CN116440918A - Hydrogenation catalyst grading method and application thereof - Google Patents

Hydrogenation catalyst grading method and application thereof Download PDF

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Publication number
CN116440918A
CN116440918A CN202210012187.1A CN202210012187A CN116440918A CN 116440918 A CN116440918 A CN 116440918A CN 202210012187 A CN202210012187 A CN 202210012187A CN 116440918 A CN116440918 A CN 116440918A
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Prior art keywords
catalyst
hydrogenation catalyst
content
alumina carrier
temperature
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CN202210012187.1A
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Chinese (zh)
Inventor
吕振辉
薛冬
杨涛
朱慧红
金浩
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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 CN202210012187.1A priority Critical patent/CN116440918A/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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
    • B01J35/615—
    • B01J35/647—
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • 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

Abstract

The invention discloses a hydrogenation catalyst grading method and application thereof. The grading method comprises a multi-stage sulfided hydrogenation catalyst, wherein each stage of catalyst comprises an alumina carrier and a metal active component, and the alumina carrier contains three coordination types of aluminum ions: three-coordinated aluminum ion Al 3+ Ⅲ Four-coordinated aluminum ion Al 3+ Ⅳ And penta-coordinated aluminum ion Al 3+ Ⅴ In the flow direction of the liquid phase reactant, the content of penta-coordinated aluminum ions is based on the total amount of three ligand aluminum in the alumina carrierGradually decreasing by 5-15 percentage points, increasing the average length of metal active phase plate crystal, and increasing the average layer number of plate crystalThe stage is reduced. The grading method is applied to the hydrogenation treatment of the inferior raw materials, can obviously reduce the steric hindrance effect and improve the utilization rate of the active metal phase.

Description

Hydrogenation catalyst grading method and application thereof
Technical Field
The invention relates to a grading method of a hydrogenation catalyst and application thereof, in particular to a grading method of a heavy oil hydrogenation catalyst for long-period running of poor raw materials and application thereof.
Background
In the hydrogenation process of heavy oil, as the heavy and inferior raw materials are increased, the contents of Fe, si, na, ca and other metal impurities and inorganic salts in the raw materials are increased continuously, the metals mainly exist in the forms of colloid and asphaltene, and secondly, the saturated hydrocarbon content in the heavy and inferior raw materials is low, the aromatic hydrocarbon content is high, the colloid content is high, especially the heavy aromatic hydrocarbon content is high, and the heavy raw materials have complex molecular structure, larger steric hindrance and easier removal of impurities; along with hydrogenation and hydrogenolysis reaction, reactant molecules are gradually opened and broken, the molecular structure is gradually simplified, the steric hindrance is smaller, and impurities are more difficult to remove. The existing grading method of heavy oil hydrogenation catalyst is often researched from the aspects of apparent layers, namely catalyst particle size, pore canal size, activity transition and the like, is not considered from the actual reactant molecular structure layers and catalyst microstructures, and the reactant molecular structures and the catalyst microstructures cannot be well matched with each other along with the progress of the reaction, so that the depth of hydrogenation reaction is limited.
CN103773437a discloses a process for the grading of a hydrodesulphurisation catalyst, said process comprising: the hydrogenation reactor comprises at least two catalyst beds, and the upstream catalyst bed is a catalyst bed with low pile ratio according to the contact sequence with the reaction materials, and the pile ratio of the downstream catalyst bed is higher than that of the adjacent upstream catalyst bed; and more than two catalysts with different diameters are filled in each catalyst bed layer in a grading way. These physical mixtures have smaller void fractions and larger packing ratios than their single diameter catalysts, improving the hydrodesulfurization performance of the overall reaction system, but are difficult to achieve long-cycle stable operation for processing poor quality feedstocks with high solid impurity levels.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a grading method of a hydrogenation catalyst so as to solve the problem of long-period operation of poor raw materials, effectively optimize the active grading of the whole hydrogenation catalyst, and realize reasonable distribution of impurities in the whole system, thereby realizing the aim of synchronous inactivation of the whole catalyst system as much as possible, so as to improve the utilization rate of the hydrogenation catalyst and realize long-period operation of a device.
In order to achieve the above purpose, the present invention provides a grading method of a hydrogenation catalyst, which comprises a grading system composed of n-stage sulfided hydrogenation catalysts, wherein n is greater than or equal to 3, preferably n is 3 or 4, each stage of sulfided hydrogenation catalyst comprises an alumina carrier and a metal active component, and the alumina carrier contains three coordination types of aluminum ions: three-coordinated aluminum ion Al 3+ Ⅲ Four-coordinated aluminum ion Al 3+ IV And penta-coordinated aluminum ion Al 3+ Ⅴ The hydrogenation catalyst of each stage takes the total amount of three ligand aluminum in the alumina carrier as the reference, and the content of penta-coordination aluminum ions along the flow direction of the liquid phase reactantGradually decreasing with the amplitude of 5-15 percentage points; the average length of metal active phase platelets of each level of hydrogenation catalyst is gradually increased along the flow direction of liquid phase reactants, the average layer number of platelets is gradually reduced, and the metal active phase is active metal sulfide.
Further, the sulfided hydrogenation catalyst is obtained by sulfiding an oxidation state hydrogenation catalyst.
Further, the content of three-coordinated aluminum ions is based on the total amount of three-coordinated aluminum in the alumina carrier along the flow direction of the liquid-phase reactantGradually increasing the scale-up with the amplitude of 1-10 percentage points.
Further, in the flow direction of the liquid phase reactant, the content of tetra-coordinated aluminum ions is based on the total amount of three ligand aluminum in the alumina carrierThere is no particular requirement and may be increased, decreased or unchanged.
Further, in the alumina carrier of each stage of hydrogenation catalyst, the content of penta-coordinated aluminum ions is based on the total content of three ligand aluminum 40-60% of tetra-coordinated aluminum ion content>30-50% of three-coordination aluminum ion content>10 to 30 percent.
Further, the contents of various types of coordinated aluminum ions are calculated as shown in formulas I, II and III:
wherein θ represents the number of moles of the coordinated aluminum ion,is the coordinated aluminum ion content.
Further, in the alumina carrier of the same-stage hydrogenation catalyst, the content of penta-coordinated aluminum ionsContent of tetra-coordinated aluminum ion ≡>Content of tri-coordinated aluminum ion>
Further, in the alumina carrier of the same-stage hydrogenation catalyst, the difference between the penta-coordination aluminum ion content and the tri-coordination aluminum ion content is 15% -50%.
Further, in each stage of the sulfidic hydrogenation catalyst, the average length of the metal active photo crystal is 1-9 nm, and the stepwise increasing amplitude is 1-5 nm, preferably 2-4 nm.
Further, in each stage of the sulfided hydrogenation catalyst, the average number of metal active photo-crystalline layers is 1-9, and the stepwise reduction range is 1-5, preferably 2-4.
Further, n is preferably 3, that is, the grading system contains three hydrogenation catalysts in a sulfided state, and the three-stage filling ratio is 10% -90% based on the total volume of the catalysts in the reactor along the flowing direction of the liquid phase reactant: 5% -40%: 5% -80%, and the sum of the filling ratios of all stages is 100%.
Further, n is preferably 4, that is, the grading system contains four hydrogenation catalysts in a sulfided state, and the four-stage filling ratio is as follows in the flow direction of the liquid phase reactant based on the total volume of the catalysts in the reactor: 10% -70%: 10% -40%: 10% -40%: 10% -70%, and the sum of the filling proportion of each level is 100%; the preferred loading ratios are: 10% -40%: 10% -40%: 10% -40%: 10% -40%, and the sum of the filling ratios of all levels is 100%.
Further, the alumina carrier is prepared by molding/modifying hydrated alumina and/or alumina composition; wherein the hydrated alumina and/or alumina composition contains tri-, tetra-, and penta-coordinated aluminum ions.
Further, the hydrogenation catalyst is preferably a heavy oil hydrogenation catalyst commonly used in the art, wherein the pore volume of each stage of hydrogenation catalyst is gradually reduced, the pore diameter is gradually reduced, the activity is gradually increased, and the particle size is gradually reduced along the flowing direction of reactants. Such as hydrodesulfurization agents, hydrodecarbonization agents, hydrodenitrogenation agents, aromatic saturation agents, and the like.
Further, in each stage of hydrogenation catalyst, the active metal is at least one of metal elements of VIII group and/or VIB group, the content of the metal of VIII group is 0.2-9.0 wt%, preferably 0.5-9.0 wt% and the content of the metal of VIB group is 4-50 wt%, preferably 4-45 wt% based on the weight of the hydrogenation catalyst.
Further, in each stage of hydrogenation catalyst, the content of the alumina carrier is 45wt% to 95wt%, preferably 50wt% to 95wt%, based on the weight of the hydrogenation catalyst.
Further, in the alumina carrier, the control of the content of different coordination aluminum mainly depends on the roasting temperature in the preparation process of the alumina carrier, when the roasting temperature is increased, the content of penta-ligand aluminum is increased, and when the roasting temperature is reduced, the content of tri-ligand aluminum is increased.
Furthermore, the content of different coordination aluminum in the alumina carrier can be controlled by regulating and controlling the pH value of the alumina carrier in the preparation process.
Further, in the sulfided hydrogenation catalyst, the average length of metal active photo-crystals and the average number of layers of the photo-crystals mainly depend on the preparation method or the sulfiding mode of the hydrogenation catalyst, and the sulfiding mode can be wet sulfiding or dry sulfiding.
Further, the roasting temperature in the preparation process of the alumina carrier is 300-1000 ℃.
Further, the hydrogenation catalyst grading system preferably comprises three-stage sulfided hydrogenation catalysts, wherein the three-stage sulfided hydrogenation catalysts comprise alumina carriers, and the three-stage sulfided hydrogenation catalysts are respectively: the alumina carrier I, the alumina carrier II and the alumina carrier III, wherein the roasting temperature of the alumina carrier I is preferably 700-1000 ℃ and the roasting time is 2-10 h; the roasting temperature of the alumina carrier II is preferably 500-700 ℃ and the roasting time is 2-10 h; the calcination temperature of the alumina carrier III is preferably 300-500 ℃, and the calcination time is 2-10 h.
In the method of the invention, the synthesis method of the alumina used for the alumina carrier I refers to the reaction for preparing the aluminum hydroxide gel, and specifically, one or more of a precipitation method (including an acid method and an alkali method), a hydrolysis method and the like can be adopted. The precipitation method can be one or more of an aluminum sulfate method, a carbonization method, an aluminum chloride method, an aluminum nitrate method and the like; the hydrolysis may be a hydrolysis reaction of an aluminum-containing compound, such as hydrolysis of lower aluminum alkoxides, higher aluminum alkoxides. Kneading and extruding the prepared alumina raw material into a plastic body, and finally drying and roasting to obtain the required alumina carrier precursor, wherein the drying temperature is 100-200 ℃, the roasting temperature is 700-1000 ℃, and the roasting time is 2-10 h.
In the method of the invention, the preparation method of the oxidation state hydrogenation catalyst I comprises the following steps: supersaturating the alumina carrier I with a solution containing an active metal component to obtain a catalyst precursor, drying and roasting to obtain the required oxidation state hydrogenation catalyst I, wherein the drying temperature is 100-300 ℃, preferably 200-300 ℃, and the drying time is 1-5 h, preferably 4-5 h; the roasting temperature is 500-600 ℃, preferably 550-580 ℃, and the roasting time is 1-5 h, preferably 4-5 h; the temperature rising rate is 2-5 ℃/min.
The preparation method of the sulfided hydrogenation catalyst I comprises the following steps: filling an oxidation state hydrogenation catalyst I into a vulcanization reactor, introducing vulcanized oil (such as at least one of gasoline, diesel oil and wax oil) into the vulcanization reactor, and wetting a catalyst bed; then adjusting the temperature of the bed layer to 150-170 ℃ and injecting a vulcanizing agent (such as at least one of carbon disulfide and dimethyl disulfide); after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is raised to 250-270 ℃ at 2-5 ℃/h, and the temperature is kept constant for 8-10 hours; raising the temperature of the catalyst bed to 350-360 ℃ at 5-10 ℃/h, and keeping the temperature for 8-10 hours to obtain the sulfided hydrogenation catalyst I.
In the method of the invention, the synthesis method of the alumina used for the alumina carrier II refers to the reaction for preparing the aluminum hydroxide gel, and specifically, one or more of a precipitation method (including an acid method and an alkali method), a hydrolysis method and the like can be adopted. The precipitation method can be one or more of an aluminum sulfate method, a carbonization method, an aluminum chloride method, an aluminum nitrate method and the like; the hydrolysis may be a hydrolysis reaction of an aluminum-containing compound, such as hydrolysis of lower aluminum alkoxides, higher aluminum alkoxides. Then extruding the prepared alumina raw material into a plastic body, and finally drying and roasting to obtain the required alumina carrier precursor, wherein the drying temperature is 100-200 ℃, the roasting temperature is 500-700 ℃, and the roasting time is 2-10 h.
In the method of the invention, the preparation method of the oxidation state hydrogenation catalyst II comprises the following steps: impregnating an alumina carrier II with an organic compound solution; carrying out heat treatment on the obtained carrier loaded with the organic compound additive; and then loading active metal components on the obtained carrier loaded with the organic matters to obtain a catalyst precursor, and drying and roasting to obtain the required oxidation state hydrogenation catalyst II. The organic compound may specifically be a compound containing at least two oxygen atom groups and 2 to 5 carbon atoms, and preferably a compound containing at least two hydroxyl groups and 2 to 5 carbon atoms. The organic matter additive comprises at least one of alcohols, ethers or saccharides, wherein the alcohols can comprise at least one of ethylene glycol, propylene glycol, glycerol and the like, the ethers can comprise at least one of diethylene glycol, propylene glycol and the like, the saccharides comprise monosaccharides, and the organic compounds can be selected from one or more of the above. The drying temperature is 100-300 ℃, preferably 150-200 ℃, and the drying time is 1-5 h, preferably 2-3 h; the roasting temperature is 400-500 ℃, preferably 450-480 ℃, and the roasting time is 1-5 h, preferably 2-3 h; the temperature rising rate is 5-10 ℃/min. The dosage of the organic compound is 5-10% of the weight of the hydrogenation catalyst carrier.
The preparation method of the sulfur state hydrogenation catalyst II comprises the following steps: filling the oxidation state hydrogenation catalyst II into a vulcanization reactor, introducing vulcanized oil (such as at least one of gasoline, diesel oil and wax oil) into the vulcanization reactor, and wetting a catalyst bed; then adjusting the temperature of the bed layer to 150-170 ℃ and injecting a vulcanizing agent (such as at least one of carbon disulfide and dimethyl disulfide); after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is raised to 210-230 ℃ at 5-10 ℃/h, and the temperature is kept constant for 5-7 hours; raising the temperature of the catalyst bed to 330-340 ℃ at 10-15 ℃/h, and keeping the temperature for 5-7 hours to obtain the vulcanized hydrogenation catalyst II.
In the method of the invention, the synthesis method of the alumina used for the alumina carrier III refers to the reaction for preparing the aluminum hydroxide gel, and specifically, one or more of a precipitation method (including an acid method and an alkali method), a hydrolysis method and the like can be adopted. The precipitation method can be one or more of an aluminum sulfate method, a carbonization method, an aluminum chloride method, an aluminum nitrate method and the like; the hydrolysis may be a hydrolysis reaction of an aluminum-containing compound, such as hydrolysis of lower aluminum alkoxides, higher aluminum alkoxides. Kneading and extruding the prepared alumina raw material into a plastic body, and finally drying and roasting to obtain the required alumina carrier precursor, wherein the drying temperature is 100-200 ℃, the roasting temperature is 300-500 ℃, and the roasting time is 2-10 h.
In the method of the invention, the preparation method of the oxidation state hydrogenation catalyst III comprises the following steps: and (3) saturating and impregnating the alumina carrier III with a solution containing an active metal component and an organic compound to obtain a hydrogenation catalyst precursor, and drying to obtain the required oxidation state hydrogenation catalyst III. The organic compound may specifically be a compound containing at least two oxygen atom groups and 5 to 20 carbon atoms, preferably a compound containing at least two hydroxyl groups and 5 to 20 carbon atoms. The organic matter additive comprises at least one of alcohols, ethers or saccharides, wherein the alcohols can comprise glycerol, the ethers can comprise at least one of triethylene glycol, tributylene glycol or tetraethylene glycol, the saccharides comprise polysaccharide, the polysaccharide can comprise at least one of lactose, maltose or sucrose, and the organic compounds can be selected from one or more of the above. The drying temperature is 100-300 ℃, preferably 100-150 ℃, and the drying time is 1-5 h, preferably 1-1.5 h; the temperature rising rate is 2-5 ℃/min. The dosage of the organic compound is 15-20% of the weight of the carrier of the hydrogenation catalyst III.
The preparation method of the sulfur state hydrogenation catalyst III comprises the following steps: filling the oxidation state hydrogenation catalyst III into a vulcanization reactor, introducing vulcanized oil (such as at least one of gasoline, diesel oil and wax oil) into the vulcanization reactor, and wetting a catalyst bed; then adjusting the temperature of the bed layer to 150-170 ℃ and injecting a vulcanizing agent (such as at least one of carbon disulfide and dimethyl disulfide); after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is increased to 180-200 ℃ at 10-15 ℃/h, and the temperature is kept constant for 2-4 hours; raising the temperature of the catalyst bed to 310-320 ℃ at 15-20 ℃/h, and keeping the temperature for 2-4 hours to obtain the vulcanized hydrogenation catalyst III.
The second aspect of the invention is to provide an application of the hydrogenation catalyst grading method in the hydrogenation treatment of poor raw materials.
Further, the inferior raw materials include: heavy inferior raw materials such as gasoline, diesel oil, wax oil, residual oil, coal tar, coal liquefied oil and the like, in particular residual oil raw materials.
Further, the hydrogenation catalyst fractionation process of the present invention may be used under any suitable hydrotreating reaction conditions in the art.
Further, the hydrotreating reaction conditions are: the average reaction temperature is 200-450 ℃, preferably 250-430 ℃; the partial pressure of the reaction hydrogen is 4.0MPa to 20.0MPa, preferably 8.0MPa to 18.0MPa; the liquid hourly space velocity is 0.15h- 1 ～3.0h- 1 Preferably 0.2h- 1 ～2.0h- 1 The method comprises the steps of carrying out a first treatment on the surface of the The volume ratio of hydrogen to oil is 300-1500, preferably 500-1200.
Compared with the prior art, the method has the following advantages:
in the method, along the flow direction of a liquid phase reactant, the five-coordination aluminum ion content of a modified aluminum oxide carrier in the hydrogenation catalyst is higher, the four-coordination aluminum ion content is moderate, the three-coordination aluminum ion content is lower, the interaction between metal and aluminum oxide defects is enhanced, and the interaction between hydrogen and the aluminum oxide surface is weakened, so that the overflow of hydrogen on the surface of the catalyst is increased, the catalytic performance of the catalyst can be enhanced by overflow hydrogen, the deactivation of the catalyst is inhibited, more metals such as Ni, fe, V and the like are removed, the surface carbon deposition is reduced, the metal active phase plate crystal length in the vulcanized hydrogenation catalyst is shorter, the plate crystal layer number is more, the steric hindrance effect can be obviously reduced, and the utilization rate of an active phase is improved; and finally, the modified alumina carrier in the hydrogenation catalyst has less penta-coordination aluminum ion content, moderate tetra-coordination aluminum ion content and increased tri-coordination aluminum ion content, weakens interaction between metal and alumina defects, increases active sites, reduces the steric hindrance of reactants, is beneficial to removing impurities such as O, S, N and the like which are difficult to remove in small molecules, has longer metal active phase platelet length and fewer platelet layers in the sulfurized hydrogenation catalyst, further carries out hydrogenation reaction on the small molecules with smaller steric hindrance, improves the utilization rate of active metals, and realizes effective reaction on reactant molecules.
Drawings
FIG. 1 shows the results of a nuclear magnetic analysis of alumina support I of the catalyst used in example 1;
FIG. 2 shows the results of a nuclear magnetic analysis of alumina carrier II of the catalyst used in example 1;
FIG. 3 shows the results of a nuclear magnetic analysis of alumina carrier III of the catalyst used in example 1;
FIG. 4 is a transmission electron microscope image of the sulfided hydrogenation catalyst I used in example 1;
FIG. 5 is a transmission electron microscope image of the sulfided hydrogenation catalyst II used in example 1;
FIG. 6 is a transmission electron micrograph of the sulfided hydrogenation catalyst III used in example 1.
Detailed Description
The method for preparing the catalyst of the present invention will be described in more detail by means of specific examples. The examples are merely illustrative of specific embodiments of the method of the invention and do not constitute a limitation on the scope of the invention.
In the invention, the content of the coordinated aluminum ions is molar content unless otherwise specified.
In the invention, bruker AVANCE III 500 nuclear magnetic resonance spectrometer is used for measuring the type and the quantity of aluminum ions. Experimental conditions: BBO normal phase observation broadband probe, H decoupling, deuterium lock channel; standard broadband range: bb=31p-15N; sensitivity: 367S/N1H NMR,0.1EB 263S/N13C NMR, ASTM; resolution ratio: 0.38HZ1 H,0.1CHCL3,0.13 13C NMR,ASTM.
In the method, the specific surface area and pore structure of the hydrogenation catalyst are measured by adopting a low-temperature liquid nitrogen adsorption method.
In the method, the average length and the average layer number of the platelets of the metal active phase in the hydrogenation catalyst are statistically analyzed by a Transmission Electron Microscope (TEM), and the type of an electron gun is as follows: a LaB6 gun; acceleration voltage: 200kV; dot resolution: 0.23nm; common accessories: gatan 832 CCD camera, EDAX EDS spectrometer; single/double tilting sample stations; line resolution: 0.14nm; magnification factor: 50-1500000. In the test process, the length and the number of layers of active phase platelets in 100 electron microscope pictures are counted and an average value is obtained.
Example 1
The embodiment provides a catalyst grading scheme for solving the problem of long-period operation of poor-quality raw materials, namely, a catalyst is filled in a reactor, a bed layer is filled with a sulfided hydrogenation catalyst I, a sulfided hydrogenation catalyst II and a sulfided hydrogenation catalyst III from top to bottom along the flowing direction of a liquid-phase reactant, wherein the filling volume ratio of the sulfided hydrogenation catalyst I, the sulfided hydrogenation catalyst II and the sulfided hydrogenation catalyst III is 50%:25%:25%.
The alumina raw material used for the alumina carrier I is prepared by hydrolysis of aluminum isopropoxide, is kneaded and extruded into a plastic body, is dried at 120 ℃ for 3 hours, and is roasted at 900 ℃ for 3 hours, so that the required alumina carrier I is obtained. Five-coordination aluminum ion content phi in prepared alumina carrier I V The value is 55 percent, and the content phi of four coordination aluminum ions IV The value is 35%, and the content phi of three-coordination aluminum ions is III The value was 10%.
The preparation method of the sulfided hydrogenation catalyst I comprises the following steps: supersaturating the alumina carrier I with an impregnating solution containing Mo and Ni active components to obtain a catalyst precursor, drying the precursor at 150 ℃ for 4.5h, heating to 550 ℃ at 2 ℃/min, and roasting at constant temperature for 5h to obtain the required catalyst. MoO in the prepared catalyst 3 The mass content is 6.0%, the mass content of NiO is 0.9%, and the alumina carrier content is 93.1%; the properties of the catalyst are as follows: specific surface area of 110m 2 And/g, the pore diameter can be 18.7nm. The catalyst is used for promotingFilling a catalyst into a vulcanization reactor, introducing vulcanized oil wax into the vulcanization reactor, and wetting a catalyst bed; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent carbon disulfide; after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is raised to 260 ℃ at 5 ℃/h, and the temperature is kept constant for 9 hours; and (3) raising the temperature of the catalyst bed to 350 ℃ at a speed of 10 ℃/h, and keeping the temperature for 10 hours to obtain the sulfided hydrogenation catalyst I. In the sulfided hydrogenation catalyst I, the average number of active phase platelets was 8.6, and the average length of the platelets was 2.4nm.
The alumina raw material used for the alumina carrier II is prepared by an aluminum sulfate method, urea is added in the mixing and kneading process to form a plastic body, and then the plastic body is dried for 2 hours at 120 ℃ and baked for 3 hours at 700 ℃ to obtain the required alumina carrier II. Five-coordination aluminum ion content phi in prepared alumina carrier II V The value is 45%, and the content phi of tetra-coordinated aluminum ions is IV The value is 40%, and the content phi of three-coordination aluminum ions is III The value was 15%.
The preparation method of the sulfided hydrogenation catalyst II comprises the following steps: and (3) saturating the alumina carrier II with a mixed solution containing Mo and Ni active components and propylene glycol (the dosage of the propylene glycol is 6% of the mass of the catalyst carrier), so as to obtain a catalyst precursor, drying the precursor at 150 ℃ for 2.5h, heating the precursor to 400 ℃ at 5 ℃/min, and roasting the precursor at constant temperature for 3.0h to obtain the required catalyst. MoO in the prepared catalyst 3 13.0% of NiO, 2.4% of alumina carrier and 84.6%; the properties of the catalyst are as follows: specific surface area of 180m 2 And/g, the pore diameter can be 11.8nm. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil and diesel oil into the vulcanization reactor, and wetting a catalyst bed; then adjusting the temperature of the bed layer to 160 ℃, and injecting a vulcanizing agent carbon disulfide; after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is increased to 220 ℃ at 10 ℃/h, and the temperature is kept constant for 7 hours; and (3) raising the temperature of the catalyst bed to 330 ℃ at 15 ℃/h, and keeping the temperature for 7 hours to obtain the sulfided hydrogenation catalyst II. In the sulfided hydrogenation catalyst II, the average number of active phase platelets was 5.7 and the average platelet length was 4.9nm.
The alumina raw material used for alumina carrier III is prepared by carbonization method and is formed by kneading and extruding stripsDrying the plastic body at 150 ℃ for 2 hours, and roasting at 500 ℃ for 3 hours to obtain the required aluminum oxide carrier III. Five-coordination aluminum ion content phi in prepared modified alumina carrier III V The value is 40%, and the content phi of tetra-coordinated aluminum ions is IV The value is 35%, and the content phi of three-coordination aluminum ions is III The value was 25%.
The preparation method of the sulfided hydrogenation catalyst III comprises the following steps: the carrier III is saturated and impregnated with a mixed solution containing Mo, ni active components and lactose (the lactose amount is 16% of the mass of the catalyst carrier), so as to obtain a catalyst precursor, and the precursor is dried at 100 ℃ for 1h to obtain the required catalyst. MoO in the prepared catalyst 3 22.5% by mass, 3.7% by mass of NiO and 73.8% by mass of alumina carrier; the properties of the catalyst are as follows: specific surface area of 199m 2 And/g, the pore size of the polymer is 8.1nm. Filling the catalyst into a vulcanization reactor, introducing vulcanized gasoline into the vulcanization reactor, and wetting a catalyst bed; then adjusting the temperature of the bed layer to 160 ℃, and injecting a vulcanizing agent carbon disulfide; after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is increased to 190 ℃ at 15 ℃/h, and the temperature is kept constant for 4 hours; and (3) raising the temperature of the catalyst bed to 315 ℃ at 20 ℃/h, and keeping the temperature for 3 hours to obtain the sulfided hydrogenation catalyst III. In the sulfided hydrogenation catalyst III, the average number of active phase platelets was 2.4, and the average platelet length was 8.1nm.
Example 2
The embodiment provides a catalyst grading scheme for solving the problem of long-period operation of poor-quality raw materials, namely, a catalyst is filled in a reactor, a bed layer is filled with a sulfided hydrogenation catalyst I, a sulfided hydrogenation catalyst II and a sulfided hydrogenation catalyst III from top to bottom along the flowing direction of a liquid-phase reactant, wherein the filling volume ratio of the sulfided hydrogenation catalyst I, the sulfided hydrogenation catalyst II and the sulfided hydrogenation catalyst III is 50%:30%:20%.
The alumina raw material used for the alumina carrier I is prepared by hydrolysis of aluminum isopropoxide, is kneaded and extruded into a plastic body, is dried for 3 hours at 150 ℃ and is roasted for 4 hours at 950 ℃ to obtain the required alumina carrier I, and the prepared alumina carrier I has five coordination aluminum ion content phi V The value is 60 percent, and the content phi of tetra-coordinated aluminum ions IV The value is 30%, and the content phi of three-coordination aluminum ions is III The value was 10%.
The preparation method of the sulfided hydrogenation catalyst I comprises the following steps: and (3) supersaturating the carrier I with an impregnating solution containing Mo and Ni active components to obtain a catalyst precursor, drying the precursor at 250 ℃ for 4.5h, heating to 500 ℃ at 4 ℃/min, and roasting at constant temperature for 4.5h to obtain the required catalyst. MoO in the prepared catalyst 3 The mass content is 5.5%, the mass content of NiO is 0.8%, the mass content of alumina carrier is 93.7%, and the catalyst has the following properties: specific surface area of 118m 2 And/g, the pore diameter can be 17.9nm. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil and diesel oil into the vulcanization reactor, and wetting a catalyst bed; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent carbon disulfide; after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is raised to 255 ℃ at 3 ℃/h, and the temperature is kept constant for 10 hours; and (3) raising the temperature of the catalyst bed to 350 ℃ at a speed of 5 ℃/h, and keeping the temperature for 10 hours to obtain the sulfided hydrogenation catalyst I. In the sulfided hydrogenation catalyst I, the average number of active phase platelets was 9.0, and the average length of the platelets was 2.1nm.
The alumina raw material used for the alumina carrier II is prepared by an aluminum sulfate method, ethylenediamine is added in the mixing and kneading process to form a plastic body, the plastic body is dried for 2 hours at 120 ℃, and the plastic body is roasted for 3 hours at 600 ℃ to obtain the required alumina carrier II, wherein the five-coordination aluminum ion content phi in the prepared alumina carrier II V The value is 50%, and the content phi of tetra-coordinated aluminum ions is IV The value is 40%, and the content phi of three-coordination aluminum ions is III The value was 15%.
The preparation method of the sulfided hydrogenation catalyst II comprises the following steps: and (3) saturating and impregnating the carrier II with a mixed solution containing Mo and Ni active components and ethylene glycol (the using amount of the ethylene glycol is 10% of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 200 ℃ for 3.0h, heating the precursor to 480 ℃ at 10 ℃/min, and roasting the precursor at constant temperature for 3.0h to obtain the required catalyst. The prepared catalyst MoO 3 13.2% by mass, 2.8% by mass of NiO, 84% by mass of alumina carrier, and the catalyst has the following properties: a specific surface area of 187m 2 And/g, the pore diameter can be 13.9nm. Loading the catalyst into sulfidingIntroducing vulcanized oil diesel into the reactor, and wetting a catalyst bed; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent carbon disulfide; after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is increased to 220 ℃ at 8 ℃/h, and the temperature is kept constant for 6 hours; and (3) raising the temperature of the catalyst bed to 340 ℃ at 11 ℃/h, and keeping the temperature for 6 hours to obtain the sulfided hydrogenation catalyst II. In the sulfided hydrogenation catalyst II, the average number of active phase platelets was 6.2, and the average platelet length was 5.8nm.
The alumina raw material used for the alumina carrier III is prepared by a carbonization method, is kneaded and extruded into a plastic body, is dried for 2 hours at 150 ℃ and is roasted for 3 hours at 450 ℃ to obtain the required alumina carrier III, and the five-coordination aluminum ion content phi in the prepared modified alumina carrier III V The value is 45%, and the content phi of tetra-coordinated aluminum ions is IV The value is 35%, and the content phi of three-coordination aluminum ions is III The value was 20%.
The preparation method of the sulfided hydrogenation catalyst III comprises the following steps: the carrier III is saturated and impregnated with a mixed solution containing Mo and Ni active components and tributyl glycol (the dosage of the tributyl glycol is 18 percent of the mass of the catalyst carrier), so as to obtain a catalyst precursor, and the precursor is dried at 120 ℃ for 1.0h to obtain the required catalyst. The prepared catalyst MoO 3 23.5% of NiO, 3.8% of alumina carrier and 72.7%; the properties of the catalyst are as follows: specific surface area of 210m 2 And/g, the pore size can be 10.9nm. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil and diesel oil into the vulcanization reactor, and wetting a catalyst bed; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent carbon disulfide; after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is increased to 190 ℃ at 10 ℃/h, and the temperature is kept constant for 3 hours; and (3) raising the temperature of the catalyst bed to 310 ℃ at 17 ℃/h, and keeping the temperature for 3 hours to obtain the sulfided hydrogenation catalyst III. In the sulfided hydrogenation catalyst III, the average number of active phase platelets was 3.0, and the average platelet length was 7.9nm.
Example 3
The embodiment provides a catalyst grading scheme for solving the problem of long-period operation of poor-quality raw materials, namely, a catalyst is filled in a reactor, a bed layer is filled with a sulfided hydrogenation catalyst I, a sulfided hydrogenation catalyst II and a sulfided hydrogenation catalyst III from top to bottom along the flowing direction of a liquid-phase reactant, wherein the filling volume ratio of the sulfided hydrogenation catalyst I to the sulfided hydrogenation catalyst II is 15%:25%:60%.
The alumina raw material used for the alumina carrier I is prepared by hydrolysis of aluminum isopropoxide, is kneaded and extruded into a plastic body, is dried for 3 hours at 200 ℃ and is roasted for 3 hours at 800 ℃ to obtain the required alumina carrier I, and the prepared alumina carrier I has five coordination aluminum ion content phi V The value is 50%, and the content phi of tetra-coordinated aluminum ions is IV The value is 40%, and the content phi of three-coordination aluminum ions is III The value was 10%.
The preparation method of the sulfided hydrogenation catalyst I comprises the following steps: and (3) supersaturating the carrier I with an impregnating solution containing Mo and Ni active components to obtain a catalyst precursor, drying the precursor at 250 ℃ for 4.5h, heating to 500 ℃ at 4 ℃/min, and roasting at constant temperature for 4.5h to obtain the required catalyst. MoO in the prepared catalyst 3 The mass content is 4.2%, the mass content of NiO is 0.8%, and the alumina carrier content is 95%; the properties of the catalyst are as follows: specific surface area of 111m 2 And/g, the pore diameter can be 21.7nm. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil and diesel oil into the vulcanization reactor, and wetting a catalyst bed; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent carbon disulfide; after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is raised to 255 ℃ at 3 ℃/h, and the temperature is kept constant for 10 hours; and (3) raising the temperature of the catalyst bed to 350 ℃ at a speed of 5 ℃/h, and keeping the temperature for 10 hours to obtain the sulfided hydrogenation catalyst I. In the sulfided hydrogenation catalyst I, the average number of active phase platelets was 7.9, and the average length of the platelets was 2.5nm.
The alumina raw material used for the alumina carrier II is prepared by an aluminum sulfate method, diethylene glycol is added in the mixing and kneading process to form a plastic body, the plastic body is dried for 2 hours at 120 ℃, and the plastic body is roasted for 3 hours at 700 ℃, so that the required alumina carrier II is obtained, and the five-coordination aluminum ion content phi in the prepared alumina carrier II V The value is 45%, and the content phi of tetra-coordinated aluminum ions is IV The value is 40%, and the content phi of three-coordination aluminum ions is III The value was 15%.
The preparation method of the sulfided hydrogenation catalyst II comprises the following steps: and (3) saturating the carrier II with a mixed solution containing active components of Mo and Ni and ethylene glycol (the using amount of the ethylene glycol is 10% of the mass of the catalyst carrier), so as to obtain a catalyst precursor, drying the precursor at 200 ℃ for 3.0h, heating the precursor to 480 ℃ at 10 ℃/min, and roasting the precursor at constant temperature for 3.0h to obtain the required catalyst. The prepared catalyst MoO 3 11.3 percent of NiO, 1.8 percent of alumina carrier and 86.9 percent of alumina carrier; the properties of the catalyst are as follows: specific surface area of 154m 2 And/g, the pore size is 15.3nm. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil and diesel oil into the vulcanization reactor, and wetting a catalyst bed; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent carbon disulfide; after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is increased to 220 ℃ at 8 ℃/h, and the temperature is kept constant for 6 hours; and (3) raising the temperature of the catalyst bed to 340 ℃ at 11 ℃/h, and keeping the temperature for 6 hours to obtain the sulfided hydrogenation catalyst II. In the sulfided hydrogenation catalyst II, the average number of active phase platelets was 4.8, and the average platelet length was 5.5nm.
The alumina raw material used for the alumina carrier III is prepared by a carbonization method, is kneaded and extruded into a plastic body, is dried for 2 hours at 150 ℃ and is roasted for 3 hours at 500 ℃ to obtain the required alumina carrier III, and the five-coordination aluminum ion content phi in the prepared modified alumina carrier III V The value is 40%, and the content phi of tetra-coordinated aluminum ions is IV The value is 40%, and the content phi of three-coordination aluminum ions is III The value was 20%.
The preparation method of the sulfided hydrogenation catalyst III comprises the following steps: the carrier III is saturated and impregnated with a mixed solution containing active components of Mo and Ni and lactose (the lactose amount is 17% of the mass of the catalyst carrier), so as to obtain a catalyst precursor, and the precursor is dried at 120 ℃ for 1.5h, so that the required catalyst is obtained. MoO in the prepared catalyst 3 22.3% of NiO, 3.9% of alumina carrier and 73.8% of alumina carrier; the properties of the catalyst are as follows: specific surface area of 222m 2 And/g, the pore size is 9.0nm. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil and diesel oil into the vulcanization reactor, and wetting a catalyst bed;then adjusting the temperature of the bed layer to 160 ℃, and injecting a vulcanizing agent carbon disulfide; after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is increased to 200 ℃ at 15 ℃/h, and the temperature is kept constant for 4.5 hours; and (3) raising the temperature of the catalyst bed to 310 ℃ at 20 ℃/h, and keeping the temperature for 2 hours to obtain the sulfided hydrogenation catalyst III. In the sulfided hydrogenation catalyst III, the average number of active phase platelets was 2.0, and the average platelet length was 7.9nm.
Comparative example 1
The catalyst grading scheme for solving the problem of long-period operation of poor-quality raw materials is provided in the embodiment, namely, a catalyst is filled in a reactor, a bed layer is filled with a sulfided hydrogenation catalyst I, a sulfided hydrogenation catalyst II and a sulfided hydrogenation catalyst III from top to bottom, wherein the filling volume ratio of the sulfided hydrogenation catalyst I, the sulfided hydrogenation catalyst II and the sulfided hydrogenation catalyst III is 15 percent: 25%:60%.
The alumina raw material used for the alumina carrier I is prepared by a carbonization method, is kneaded and extruded into a plastic body, is dried for 2 hours at 150 ℃ and is roasted for 3 hours at 500 ℃ to obtain the required alumina carrier I, and the five-coordination aluminum ion content phi in the prepared modified alumina carrier I V The value is 40%, and the content phi of tetra-coordinated aluminum ions is IV The value is 40%, and the content phi of three-coordination aluminum ions is III The value was 20%.
The preparation method of the sulfided hydrogenation catalyst I comprises the following steps: and (3) supersaturating the carrier I with an impregnating solution containing Mo and Ni active components to obtain a catalyst precursor, drying the precursor at 250 ℃ for 4.5h, heating to 500 ℃ at 4 ℃/min, and roasting at constant temperature for 4.5h to obtain the required catalyst. MoO in the prepared catalyst 3 The mass content is 4.2%, the mass content of NiO is 0.9%, the mass content of alumina carrier is 94.9%, and the catalyst has the following properties: specific surface area of 112m 2 And/g, the pore diameter can be 21.7nm. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil and diesel oil into the vulcanization reactor, and wetting a catalyst bed; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent carbon disulfide; after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is raised to 255 ℃ at 3 ℃/h, and the temperature is kept constant for 10 hours; and (3) raising the temperature of the catalyst bed to 350 ℃ at a speed of 5 ℃/h, and keeping the temperature for 10 hours to obtain the sulfided hydrogenation catalyst I.In the sulfided hydrogenation catalyst I, the average number of active phase platelets was 7.9, and the average length of the platelets was 2.5nm.
The alumina raw material used for the alumina carrier II is prepared by an aluminum sulfate method, diethylene glycol is added in the mixing and kneading process to form a plastic body, the plastic body is dried for 2 hours at 120 ℃, and the plastic body is roasted for 3 hours at 700 ℃, so that the required alumina carrier II is obtained, and the five-coordination aluminum ion content phi in the prepared alumina carrier II V The value is 45%, and the content phi of tetra-coordinated aluminum ions is IV The value is 40%, and the content phi of three-coordination aluminum ions is III The value was 15%.
The preparation method of the sulfided hydrogenation catalyst II comprises the following steps: and (3) saturating and impregnating the carrier II with a mixed solution containing Mo and Ni active components and ethylene glycol (the using amount of the ethylene glycol is 10% of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 200 ℃ for 3.0h, heating the precursor to 480 ℃ at 10 ℃/min, and roasting the precursor at constant temperature for 3.0h to obtain the required catalyst. MoO in the prepared catalyst 3 11.3% of NiO, 1.8% of alumina carrier and 86.9% of catalyst, and the catalyst has the following properties: specific surface area of 159m 2 And/g, the pore diameter can be 16.2nm. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil and diesel oil into the vulcanization reactor, and wetting a catalyst bed; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent carbon disulfide; after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is increased to 220 ℃ at 8 ℃/h, and the temperature is kept constant for 6 hours; and (3) raising the temperature of the catalyst bed to 340 ℃ at 11 ℃/h, and keeping the temperature for 6 hours to obtain the sulfided hydrogenation catalyst II. In the sulfided hydrogenation catalyst II, the average number of active phase platelets was 4.8, and the average platelet length was 5.5nm.
The alumina raw material used in the alumina carrier III is prepared by hydrolysis of aluminum isopropoxide, is kneaded and extruded into a plastic body, is dried for 3 hours at 200 ℃ and is roasted for 3 hours at 800 ℃ to obtain the required alumina carrier II, and the five-coordination aluminum ion content phi in the prepared alumina carrier II V The value is 50%, and the content phi of tetra-coordinated aluminum ions is IV The value is 40%, and the content phi of three-coordination aluminum ions is III The value was 10%.
Preparation method of sulfided hydrogenation catalyst IIIThe following are provided: the carrier III is saturated and impregnated with a mixed solution containing Mo and Ni active components and lactose (the lactose amount is 17% of the mass of the catalyst carrier), so as to obtain a catalyst precursor, and the precursor is dried at 120 ℃ for 1.5h, so that the required catalyst is obtained. MoO in the prepared catalyst 3 21.3% by mass, 3.7% by mass of NiO, 75% by mass of alumina carrier, and the catalyst has the following properties: specific surface area of 221m 2 And/g, the pore size can be 10.2nm. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil and diesel oil into the vulcanization reactor, and wetting a catalyst bed; then adjusting the temperature of the bed layer to 160 ℃, and injecting a vulcanizing agent carbon disulfide; after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is increased to 200 ℃ at 15 ℃/h, and the temperature is kept constant for 4.5 hours; and (3) raising the temperature of the catalyst bed to 310 ℃ at 20 ℃/h, and keeping the temperature for 2 hours to obtain the sulfided hydrogenation catalyst III. In the sulfided hydrogenation catalyst III, the average number of active phase platelets was 2.0, and the average platelet length was 7.9nm.
Comparative example 2
The catalyst grading scheme for solving the problem of long-period operation of poor-quality raw materials is provided in the embodiment, namely, a catalyst is filled in a reactor, a bed layer is filled with a sulfided hydrogenation catalyst I, a sulfided hydrogenation catalyst II and a sulfided hydrogenation catalyst III from top to bottom, wherein the filling volume ratio of the sulfided hydrogenation catalyst I, the sulfided hydrogenation catalyst II and the sulfided hydrogenation catalyst III is 15 percent: 25%:60%.
The alumina raw material used for the alumina carrier I is prepared by hydrolysis of aluminum isopropoxide, is kneaded and extruded into a plastic body, is dried for 3 hours at 200 ℃ and is roasted for 3 hours at 800 ℃ to obtain the required alumina carrier I, and the prepared alumina carrier I has five coordination aluminum ion content phi V The value is 50%, and the content phi of tetra-coordinated aluminum ions is IV The value is 40%, and the content phi of three-coordination aluminum ions is III The value was 10%.
The preparation method of the sulfided hydrogenation catalyst I comprises the following steps: and (3) supersaturating the carrier I with an impregnating solution containing Mo and Ni active components to obtain a catalyst precursor, drying the precursor at 250 ℃ for 4.5h, heating to 500 ℃ at 4 ℃/min, and roasting at constant temperature for 4.5h to obtain the required catalyst. MoO in the prepared catalyst 3 The mass containsThe amount is 4.4%, the mass content of NiO is 0.9%, the content of alumina carrier is 94.7%, and the catalyst has the following properties: specific surface area of 121m 2 And/g, the pore diameter can be 22.7nm. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil and diesel oil into the vulcanization reactor, and wetting a catalyst bed; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent carbon disulfide; after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is raised to 255 ℃ at 3 ℃/h, and the temperature is kept constant for 10 hours; and (3) raising the temperature of the catalyst bed to 350 ℃ at a speed of 5 ℃/h, and keeping the temperature for 10 hours to obtain the sulfided hydrogenation catalyst I. In the sulfided hydrogenation catalyst I, the average number of active phase platelets was 7.9, and the average length of the platelets was 2.5nm.
The alumina raw material used for the alumina carrier II is prepared by an aluminum sulfate method, diethylene glycol is added in the mixing and kneading process to form a plastic body, the plastic body is dried for 2 hours at 120 ℃, and the plastic body is roasted for 3 hours at 700 ℃, so that the required alumina carrier II is obtained, and the five-coordination aluminum ion content phi in the prepared alumina carrier II V The value is 50%, and the content phi of tetra-coordinated aluminum ions is IV The value is 40%, and the content phi of three-coordination aluminum ions is III The value was 10%.
The preparation method of the sulfided hydrogenation catalyst II comprises the following steps: and (3) saturating and impregnating the carrier II with a mixed solution containing Mo and Ni active components and ethylene glycol (the using amount of the ethylene glycol is 10% of the mass of the catalyst carrier) to obtain a catalyst precursor, drying the precursor at 200 ℃ for 3.0h, heating the precursor to 480 ℃ at 10 ℃/min, and roasting the precursor at constant temperature for 3.0h to obtain the required catalyst. MoO in the prepared catalyst 3 11.3% of NiO, 1.8% of alumina carrier and 86.9% of catalyst, and the catalyst has the following properties: specific surface area of 159m 2 And/g, the pore size is 15.7nm. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil and diesel oil into the vulcanization reactor, and wetting a catalyst bed; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent carbon disulfide; after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is increased to 220 ℃ at 8 ℃/h, and the temperature is kept constant for 6 hours; and (3) raising the temperature of the catalyst bed to 340 ℃ at 11 ℃/h, and keeping the temperature for 6 hours to obtain the sulfided hydrogenation catalyst II. In the sulfided hydrogenation catalyst II, livingThe average number of layers of the chiral photo crystals was 4.8, and the average length of the platelets was 5.5nm.
The alumina raw material used for the alumina carrier III is prepared by a carbonization method, is kneaded and extruded into a plastic body, is dried for 2 hours at 150 ℃ and is roasted for 3 hours at 500 ℃, and the required alumina carrier III is obtained, and the five-coordination aluminum ion content phi in the prepared modified alumina carrier III V The value is 50%, and the content phi of tetra-coordinated aluminum ions is IV The value is 40%, and the content phi of three-coordination aluminum ions is III The value was 10%.
The preparation method of the sulfided hydrogenation catalyst III comprises the following steps: the carrier III is saturated and impregnated with a mixed solution containing Mo and Ni active components and lactose (the lactose amount is 17% of the mass of the catalyst carrier), so as to obtain a catalyst precursor, and the precursor is dried at 120 ℃ for 1.5h, so that the required catalyst is obtained. MoO in the prepared catalyst 3 22.3% of NiO, 3.4% of alumina carrier and 74.3% of catalyst, and the catalyst has the following properties: specific surface area of 221m 2 And/g, the pore size is 9.8nm. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil and diesel oil into the vulcanization reactor, and wetting a catalyst bed; then adjusting the temperature of the bed layer to 160 ℃, and injecting a vulcanizing agent carbon disulfide; after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is increased to 200 ℃ at 15 ℃/h, and the temperature is kept constant for 4.5 hours; and (3) raising the temperature of the catalyst bed to 310 ℃ at 20 ℃/h, and keeping the temperature for 2 hours to obtain the sulfided hydrogenation catalyst III. In the sulfided hydrogenation catalyst III, the average number of active phase platelets was 2.0, and the average platelet length was 7.9nm.
Comparative example 3
The catalyst grading scheme for solving the problem of long-period operation of poor-quality raw materials is provided in the embodiment, namely, a catalyst is filled in a reactor, a bed layer is filled with a sulfided hydrogenation catalyst I, a sulfided hydrogenation catalyst II and a sulfided hydrogenation catalyst III from top to bottom, wherein the filling volume ratio of the sulfided hydrogenation catalyst I, the sulfided hydrogenation catalyst II and the sulfided hydrogenation catalyst III is 15 percent: 25%:60%.
The alumina raw material used for the alumina carrier I is prepared by hydrolysis of aluminum isopropoxide, is kneaded and extruded into a plastic body, is dried for 3 hours at 200 ℃ and is roasted for 3 hours at 800 ℃ to obtain the required alumina carrierBody I, which is prepared from the body I, and the content phi of penta-coordinated aluminum ions in the alumina carrier I V The value is 50%, and the content phi of tetra-coordinated aluminum ions is IV The value is 40%, and the content phi of three-coordination aluminum ions is III The value was 10%.
The preparation method of the hydrogenation catalyst I comprises the following steps: and (3) supersaturating the carrier I with an impregnating solution containing Mo and Ni active components to obtain a catalyst precursor, drying the precursor at 250 ℃ for 4.5h, heating to 500 ℃ at 4 ℃/min, and roasting at constant temperature for 4.5h to obtain the required catalyst. MoO in the prepared catalyst 3 The mass content is 4.2%, the mass content of NiO is 0.8%, the mass content of alumina carrier is 95%, and the catalyst has the following properties: specific surface area of 102m 2 And/g, the pore diameter can be 21.7nm. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil and diesel oil into the vulcanization reactor, and wetting a catalyst bed; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent carbon disulfide; after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is raised to 255 ℃ at 3 ℃/h, and the temperature is kept constant for 10 hours; and (3) raising the temperature of the catalyst bed to 350 ℃ at a speed of 5 ℃/h, and keeping the temperature for 10 hours to obtain the sulfided hydrogenation catalyst I. In the sulfided hydrogenation catalyst I, the average number of active phase platelets was 2.2, and the average length of the platelets was 7.8nm.
The alumina raw material used for the alumina carrier II is prepared by an aluminum sulfate method, diethylene glycol is added in the mixing and kneading process to form a plastic body, the plastic body is dried for 2 hours at 120 ℃, and the plastic body is roasted for 3 hours at 700 ℃, so that the required alumina carrier II is obtained, and the five-coordination aluminum ion content phi in the prepared alumina carrier II V The value is 45%, and the content phi of tetra-coordinated aluminum ions is IV The value is 40%, and the content phi of three-coordination aluminum ions is III The value was 15%.
The preparation method of the sulfided hydrogenation catalyst II comprises the following steps: supersaturating the carrier II with an impregnating solution containing Mo and Ni active components to obtain a catalyst precursor, drying the precursor at 250 ℃ for 4.5h, heating to 500 ℃ at 4 ℃/min, and roasting at constant temperature for 4.5h to obtain the required catalyst. MoO in the prepared catalyst 3 11.3% of NiO, 1.8% of alumina carrier and 86.9% of catalyst, and the catalyst has the following properties: specific surface area of157m 2 And/g, the pore diameter can be 16.2nm. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil and diesel oil into the vulcanization reactor, and wetting a catalyst bed; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent carbon disulfide; after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is raised to 255 ℃ at 3 ℃/h, and the temperature is kept constant for 10 hours; and (3) raising the temperature of the catalyst bed to 350 ℃ at a speed of 5 ℃/h, and keeping the temperature for 10 hours to obtain the sulfided hydrogenation catalyst II. In the sulfided hydrogenation catalyst II, the average number of active phase platelets was 2.2, and the average platelet length was 8.0nm.
The alumina raw material used for the alumina carrier III is prepared by a carbonization method, is kneaded and extruded into a plastic body, is dried for 2 hours at 150 ℃ and is roasted for 3 hours at 500 ℃, and the required alumina carrier III is obtained, and the five-coordination aluminum ion content phi in the prepared modified alumina carrier III V The value is 40%, and the content phi of tetra-coordinated aluminum ions is IV The value is 40%, and the content phi of three-coordination aluminum ions is III The value was 20%.
The preparation method of the sulfided hydrogenation catalyst III comprises the following steps: and (3) supersaturating the carrier II with an impregnating solution containing Mo and Ni active components to obtain a catalyst precursor, drying the precursor at 250 ℃ for 4.5h, heating to 500 ℃ at 4 ℃/min, and roasting at constant temperature for 4.5h to obtain the required catalyst. MoO in the prepared catalyst 3 22.3% by mass, 3.9% by mass of NiO, 73.8% by mass of alumina carrier, and the catalyst has the following properties: specific surface area of 221m 2 And/g, the pore size can be 10.2nm. Filling the catalyst into a vulcanization reactor, introducing vulcanized oil and diesel oil into the vulcanization reactor, and wetting a catalyst bed; then adjusting the temperature of the bed layer to 170 ℃, and injecting a vulcanizing agent carbon disulfide; after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is raised to 255 ℃ at 3 ℃/h, and the temperature is kept constant for 10 hours; and (3) raising the temperature of the catalyst bed to 350 ℃ at a speed of 5 ℃/h, and keeping the temperature for 10 hours to obtain the sulfided hydrogenation catalyst III. In the sulfided hydrogenation catalyst III, the average number of active phase platelets was 2.0, and the average platelet length was 7.9nm.
Example 4
This example is a comparative test of the activity and stability of the catalyst combination systems of examples 1, 2, and 3 and comparative examples 1, 2, and 3 on a 100mL fixed bed compact hydrogenation unit, using the top feed. The properties of the raw oil were evaluated as shown in table 1; the evaluation conditions are shown in Table 2; the catalyst assembly protocol is shown in Table 3; the evaluation results of the catalyst combination scheme are shown in Table 4.
TABLE 1 oil Properties of raw materials
Raw oil Residuum
Density (20 ℃), g.cm- 3 1.034
Carbon residue, wt% 20.11
S，wt％ 5.22
Ni+V，μg·g- 1 178.5
Table 2 evaluation of process conditions
Reaction temperature, DEG C 380
Partial pressure of reaction hydrogen, MPa 15.0
Liquid hourly space velocity, h- 1 0.7
Hydrogen to oil volume ratio 800:1
Table 3 evaluation results of catalyst combinations of examples
The above describes in detail the specific embodiments of the present invention, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (12)

1. The grading method of the hydrogenation catalyst is characterized by comprising a grading system consisting of n-level sulfur-state hydrogenation catalysts, wherein n is more than or equal to 3, preferably n is 3 or 4, each level of hydrogenation catalyst comprises an alumina carrier and a metal active component, and the alumina carrier contains three coordination types of aluminum ions: three-coordinated aluminum ion Al 3+ Ⅲ Four-coordinated aluminum ion Al 3+ Ⅳ And penta-coordinated aluminum ion Al 3+ Ⅴ The hydrogenation catalyst of each stage takes the total amount of three ligand aluminum in the alumina carrier as the reference, and the content of penta-coordination aluminum ions along the flow direction of the liquid phase reactantGradually decreasing with the amplitude of 5-15 Percentage points; the average length of metal active phase platelets of each stage of sulfided hydrogenation catalyst is gradually increased along the flow direction of the liquid phase reactant, and the average number of platelets is gradually reduced.
2. The method of gradation according to claim 1, wherein the content of the three-coordinated aluminum ions is based on the total amount of three-coordinated aluminum in the alumina carrier in the flow direction of the liquid phase reactantGradually increasing the scale-up with the amplitude of 1-10 percentage points.
3. The grading method according to claim 1, wherein in each stage of the sulfided hydrogenation catalyst in the flow direction of the liquid phase reactant, the average length of the metal active photo crystals is 1 to 9nm, the stepwise increase range is 1 to 5nm, preferably 2 to 4nm, the average number of layers of the metal active photo crystals is 1 to 9, and the stepwise decrease range is 1 to 5, preferably 2 to 4.
4. The grading method according to claim 1, wherein the alumina carrier of each hydrogenation catalyst has a pentadentate aluminum ion content based on the total content of three kinds of ligand aluminum40-60% of tetra-coordinated aluminum ion content>30-50% of three-coordination aluminum ion content>10 to 30 percent.
5. The grading process according to claim 1, characterized in that in the alumina support of the same grade of catalyst, five coordinates are present Content of aluminum ionContent of tetra-coordinated aluminum ion ≡>Content of tri-coordinated aluminum ion>
6. The grading method according to claim 1 or 5, wherein the difference between the penta-coordinated aluminum ion content and the tri-coordinated aluminum ion content in the alumina carrier of the same grade of catalyst is 15% to 50%.
7. The grading method according to claim 1, wherein the grading system comprises three hydrogenation catalysts in a sulfided state, and the three-stage filling ratio is 10% -90% in the flowing direction of the liquid phase reactant based on the total volume of the catalysts in the reactor: 5% -40%: 5% -80%, and the sum of the filling ratios of all stages is 100%.
8. The grading method according to claim 1, wherein the grading system comprises four hydrogenation catalysts in a sulfided state, and the four-stage packing ratio in the flow direction of the liquid phase reactant is as follows, based on the total volume of the catalysts in the reactor: 10% -70%: 10% -40%: 10% -40%: 10% -70%, and the sum of the filling proportion of each level is 100%; the preferred loading ratios are: 10% -40%: 10% -40%: 10% -40%: 10% -40%, and the sum of the filling ratios of all levels is 100%.
9. The grading method according to claim 1, characterized in that in each stage of hydrogenation catalyst the active metal is selected from at least one of the group VIII and/or group VIB metal elements, the active metal being in the form of oxide, based on the weight of the hydrogenation catalyst, the group VIII metal content being 0.2 to 9.0wt%, preferably 0.5 to 9.0wt%, the group VIB metal content being 4 to 50wt%, preferably 4 to 45wt%.
10. The grading method according to claim 1, characterized in that the alumina carrier is present in the respective stages of hydrogenation catalysts in an amount of 45 to 95wt%, preferably 50 to 90wt%, based on the weight of the hydrogenation catalyst.
11. Use of the catalyst fractionation process of any one of claims 1-10 in the hydroprocessing of poor quality feedstocks.
12. The use according to claim 11, wherein the reaction conditions of the hydrotreatment are: the average reaction temperature is 200-450 ℃, preferably 250-430 ℃; the partial pressure of the reaction hydrogen is 4.0MPa to 20.0MPa, preferably 8.0MPa to 18.0MPa; the liquid hourly space velocity is 0.15h -1 ～3.0h -1 Preferably 0.2h -1 ～2.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The volume ratio of hydrogen to oil is 300-1500, preferably 500-1200.
CN202210012187.1A 2022-01-06 2022-01-06 Hydrogenation catalyst grading method and application thereof Pending CN116440918A (en)

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