936 A CN 202111278936A CN 116060093 A CN116060093 A CN 116060093A
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catalyst
molecular sieve
hydrocracking catalyst
sulfide
group
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Inventor
郭蓉
陈�光
刘丽
郑步梅
陈晓贞
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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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Priority to CN202111278936.7A priority Critical patent/CN116060093A/en
Publication of CN116060093A publication Critical patent/CN116060093A/en
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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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/146—Y-type faujasite
    • 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
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group metals
    • 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
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • 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
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/044—Iron group metals or copper
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7615—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
    • 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
    • C10G47/04—Oxides
    • 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
    • C10G47/06—Sulfides
    • 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
    • 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
    • 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
    • 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

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  • Organic Chemistry (AREA)
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  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The hydrocracking catalyst takes alumina as a carrier, molecular sieve and active components are loaded on the catalyst, the molecular sieve accounts for 1.5-15wt% based on the total weight of the catalyst, the sulfide of the VIB group metal accounts for 10-30%, the oxide of the VIII group metal accounts for 2-10%, the sulfide of the VIB group metal is loaded on the alumina carrier, and the molecular sieve is loaded on the sulfide of the VIB group metal and the carrier alumina. The catalyst is prepared by loading the VIB group metal on a carrier, then vulcanizing the carrier, loading the molecular sieve, and finally loading the VIII group metal, wherein the VIB group metal-VIII group metal-S phase has a large number of active sites and good hydrogenation performance, and the molecular sieve is loaded on the VIB group metal sulfide and the carrier alumina instead of being kneaded with the carrier, so that the probability of contacting the carrier with reactants is improved, the dosage of the molecular sieve is greatly reduced, and the cost of the cracking catalyst is reduced.

Description

Hydrocracking catalyst and preparation method thereof
Technical Field
The invention relates to the technical field of oil product hydrogenation, in particular to a hydrocracking catalyst and a preparation method thereof.
Background
Along with the surplus production of diesel oil and the shortage of chemical raw materials, more oil refining enterprises adopt a hydrocracking technology to convert the raw materials into naphtha, so that the yield of diesel oil is reduced. The performance of catalysts in hydrocracking technology has a significant impact on product architecture.
CN202011162134.5 discloses a medium oil type hydrocracking catalyst and a preparation method thereof. The hydrocracking catalyst is prepared by mixing a modified Y molecular sieve, a beta molecular sieve and an SSZ-32 molecular sieve, and although the catalyst can improve the yield and income of a medium oil type hydrocracking process, the performance of the molecular sieve in the catalyst is not fully utilized, a plurality of molecular sieves are wrapped by alumina to lose activity, and meanwhile, the improvement of the activity of the catalyst mainly comes from the improvement of the total content of the molecular sieves, which also leads to the increase of the cost of the catalyst. Meanwhile, the catalyst has high requirements on the nitrogen content in the raw oil in the use process so as to prevent the poisoning of the molecular sieve in the catalyst.
CN201611011276.5 discloses a method for preparing a hydrocracking catalyst. The method comprises the following steps: (1) Mixing, pulping and filtering at least one of amorphous silica-alumina or a precursor thereof and macroporous alumina or a precursor thereof with a molecular sieve, wherein the dry basis of the amorphous silica-alumina or the precursor thereof and the macroporous alumina or the precursor thereof is 15-30%, and the dry basis of the molecular sieve is 35-50%; (2) Adding small-pore alumina into a rolling machine, adding a proper amount of peptizing agent, rolling, adding the material obtained in the step (1), continuously rolling, extruding strips, forming, drying and roasting to obtain a hydrocracking catalyst carrier; (3) And (3) introducing a hydrogenation active metal component on the hydrocracking catalyst carrier prepared in the step (2) by adopting an impregnation method to obtain the hydrocracking catalyst. The method can omit the drying and crushing processes of the powder, but the molecular sieve with higher acid content can be wrapped by alumina and can not play a role, so that part of the molecular sieve can not play a role in the reaction process.
Disclosure of Invention
Aiming at the defects of the prior art, the invention discloses a hydrocracking catalyst and a preparation method thereof, wherein the catalyst is low in price, has high selectivity, can accurately control the hydrogenation saturation depth and the cracking degree, and has high nitrogen poisoning resistance.
In the context of the present specification, the content of group VIII metal oxides on group VIB metal sulfide wafers was analyzed using CO-FTIR (carbon monoxide in situ infrared analysis). The measurement conditions of the CO-FTIR include: the catalyst is ground and then pressed into self-supporting sheets of phi 13mm, and the self-supporting sheets are placed on an in-situ cell sample holder. With 3.0% H 2 S is vulcanized for 3 hours at 320 ℃, then H 2 And cooling to room temperature in the S atmosphere, vacuumizing to 300 ℃, purifying by 2h, and adsorbing CO under the condition of reducing the temperature by liquid nitrogen. Introducing a small amount of CO gas into the in-situ tank, and desorbing to 10 after adsorption balance is carried out for 30min -4 Pa. And collecting infrared spectrums before and after CO adsorption, wherein the difference spectrum of the infrared spectrums before and after CO adsorption is the infrared spectrum result of CO adsorption by the catalyst. The experiment adopts a Nicolet 6700 Fourier transform infrared spectrometer, the scanning times are 32 times, and the resolution is 4cm -1 ，4000~650 cm -1 The detector was MCT/A measured.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
the technical purpose of the first aspect of the invention is to provide a hydrocracking catalyst, which takes alumina as a carrier, and loads molecular sieve and active components on the alumina, wherein the active components are VIB group metal sulfide and VIII group metal oxide; the molecular sieve comprises 1.5 to 15wt%, preferably 2 to 12wt%, more preferably 3 to 8wt%, based on the total weight of the catalyst; the group VIB metal sulfide is 10-30%, preferably 15-28% in terms of sulfide, and the group VIII metal oxide is 2-10%, preferably 4-8% in terms of oxide; the VIB metal sulfide is loaded on an alumina carrier, and the molecular sieve is loaded on the VIB metal sulfide and the carrier alumina; the content of the VIII group metal oxide on the VIB group metal sulfide wafer is 60-100% of the VIII group metal oxide.
Further, the hydrocracking catalyst, when analyzed by CO-FTIR, has a group VIB metal-group VIII metal-S phase in the range of 60 to 100%, preferably 65% to 90%, more preferably 70% to 90%, and most preferably 80% to 90% of the group VIII metal.
Further, the molecular sieve is at least one selected from the group consisting of a Y-type molecular sieve, a ZSM-5 molecular sieve, a beta-type molecular sieve and an MCM-41 molecular sieve.
Further, the VIB group metal sulfide is molybdenum sulfide or/and tungsten sulfide, and the VIII group metal oxide is nickel oxide or/and cobalt oxide.
The technical object of the second aspect of the present invention is to provide a method for preparing the hydrocracking catalyst, comprising the steps of:
(1) Impregnating an alumina carrier with impregnating solution containing VIB group metal salt, and drying and vulcanizing to obtain a catalyst precursor A;
(2) Carrying out hydrothermal treatment on the catalyst precursor A and the molecular sieve precursor, and then drying and roasting in an inert atmosphere to obtain a catalyst precursor B;
(3) Impregnating the catalyst precursor B with an impregnating solution containing a group VIII metal salt and an organic aid, and then drying in an inert atmosphere to obtain the hydrocracking catalyst.
Further, the impregnating solution containing the group VIB metal salt in the step (1) is a phosphate or ammonium salt solution of the group VIB metal, and the preparation method thereof is well known to those skilled in the art, and an equal volume impregnation or supersaturation impregnation mode is adopted. The group VIB metal is preferably Mo and/or W.
Further, the drying conditions in the step (1) are as follows: drying at 90-200deg.C for 3-6 hr.
Further, the vulcanization treatment in the step (1) is dry vulcanization or wet vulcanization. The dry vulcanizing agent is hydrogen sulfide, and the wet vulcanizing agent is one or two of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide; the vulcanization pressure is 3.2-6.4MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12h.
Further, the molecular sieve precursor in the step (2) is gel formed by mixing a silicon source and/or an aluminum source, a precipitator, a template agent and water, and the preparation method is well known to those skilled in the art, and the molecular sieve is formed by adopting a precipitation method or a sol-gel method. The silicon source is selected from one or more of sodium silicate, tetraethoxysilane, silica sol and chromatographic silica gel; the aluminum source is selected from one or more of sodium metaaluminate, aluminum hydroxide and pseudo-boehmite; the precipitant is at least one of sodium hydroxide, ammonia water and potassium hydroxide; the template agent is one or more selected from cetyl trimethyl ammonium bromide, ethylenediamine, n-butylamine, tetrapropyl ammonium bromide, ethanol, tetraethylammonium hydroxide, tetraethylammonium bromide, triethylamine, di-n-propylamine, diisopropylamine and methylcellulose.
Further, the hydrothermal treatment conditions of step (2): the temperature is 90-200deg.C, preferably 130-200deg.C, the pressure is 0.1-2.0MPa, the pH is 7.5-9.0, and the time is 5-48 hr.
Further, the inert atmosphere in the step (2) is N 2 And one or more of inert gases; the drying temperature of the step (2) is 20-90 ℃ and the drying time is 4-16 hours; the roasting temperature is 300-500 ℃ and the roasting time is 2-5 hours.
Further, the impregnating solution containing the group VIII metal salt in the step (3) is a nitrate, acetate or sulfate solution of the group VIII metal, etc., and an equal volume impregnation mode may be adopted, where the group VIII metal is Ni and/or Co.
Further, the organic auxiliary agent in the step (3) is as follows: alcohols or organic acids containing hydroxyl and/or carboxyl groups, wherein the number of carbon atoms is 3-10. Specifically, at least one selected from ethylene glycol, glycerol, butanediol, pentanediol, acetic acid, citric acid, malonic acid, succinic acid and glutaric acid.
Further, the inert atmosphere in the step (3) is N 2 And one or more of inert gases; the drying temperature of the step (3) is 90-150 ℃ and the drying time is 4-16 hours.
The technical purpose of the third aspect of the invention is to provide the application of the hydrocracking catalyst, which is used for the hydrocracking process of various heavy raw oil such as catalytic diesel oil, vacuum gas oil, catalytic cracking gas oil and thermal cracking gas oil, wherein the boiling point of the raw material is 250-500 ℃ and the nitrogen content is 100-1000ppm.
Further, the hydrocracking catalyst does not have to be sulfided prior to use. The metal oxide is in a semi-vulcanized state, and the VIII metal oxide is easy to sulfide, so that the hydrogen sulfide in the raw oil can be utilized for vulcanization in a starting stage.
Compared with the prior art, the catalyst provided by the invention has the following advantages:
(1) In the catalyst, the VIII metal oxide is mainly loaded on the VIB metal sulfide wafer, so that the number of active sites formed by the VIB metal-VIII metal-S phase is large, and the hydrogenation performance of the catalyst is improved; the molecular sieve is loaded on the VIB group metal sulfide and the carrier alumina instead of being kneaded with the carrier, so that the probability of contact with reactants is improved, the utilization rate of the molecular sieve is increased, and compared with the molecular sieve consumption of at least 50% in the hydrocracking catalyst in the prior art, the molecular sieve consumption is greatly reduced, thereby reducing the cost of the cracking catalyst.
(2) The catalyst is in a semi-vulcanized state, the catalyst does not need to be vulcanized in the use process, sulfide in raw oil can be used for vulcanizing the VIII family metal oxide, so that the temperature runaway in the vulcanization process is prevented, and meanwhile, the phenomena of the temperature runaway of a catalyst bed and carbon deposition of the catalyst caused by the excessive initial activity of the hydrocracking catalyst are prevented; and meanwhile, the catalyst is obtained after the VIII group metal solution is immersed and dried, no roasting process exists, and the VIII group metal is prevented from interacting with aluminum in the molecular sieve to generate spinel, so that the vulcanization of the VIII group metal is facilitated.
(2) In the preparation method of the catalyst, firstly, the VIB group metal is loaded on a carrier, then vulcanized to generate a large number of VIB group metal sulfide wafers, then a molecular sieve is loaded, and finally the VIII group metal is loaded, so that on one hand, the VIB group metal which is difficult to vulcanize can be vulcanized firstly, and the vulcanizing degree of the VIB group metal is improved; on the other hand, the contact surface between the molecular sieve and the VIII group metal and the VIB group metal is improved, the synergistic effect of the hydrogenation performance and the cracking performance of the catalyst is improved, the hydrocracking activity of the catalyst is improved, and meanwhile, the influence of nitride in the raw material on the molecular sieve can be reduced; the third aspect can improve the quantity of molecular sieves loaded on the active sites of the active metal sulfide, fully exert the capability of the molecular sieves for providing H protons and improve the cracking performance of the catalyst; in the fourth aspect, the VIB group metal solution is directly vulcanized after being immersed and dried, and no roasting process is adopted, so that the interaction between the metal oxide and the carrier is prevented, and the metal vulcanization degree is improved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
The composition of the catalyst provided by the invention can be characterized by combining inductively coupled plasma ICP and XPS energy spectrum, wherein the total content of VIB group metal and the total content of VIII group metal in the catalyst are firstly characterized by ICP, and then the content of metal elements with different valence states in the catalyst is quantitatively characterized by an XPS energy spectrum.
The invention uses CO-FTIR (carbon monoxide in situ infrared analysis) to analyze the content of VIII family metal oxide on VIB family metal oxide wafer. The measurement conditions of the CO-FTIR include: catalyst is groundAfter grinding, pressing into self-supporting sheets with the diameter of 13mm, and placing the self-supporting sheets on an in-situ cell sample holder. With 3.0% H 2 S is vulcanized for 3 hours at 320 ℃, then H 2 And cooling to room temperature in the S atmosphere, vacuumizing to 300 ℃, purifying for 2 hours, and carrying out CO adsorption under the condition of reducing the temperature by liquid nitrogen. Introducing a small amount of CO gas into the in-situ tank, and desorbing to 10 after adsorption balance is carried out for 30min -4 Pa. And collecting infrared spectrums before and after CO adsorption, wherein the difference spectrum of the infrared spectrums before and after CO adsorption is the infrared spectrum result of CO adsorption by the catalyst. The experiment adopts a Nicolet 6700 Fourier transform infrared spectrometer, the scanning times are 32 times, and the resolution is 4cm -1 ，4000~650cm -1 The detector was MCT/A measured.
Example 1
(1) An ammonium heptamolybdate solution was impregnated into an alumina support, then dried at 110 ℃ for 2 hours, then treated with a solution containing 1.5% h 2 S, hydrogen is vulcanized, the vulcanization temperature is 320 ℃, the vulcanization pressure is 4.2MPa, the vulcanization time is 4h, and then the vulcanization is carried out on N 2 And cooling to room temperature in the atmosphere to obtain the catalyst precursor A.
(2) Adding sodium hydroxide, silica sol, sodium metaaluminate and ethylenediamine into deionized water, wherein the molar ratio of each component is n (SiO 2 ):n(Al 2 O 3 ):n(Na 2 O): n (ethylenediamine): n (H) 2 O) =15:1:6:4:200, stirring to form a uniform sol, namely a precursor of the Y molecular sieve, mixing with the catalyst precursor a prepared in the step (1), and performing hydrothermal treatment for 10 hours at 150 ℃, 1.0MPa and ph=8.0; and then filtering, washing with deionized water for three times, drying for 3 hours at 120 ℃ in a nitrogen atmosphere, and roasting for 3 hours at 450 ℃ to obtain the catalyst precursor B.
(3) And (3) immersing nickel nitrate and glycerol solution into the catalyst precursor B prepared in the step (2), and then drying for 3 hours at 110 ℃ in a nitrogen atmosphere to obtain the catalyst C-1.
The catalyst C-1 comprises the following components in percentage by weight: moS (MoS) 2 26 percent of NiO, 5.2 percent of Y molecular sieve, 6.0 percent of Y molecular sieve and the balance of alumina carrier.
Example 2
(1) The ammonium heptamolybdate solution was impregnated into an alumina support and then dried at 110 c2 hours, then 1.5% H is used 2 S, hydrogen is vulcanized, the vulcanization temperature is 330 ℃, the vulcanization pressure is 3.8MPa, the vulcanization time is 4 hours, and then the vulcanization is carried out on N 2 And cooling to room temperature in the atmosphere to obtain the catalyst precursor A.
(2) Adding sodium hydroxide, silica sol, sodium metaaluminate and ethylenediamine into deionized water, wherein the molar ratio of each component is n (SiO 2 ):n(Al 2 O 3 ):n(Na 2 O): n (n-butylamine): n (H) 2 O) =25:1:7.5:7:220, stirring to form a uniform sol, namely a precursor of the ZSM-5 molecular sieve, mixing with the catalyst precursor a prepared in the step (1), and performing hydrothermal treatment for 10 hours at 150 ℃, 1.0MPa and ph=8.0; and then filtering, washing with deionized water for three times, drying at 120 ℃ for 3 hours in a nitrogen atmosphere, and roasting at 500 ℃ for 3 hours to obtain the catalyst precursor B.
(3) And (3) immersing nickel nitrate and glycol solution into the catalyst precursor B prepared in the step (2), and then drying at 130 ℃ for 3 hours in a nitrogen atmosphere to obtain the catalyst C-2.
The catalyst C-2 comprises the following components in percentage by weight: moS (MoS) 2 25 percent of NiO, 5.2 percent of ZSM-5 molecular sieve, 6.8 percent of ZSM-5 molecular sieve and the balance of alumina carrier.
Example 3
(1) An ammonium heptamolybdate solution was impregnated into an alumina support, then dried at 110 ℃ for 2 hours, then treated with a solution containing 1.5% h 2 S, hydrogen is vulcanized, the vulcanization temperature is 350 ℃, the vulcanization pressure is 3.8MPa, the vulcanization time is 4h, and then the vulcanization is carried out on N 2 And cooling to room temperature in the atmosphere to obtain the catalyst precursor A.
(2) Dissolving sodium metaaluminate and sodium hydroxide into deionized water, then adding tetraethylammonium bromide, stirring vigorously, slowly dropwise adding silica sol, and aging for 3 hours, wherein the molar ratio of each component is n (SiO) 2 ):n(Al 2 O 3 ):n(Na 2 O) n (tetraethylammonium bromide) n (H) 2 O) =20:1:6:4:200, forming a precursor of the beta-type molecular sieve, then mixing with the catalyst precursor a prepared in the step (1), and then performing hydrothermal treatment for 10 hours under the conditions of 150 ℃, 1.0MPa and ph=8.0; then filtering and washing with deionized water for three times, inDrying for 3h at 120 ℃ in nitrogen atmosphere, and roasting for 3h at 500 ℃ to obtain the catalyst precursor B.
(3) And (3) immersing nickel nitrate and glycol solution into the catalyst precursor B prepared in the step (2), and then drying at 130 ℃ for 3 hours in a nitrogen atmosphere to obtain the catalyst C-3.
The catalyst C-3 comprises the following components in percentage by weight: moS (MoS) 2 24 percent of NiO, 3.2 percent of beta-type molecular sieve, 7.1 percent of beta-type molecular sieve and the balance of alumina carrier.
Example 4
(1) An ammonium heptamolybdate solution was impregnated into an alumina support, then dried at 110 ℃ for 2 hours, then treated with a solution containing 1.5% h 2 S, hydrogen is vulcanized, the vulcanization temperature is 350 ℃, the vulcanization pressure is 3.8MPa, the vulcanization time is 4h, and then the vulcanization is carried out on N 2 And cooling to room temperature in the atmosphere to obtain the catalyst precursor A.
(2) Mixing cetyl trimethyl ammonium bromide with sodium hydroxide, adding into deionized water, stirring, dropwise adding ethyl orthosilicate into the mixed solution, stirring for 30min, wherein the molar ratio of each component is n (SiO) 2 ):n(Na 2 O) n (hexadecyl trimethyl ammonium bromide) n (H) 2 O) =12:2:3:220 to form MCM-41 molecular sieve precursor, then mixing with the catalyst precursor a prepared in step (1), and then performing hydrothermal treatment for 10h under the conditions of 150 ℃, 1.0MPa and ph=8.0; and then filtering, washing with deionized water for three times, drying for 3 hours at 120 ℃ in a nitrogen atmosphere, and roasting for 3 hours at 450 ℃ to obtain the catalyst precursor B.
(3) And (3) immersing nickel nitrate and glycol solution into the catalyst precursor B prepared in the step (2), and then drying for 3 hours at 120 ℃ in nitrogen atmosphere to obtain the catalyst C-4.
The catalyst C-4 comprises the following components in percentage by weight: moS (MoS) 2 22 percent of NiO, 4.8 percent of MCM-41 molecular sieve, 6.8 percent of MCM-41 molecular sieve and the balance of alumina carrier.
Example 5
(1) An ammonium heptamolybdate solution was impregnated into an alumina support, then dried at 110 ℃ for 2 hours, then treated with a solution containing 1.5% h 2 S, hydrogen is vulcanized, the vulcanization temperature is 330 ℃, and the vulcanization is carried outThe pressure was 3.8MPa and the curing time was 6h, followed by N 2 And cooling to room temperature in the atmosphere to obtain the catalyst precursor A.
(2) Adding sodium hydroxide, silica sol, sodium metaaluminate and ethylenediamine into deionized water, wherein the molar ratio of each component is n (SiO 2 ):n(Al 2 O 3 ):n(Na 2 O): n (ethylenediamine): n (H) 2 O) =15:1:6:4:200, stirring to form a uniform sol, namely a precursor of the Y molecular sieve, mixing with the catalyst precursor a prepared in the step (1), and performing hydrothermal treatment for 10 hours at 150 ℃, 1.0MPa and ph=8.5; and then filtering, washing with deionized water for three times, drying for 3 hours at 110 ℃ in nitrogen atmosphere, and roasting for 3 hours at 450 ℃ to obtain the catalyst precursor B.
(3) And (3) immersing cobalt nitrate and citric acid solution into the catalyst precursor B prepared in the step (2), and then drying for 3 hours at 130 ℃ in a nitrogen atmosphere to obtain the catalyst C-5.
The catalyst C-5 comprises the following components in percentage by weight: moS (MoS) 2 22%, coO 5.0%, Y molecular sieve 5.0%, and alumina carrier for the rest.
Example 6
(1) The ammonium metatungstate solution was impregnated into the alumina carrier, then dried at 110℃for 2 hours, and then a solution containing 1.5% H was used 2 S, hydrogen is vulcanized, the vulcanization temperature is 350 ℃, the vulcanization pressure is 3.8MPa, the vulcanization time is 4h, and then the vulcanization is carried out on N 2 And cooling to room temperature in the atmosphere to obtain the catalyst precursor A.
(2) Adding sodium hydroxide, silica sol, sodium metaaluminate and ethylenediamine into deionized water, wherein the molar ratio of each component is n (SiO 2 ):n(Al 2 O 3 ):n(Na 2 O): n (n-butylamine): n (H) 2 O) =25:1:7.5:7:220, stirring to form a uniform sol, namely a precursor of the ZSM-5 molecular sieve, mixing with the catalyst precursor a prepared in the step (1), and performing hydrothermal treatment for 10 hours at 150 ℃, 1.0MPa and ph=8.5; and then filtering, washing with deionized water for three times, drying for 3 hours at 120 ℃ in a nitrogen atmosphere, and roasting for 3 hours at 450 ℃ to obtain the catalyst precursor B.
(3) And (3) immersing nickel nitrate and glycol solution into the catalyst precursor B prepared in the step (2), and then drying at 130 ℃ for 3 hours in a nitrogen atmosphere to obtain the catalyst C-6.
The catalyst C-6 comprises the following components in percentage by weight: WS (WS) 2 24 percent of NiO, 4.8 percent of ZSM-5 molecular sieve, 7.6 percent of ZSM-5 molecular sieve and the balance of alumina carrier.
Example 7
(1) The ammonium metatungstate solution was impregnated into the alumina carrier, then dried at 110℃for 2 hours, and then a solution containing 1.5% H was used 2 S, hydrogen is vulcanized, the vulcanization temperature is 330 ℃, the vulcanization pressure is 4.8MPa, the vulcanization time is 4h, and then the vulcanization is carried out on N 2 And cooling to room temperature in the atmosphere to obtain the catalyst precursor A.
(2) Adding sodium hydroxide, silica sol, sodium metaaluminate and ethylenediamine into deionized water, wherein the molar ratio of each component is n (SiO 2 ):n(Al 2 O 3 ):n(Na 2 O): n (ethylenediamine): n (H) 2 O) =15:1:6:4:200, stirring to form a uniform sol, namely a precursor of the Y molecular sieve, mixing with the catalyst precursor a prepared in the step (1), and performing hydrothermal treatment for 10 hours at 190 ℃, 1.0MPa and ph=8.0; and then filtering, washing with deionized water for three times, drying at 120 ℃ for 3 hours in a nitrogen atmosphere, and roasting at 500 ℃ for 3 hours to obtain the catalyst precursor B.
(3) And (3) immersing cobalt nitrate and glycerol solution into the catalyst precursor B prepared in the step (2), and then drying for 3 hours at 130 ℃ in a nitrogen atmosphere to obtain the catalyst C-7.
The catalyst C-7 comprises the following components in percentage by weight: WS (WS) 2 24%, coO 4.8%, Y molecular sieve 6.8%, and alumina carrier for the rest.
Comparative example 1
(1) Uniformly mixing a Y-type molecular sieve with alumina powder, nitric acid, starch and deionized water, wherein the Y-type molecular sieve is as follows: alumina powder: nitric acid: starch: the mass ratio of deionized water is 20:80:4:3:60, then kneading and extruding strips for molding, then drying at 80 ℃ for 10 hours, and roasting at 650 ℃ for 3 hours to obtain the modified alumina carrier, wherein the content of the Y-type molecular sieve is 20%.
(2) Heptamolybdic acid is addedThe ammonium solution was impregnated into the modified alumina carrier prepared in step (1) and then dried at 120℃for 2 hours, followed by the use of a solution containing 1.5% H 2 S, hydrogen is vulcanized, the vulcanization temperature is 320 ℃, the vulcanization pressure is 4.0MPa, the vulcanization time is 4h, and then the vulcanization is carried out on N 2 And cooling to room temperature in the atmosphere to obtain the catalyst precursor.
(3) And (3) immersing nickel nitrate solution in an equal volume into the catalyst precursor prepared in the step (2), and then drying for 3 hours at 110 ℃ in nitrogen atmosphere to obtain the catalyst DC-1.
The catalyst DC-1 comprises the following components in percentage by weight: moS (MoS) 2 24 percent of NiO, 4.8 percent of Y molecular sieve, 14.2 percent of Y molecular sieve and the balance of alumina.
Comparative example 2
(1) Uniformly mixing a Y-type molecular sieve with alumina powder, nitric acid, starch and deionized water, wherein the Y-type molecular sieve is as follows: alumina powder: nitric acid: starch: the mass ratio of deionized water is 20:80:4:3:60, then kneading and extruding strips for molding, then drying at 80 ℃ for 10 hours, and roasting at 650 ℃ for 3 hours to obtain the modified alumina carrier, wherein the content of the Y-type molecular sieve is 20%.
(2) Immersing the mixed solution of phosphomolybdic acid and nickel nitrate into the modified alumina carrier prepared in the step (1), drying at 120 ℃ for 3 hours, roasting at 450 ℃ for 3 hours, then carrying out vulcanization treatment, wherein the vulcanization temperature is 320 ℃, the vulcanization pressure is 3.0MPa, the vulcanization time is 4 hours, and then carrying out the vulcanization treatment on the modified alumina carrier in N 2 And cooling to room temperature in the atmosphere to obtain the catalyst DC-2.
The catalyst DC-2 comprises the following components in percentage by weight: moS (MoS) 2 24%, niS 4.8%, Y molecular sieve 14.2%, and alumina in balance.
Comparative example 3
(1) Uniformly mixing a Y-type molecular sieve with alumina powder, nitric acid, starch and deionized water, wherein the Y-type molecular sieve is as follows: alumina powder: nitric acid: starch: the mass ratio of deionized water is 20:80:4:3:60, then kneading and extruding strips for molding, then drying at 80 ℃ for 10 hours, and roasting at 650 ℃ for 3 hours to obtain the modified alumina carrier, wherein the content of the Y-type molecular sieve is 20%.
(2) Immersing the ammonium heptamolybdate solution into the modified alumina carrier prepared in the step (1), drying at 110 ℃ for 3 hours, and roasting at 350 ℃ for 3 hours to obtain the catalyst precursor.
(3) And (3) dipping the nickel nitrate solution into the catalyst precursor prepared in the step (2), drying at 90 ℃ for 3 hours, and roasting at 250 ℃ for 3 hours to obtain the catalyst DC-3.
The catalyst DC-3 comprises the following components in percentage by weight: moO (MoO) 3 22%, 8.0% nickel oxide, 14% Y molecular sieve and the balance alumina.
For the C-1 to C-7 catalysts prepared in the above examples, the DC-1 to DC-3 catalysts (oxidized state) prepared in the comparative examples were prepared with a molar ratio of +4 valence Mo/W to the total Mo/W (i.e., mo 4+ /W 4+ Content), mole ratio of +4 valence Mo/W of hydrogenation catalyst (sulfided) to total Mo/W (i.e., mo) 4+ /W 4+ Content) is shown in table 1.
Table 1.
Figure 421775DEST_PATH_IMAGE001
Example 9
This example illustrates the hydrocracking performance of the catalyst provided by the present invention for VGO feedstock.
The raw oil for evaluation is VGO raw material provided by some refinery for medium petrochemical industry, and has the following main properties: the distillation range is 300-490 ℃, the sulfur content is 1.5 weight percent, and the nitrogen content is 1580 mug/g. The hydrocracking reaction performance was evaluated on catalysts C-1 to C-7, comparative examples DC-1 to DC-3, respectively, using a 200mL fixed bed hydrogenation apparatus. Wherein catalysts C-1 to C-7, comparative examples DC-1 and DC-2 did not require a pretreatment, and comparative example DC-3 did require a pretreatment. The pre-vulcanization conditions were: using a catalyst containing 3wt% CS 2 Is used for aviation kerosene at an airspeed of 1.5h -1 The catalyst DC-3 was presulfided at a hydrogen oil volume ratio of 500:1 and an operating pressure of 4.0 MPa. The reaction conditions were evaluated as follows: the operating pressure is 10.0MPa, the reaction temperature is 390 ℃, the hydrogen/oil volume ratio is 900:1, and the volume space velocity is 1.0h -1 The evaluation results are shown in Table 2.
Table 2.
Figure 732671DEST_PATH_IMAGE002
As can be seen from Table 2, the hydrocracking catalysts of the present invention achieved very high hydrocracking activity with only a small amount of molecular sieves.

Claims (18)

1. The hydrocracking catalyst is characterized in that alumina is used as a carrier, a molecular sieve and an active component are loaded on the catalyst, and the active component is a VIB group metal sulfide and a VIII group metal oxide; the molecular sieve comprises 1.5 to 15wt%, preferably 2 to 12wt%, more preferably 3 to 8wt%, based on the total weight of the catalyst; the group VIB metal sulfide is 10-30%, preferably 15-28% in terms of sulfide, and the group VIII metal oxide is 2-10%, preferably 4-8% in terms of oxide; the VIB metal sulfide is loaded on an alumina carrier, and the molecular sieve is loaded on the VIB metal sulfide and the carrier alumina; the content of the VIII group metal oxide on the VIB group metal sulfide wafer is 60-100% of the VIII group metal oxide.
2. The hydrocracking catalyst according to claim 1, characterized in that it comprises a group VIB metal-group VIII metal-S phase in a molar ratio of from 60 to 100%, preferably from 65% to 90%, more preferably from 70% to 90%, most preferably from 80% to 90% of the group VIII metal when analyzed by CO-FTIR.
3. The hydrocracking catalyst of claim 1 wherein the molecular sieve is selected from at least one of a Y-type molecular sieve, a ZSM-5 molecular sieve, a beta-type molecular sieve, and an MCM-41 molecular sieve.
4. The hydrocracking catalyst as claimed in claim 1, wherein the group VIB metal sulfide is molybdenum sulfide or/and tungsten sulfide, and the group VIII metal oxide is nickel oxide or/and cobalt oxide.
5. A method for preparing a hydrocracking catalyst, comprising the steps of:
(1) Impregnating an alumina carrier with impregnating solution containing VIB group metal, and drying and vulcanizing to obtain a catalyst precursor A;
(2) Carrying out hydrothermal treatment on the catalyst precursor A and the molecular sieve precursor, and then drying and roasting in an inert atmosphere to obtain a catalyst precursor B;
(3) Impregnating the catalyst precursor B with an impregnating solution containing a group VIII metal and an organic auxiliary agent, and then drying in an inert atmosphere to obtain the hydrocracking catalyst.
6. The method according to claim 5, wherein the impregnating solution containing the group VIB metal salt in step (1) is a solution of a phosphate or ammonium salt of a group VIB metal, and is impregnated by an isovolumetric impregnation or supersaturation.
7. The hydrocracking catalyst of claim 5, wherein the drying conditions of step (1) are: drying at 90-200deg.C for 3-6 hr.
8. The hydrocracking catalyst according to claim 5, wherein the vulcanization treatment in the step (1) is dry vulcanization or wet vulcanization, the dry vulcanizing agent is hydrogen sulfide, and the wet vulcanizing agent is one or two of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide; the vulcanization pressure is 3.2-6.4MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12h.
9. The hydrocracking catalyst according to claim 5, wherein the molecular sieve precursor in the step (2) is a gel formed by mixing a silicon source and/or an aluminum source, a precipitant, a template agent and water, and the molecular sieve is formed by adopting a precipitation method or a sol-gel method.
10. The hydrocracking catalyst according to claim 9, wherein the silicon source is selected from one or more of sodium silicate, ethyl orthosilicate, silica sol and silica gel; the aluminum source is selected from one or more of sodium metaaluminate, aluminum hydroxide and pseudo-boehmite; the precipitant is at least one of sodium hydroxide, ammonia water and potassium hydroxide; the template agent is one or more selected from cetyl trimethyl ammonium bromide, ethylenediamine, n-butylamine, tetrapropyl ammonium bromide, ethanol, tetraethylammonium hydroxide, tetraethylammonium bromide, triethylamine, di-n-propylamine, diisopropylamine and methylcellulose.
11. The hydrocracking catalyst of claim 5, wherein the hydrothermal treatment conditions of step (2): the temperature is 90-200deg.C, preferably 130-200deg.C, the pressure is 0.1-2.0MPa, the pH is 7.5-9.0, and the time is 5-48 hr.
12. The hydrocracking catalyst as claimed in claim 5, wherein the drying temperature in the step (2) is 20 to 90 ℃ and the drying time is 4 to 16 hours; the roasting temperature is 300-500 ℃ and the roasting time is 2-5 hours.
13. The hydrocracking catalyst according to claim 5, wherein the impregnating solution containing the group VIII metal salt in the step (3) is a nitrate, acetate or sulfate solution of the group VIII metal in an isovolumetric impregnation manner.
14. The hydrocracking catalyst of claim 5, wherein the organic auxiliary agent of step (3) is: alcohols or organic acids containing hydroxyl and/or carboxyl groups, wherein the number of carbon atoms is 3-10.
15. The hydrocracking catalyst of claim 14, wherein the organic aid of step (3) is selected from at least one of ethylene glycol, glycerol, butylene glycol, pentylene glycol, acetic acid, citric acid, malonic acid, succinic acid, and glutaric acid.
16. The hydrocracking catalyst as claimed in claim 5, wherein the drying temperature in the step (3) is 90 to 150 ℃ and the drying time is 4 to 16 hours.
17. Use of the catalyst of any one of claims 1 to 4 or the catalyst prepared according to any one of claims 5 to 15 in a hydrocracking process for catalyzing diesel, vacuum gas oil, catalytically cracked gas oil and thermally cracked gas oil.
18. The use according to claim 17, wherein the hydrocracking catalyst does not have to be sulfided prior to use.
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Applicant before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp.