WO2024060582A1 - 加氢催化剂及其制备方法和应用 - Google Patents

加氢催化剂及其制备方法和应用 Download PDF

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WO2024060582A1
WO2024060582A1 PCT/CN2023/086555 CN2023086555W WO2024060582A1 WO 2024060582 A1 WO2024060582 A1 WO 2024060582A1 CN 2023086555 W CN2023086555 W CN 2023086555W WO 2024060582 A1 WO2024060582 A1 WO 2024060582A1
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hydrogenation catalyst
hydrogen
catalyst
component
content
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PCT/CN2023/086555
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English (en)
French (fr)
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蒋淑娇
丁思佳
袁胜华
耿新国
杨刚
张�成
隋宝宽
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中国石油化工股份有限公司
中石化（大连）石油化工研究院有限公司
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Publication of WO2024060582A1 publication Critical patent/WO2024060582A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum

Definitions

  • the invention belongs to the field of hydrogenation catalysts and relates to a hydrogenation catalyst and a preparation method and application thereof.
  • the active phase used in residual hydrotreating is mainly Co(Ni)-Mo(W)-S.
  • the active phase can be modified with heteroatoms during the catalyst preparation process. , to improve the performance of the catalyst.
  • CN101722039A discloses a hydrogenation catalyst and a preparation method thereof. During the catalyst preparation process, gallium and rare earth metal elements are introduced to modify the catalyst. The additives of this modification method are mainly modified carriers, which has limited improvement effect and will lead to serious migration of active metals during the processing of heavy oil.
  • CN113559875A discloses a hydrogenation catalyst and its preparation method. During the preparation process of the carrier, auxiliary agents phosphorus and magnesium are introduced to adjust the pore structure and the pore diffusion of the catalyst. This method is still based on carrier modification, without targeted modification of the active phase, and lacks adaptability to the hydrogenation treatment of some unconventional and inferior raw materials.
  • CN101844081A discloses a method for preparing a selective hydrogenation catalyst. During the active metal impregnation process, a zinc additive is introduced to improve the hydrodesulfurization effect of the catalyst. With this modification method, it is difficult to vulcanize zinc and nickel simultaneously, resulting in many active phases that are not modified by Zn. The desulfurization activity is insufficient when processing inferior oil products, especially residual oil with high sulfur content.
  • the present invention provides a hydrogenation catalyst and a preparation method and application thereof.
  • the hydrogenation catalyst provided by the present invention has good hydrogenation processing capacity and stability, and is suitable for the processing of various types of crude oil.
  • a first aspect of the present invention provides a hydrogenation catalyst.
  • the hydrogenation catalyst is a sulfurized hydrogenation catalyst, including a carrier, active component A, active component B and a modification auxiliary component.
  • the active component A At least one selected from the group VIII metal elements
  • the active component B is selected from at least one group VIB metal element
  • the modification auxiliary component is selected from the group consisting of IB, IIA, IIB, IIIA and At least one element from group VIA;
  • the hydrogenation catalyst is characterized by the TEM-EDS method, and the content of the modification aid component distributed in the A-B-S active phase region accounts for 60%-95% of the total modification aid component content, preferably 75%- 90%.
  • the modified auxiliary component distributed in the A-B-S active phase region has a higher content, so that the modified auxiliary component can function better and effectively combine with the A-B-S active phase.
  • the inventors of the present invention found during the research process that most of the existing technologies focus on the problem of introducing additive metals into oxidized hydrogenation catalysts, but the inventors of the present invention found that this modification is not localized and lacks specificity, and has problems such as poor effect, insufficient oil adaptability and stability, etc.
  • a second aspect of the invention provides a method for preparing a hydrogenation catalyst, which method includes the following steps:
  • step (3) Contact and react the treated catalyst obtained in step (2) with the material containing the precursor of the modification auxiliary component;
  • the modification auxiliary component is selected from at least one of the elements of groups IB, IIA, IIB, IIIA and VIA.
  • the oxidation state hydrogenation catalyst is first sulfurized and then desulfurized, so that the metal active phase that needs to be modified is in a specific sulfur loss high activity state, and the outer edge layer of the active phase is exposed.
  • the active metal can effectively retain the internal three-coordinated sulfur atoms in the hydrogenation active phase and the stable A-B-S crystal structure.
  • the modified additive component can more effectively contact the outer metal of the active phase, so that the resulting hydrogenation
  • the modification auxiliary component (represented by R) forms an R-A-B-S combined mixed active phase with A, B and S to achieve the purpose of modification.
  • a third aspect of the present invention provides the application of the hydrogenation catalyst described in the first aspect or the hydrogenation catalyst prepared by the method described in the second aspect in the hydrogenation of oil products.
  • the catalyst provided by the present invention is applied to oil hydrogenation, and has good hydrogenation processing capacity and stability.
  • the selection of different modification auxiliary components also makes the catalyst provided by the present invention have additional advantages, such as selectivity.
  • a first aspect of the present invention provides a hydrogenation catalyst.
  • the hydrogenation catalyst is a sulfurized hydrogenation catalyst, including a carrier, active component A, active component B and a modification auxiliary component.
  • the active component A At least one selected from the metal elements of Group VIII
  • the active component B is selected from at least one metal element of Group VIB
  • the modification auxiliary component is selected from IB, IIA, IIB, At least one element from Group IIIA and VIA;
  • the hydrogenation catalyst is characterized by the TEM-EDS method, and the content of the modification aid component distributed in the A-B-S active phase region accounts for 60%-98% of the total modification aid component content.
  • the A-B-S active phase has a conventional interpretation in the field of hydrogenation catalysts.
  • the A-B-S active phase refers to the effective active center of the hydrogenation catalyst. This concept was proposed by Haldor Topsoe Company in 1984.
  • the content of the modifying auxiliary components distributed in the ABS active phase area accounts for the total content of the modifying auxiliary components and is represented by RABS/R, where R represents the modifying auxiliary component and RABS represents the distribution.
  • the content of modification aid components in the ABS active phase area, R total represents the total content of modification aid components in the catalyst.
  • the RABS/R of the present invention is characterized by the TEM-EDS (Transmission Electron Microscopy-Energy Dispersion X-ray Spectroscopy) method.
  • the instrument model used is a Japanese JEOL JEM2200FS emission transmission electron microscope, equipped with a scanning transmission accessory and an American EDAX X-ray Energy Spectrum Attachment.
  • the electron microscope accelerating voltage is 200KV.
  • the condenser diaphragm In STEM mode, the condenser diaphragm is set to 2, and the Spot size is 0.5nm.
  • the measurement process is as follows: Grind the catalyst particles, prepare samples using the suspension method, put 0.1g catalyst sample into a 2mL container, ultrasonically disperse it with absolute ethanol, take the supernatant, use a dropper to take two to three drops, and drop them on the diameter 3mm sample net, dry to obtain the sample to be tested, and then use TEM to observe and analyze the sample to be tested, and then combine with EDS to make statistics on the content distribution of the modified additive components in the area where the activity is observed by TEM, and use the modified additive
  • the corresponding peak areas of the components are measured to obtain the ratio of the content of the modifying auxiliary components distributed in the ABS active phase area to the content of the total modifying auxiliary components ( represented by RABS/R).
  • the RABS/R of the present invention It is always obtained by averaging the data obtained by selecting
  • the content of the modifying aid component distributed in the A-B-S active phase region accounts for 75%-98% of the total modifying aid component content, for example, 75%, 78%, 80%, 82%, 84%, 86%, 88%, 90%, and any value in the range formed by any two of these values.
  • the modifying additive components are often introduced into the oxidation state catalyst and then vulcanized.
  • the existing technology adopts the method of combining first and then forming an active phase.
  • the proportion of the modifying additive components that truly exert an effective effect is relatively small. Smaller.
  • the inventor of the present invention found that the ratio of the content of the modifying additive components distributed in the Ni-Mo-S active phase area to the total content of the modifying additive components in the prior art is generally 30%. the following.
  • the hydrogenation catalyst is characterized by the TEM-EDS method.
  • the sulfur content at the corners of the A-B-S active phase accounts for less than 6.0% of the total sulfur content in the A-B-S active phase, preferably 0.5%-4.5%. % is, for example, 0.5%, 1%, 2%, 3%, 4%, 4.5%, and any value in the range formed by any two of these values.
  • the sulfur content at the corners of the active phase is moderately reduced, which is beneficial to exposing the empty orbitals of the atoms of the active components to the outside.
  • the adsorption of the organic matter of the active phase modification auxiliary components is enhanced, making the modification more efficient.
  • the sexual additive components are better fixed at the corners of the active phase.
  • S corner position /S total The sulfur content in the corner positions of the ABS active phase accounts for the total sulfur content in the ABS active phase, expressed as S corner position /S total , where S corner position represents the sulfur content in the corner positions of the ABS active phase, and S total represents the ABS active phase. total sulfur content.
  • S corner position /S always passes through TEM- Characterized by EDS (Transmission Electron Microscope-Energy Dispersion X-ray Spectroscopy) method, the instrument model used is the same as above.
  • the measurement process is as follows: Grind the catalyst particles, prepare samples using the suspension method, put 0.1g catalyst sample into a 2mL container, ultrasonically disperse it with absolute ethanol, take the supernatant, use a dropper to take two to three drops, and drop them on the diameter
  • the sample to be tested is obtained by drying on a 3mm sample net, and the sample to be tested is observed and analyzed using TEM, and then combined with EDS to make statistics on the S content distribution in the active phase area observed by TEM.
  • the distance less than 1 nm from the edge endpoint of the active phase is defined as the corner position of the active phase.
  • the ABS active phase is obtained.
  • the sulfur content in corner positions accounts for the total sulfur content in the ABS active phase (expressed as S corner positions /S total ).
  • the S corner position /S is always obtained by averaging the data obtained by selecting 40 TEM images combined with EDS analysis.
  • the auxiliary elements have been introduced when the active metal is in the oxide precursor state.
  • the active metal is sulfurized, the auxiliary elements are difficult to High selectivity is loaded on the active phase, and the direct modification effect is poor.
  • the sulfided catalyst provided in the prior art has a larger value of S corner position /S total .
  • the content of active component A is 1-10% in terms of elements, preferably 1.5%-6%, such as 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, and any value in the range formed by any two of these values; in terms of elements, the content of active component B is 6 %-24%, preferably 8%-18%, such as 8%, 9%, 10%, 12%, 14%, 16%, 18%, and any range consisting of any two of these values. value.
  • the content of the modification auxiliary component is 0.2%-4%, preferably 0.8%-4%, such as 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, and any value in the range formed by any two of these values.
  • the present invention can effectively improve the performance of the hydrogenation catalyst by using less modification auxiliary components.
  • the content of sulfur element is 3%-20%, preferably 4%-15%, such as 4%, 5%, 6%, 7%, 8% , 9%, 10%, 11%, 12%, 13%, 14%, 15%, and any value in the range formed by any two of these values.
  • the contents of active component A, active component B, modification aid component and sulfur element are measured by ICP, and the equipment used is OPTIMA 7000DV type atomic emission spectrometer produced by PE Company. Dissolve 0.1g sample in a mixed solution with a volume ratio of 3HCl: 1HNO3 :0.5HF, and then dilute the mixed solution with deionized water to a certain volume so that the content of the element to be measured in the solution is between 1-10ppm. Then perform the measurement.
  • the content of active component A is 1-10%, preferably 1.5%-6%; in terms of elements, the content of active component A is 1-10%, preferably 1.5%-6%;
  • the content of B is 6%-24%, preferably 8%-18%.
  • the content of the modification aid component is 0.2%-4%, preferably 0.8%-4%, and the content of sulfur element is 3%. -20%, preferably 4%- 15%, the content of carrier is 42-89%, preferably 57-85%.
  • the hydrogenation catalyst provided according to the present invention may also contain other components. It is known that the sum of the contents of all components in the hydrogenation catalyst is 100%.
  • the active component A is Co and/or Ni
  • the active component B is Mo and/or W.
  • the active component A is Ni and the active component B is Mo.
  • Using the catalyst of this preferred embodiment is more beneficial to the hydrotreating of heavy oil.
  • the present invention has a wide range of specific types of modification auxiliary components, and all of the above types can achieve the purpose of improving the hydrogenation catalyst's hydrotreating capacity and stability.
  • the hydrogenation catalyst can have additional advantages and be more suitable for the treatment of specific oil products by selecting from specific types of modifying additive components.
  • the modification auxiliary component is selected from at least one of Cu, Ag, Au, Mg, Ca, Zn, Cd, Ga and Se, more preferably one of Ag, Mg, Zn, Ga and Se At least one.
  • the inventor of the present invention found during the research process that when Ag is selected as the modification additive component, it still has good stability in a low-sulfur environment, and is especially suitable for long-term processing of low-sulfur or sulfur-free raw materials (including but not Limited to at least one of biodiesel, Fischer-Tropsch synthetic oil, low-temperature coal tar, etc.), and the catalyst has good hydrogenation saturation selectivity for aromatic hydrocarbons.
  • the catalyst when Mg is selected as the modification auxiliary component, the catalyst has better olefin hydrogenation selectivity and is particularly suitable for processing raw oils with more olefins, such as at least one of coal-based synthetic oil, coal tar, boiling bed residue oil hydrogenation tail oil, ethylene tar, etc.
  • the inventors of the present invention have found in the course of research that when Zn is selected as the modification auxiliary component, the catalyst has better hydrodesulfurization selectivity and is particularly suitable for hydrodesulfurization treatment of heavy oil such as deasphalted oil.
  • the inventor of the present invention found that when Ga is selected as the modification additive component, the hydrodenitrification selectivity of the catalyst is better, and is particularly suitable for the hydrodenitrification treatment of heavy oils such as deasphalted oil.
  • the inventor of the present invention found during the research process that when Se is selected as the modification additive component, the catalyst has better selectivity for hydrogenation and carbon residue removal, and is especially suitable for heavy feed oils with higher carbon residue content such as inferior heavy oil or Treatment of residual oil.
  • the present invention has no particular limitation on the carrier, and can be any carrier conventionally used in the art, can be a commercially available product, or can be prepared by any method in the prior art.
  • the carrier can be an inorganic refractory oxide.
  • the carrier is selected from at least one of aluminum oxide, silicon oxide, and amorphous silicon aluminum.
  • the present invention has a wide selection range for the specific surface area and pore volume of the carrier.
  • the specific surface area of the carrier is 200-500m 2 /g, preferably 250-400m 2 /g, and the pore volume is 0.4-1.0cm 3 /g. , preferably 0.6-0.8cm 3 /g.
  • the carrier may also contain doping elements.
  • the doping elements may be, for example, one or more of phosphorus, silicon, boron, fluorine, sodium and other elements.
  • the addition amount of the doping element can be a conventional addition amount, preferably accounting for 0.5%-6% of the carrier mass.
  • a second aspect of the invention provides a method for preparing a hydrogenation catalyst, which method includes the following steps:
  • step (3) Contact and react the treated catalyst obtained in step (2) with the material containing the precursor of the modification auxiliary component;
  • the modification auxiliary component is selected from at least one of group IB, IIA, IIB, IIIA and VIA elements.
  • the oxidation state hydrogenation catalyst is a variety of oxidation state hydrogenation catalysts commonly used in the art, and is not particularly limited.
  • the catalyst may be prepared by conventional methods in the art or may be purchased as a commercial catalyst.
  • the oxidation state hydrogenation catalyst is an oxidation state hydrogenation catalyst with heavy oil hydrogenation function.
  • the oxidation state hydrogenation catalyst includes a carrier and active component A and active component B.
  • the active component A is selected from at least one metal element of Group VIII, so
  • the active component B is selected from at least one metal element in Group VIB.
  • the selection range of the carrier and active component A and active component B can be the same as the selection range described in the first aspect above, and will not be described again here.
  • the content of the carrier is 50%-90%, the content of the active component B calculated as oxide is 10%-35%, and the content of the active component A calculated as oxide is 2%-8%.
  • the present invention has no special limitations on the sulfidation in step (1), which can be carried out by conventional methods in the field.
  • the sulfidation in step (1) is full sulfidation, that is, the active metal in the oxidation state hydrogenation catalyst reaches the level of complete sulfidation.
  • well-known vulcanization methods can be used, preferably the vulcanization includes dry vulcanization and/or wet vulcanization. Dry vulcanization and wet vulcanization mentioned in the present invention have conventional interpretations in this field.
  • the vulcanization conditions include: the vulcanization temperature is 240-400°C, the vulcanization time is 2-10h, the pressure of hydrogen is 2-12MPa, and the flow rate of hydrogen is 2-25mL ⁇ min -1 ⁇ g -1 oxidation state
  • the sulfurization temperature is 280-380°C
  • the sulfurization time is 3-8h
  • the pressure of hydrogen is 3-10MPa
  • the flow rate of hydrogen is 3-20mL ⁇ min -1 ⁇ g -1 oxidation state hydrogenation catalyst.
  • the vulcanization liquid used in the wet vulcanization includes sulfur-containing compounds and organic solvents.
  • the sulfur-containing compound is selected from at least one of dimethyl disulfide, carbon disulfide, diethyl sulfide, ethyl mercaptan, n-butyl mercaptan, di-tertiary polysulfide and dimethyl sulfoxide.
  • the organic solvent is selected from at least one of cyclohexane, n-heptane, aviation kerosene and diesel.
  • the mass fraction of the sulfur-containing compound in the sulfurization liquid can be selected from a wide range, preferably 2%-7%, and more preferably 4%-6%.
  • the flow rate of the sulfide liquid is preferably 0.5-5 mL ⁇ h -1 ⁇ g -1 oxidation state hydrogenation catalyst, and preferably 1-4 mL ⁇ h -1 ⁇ g -1 oxidation state hydrogenation catalyst.
  • the sulfide gas used in the dry vulcanization includes hydrogen sulfide and hydrogen.
  • the volume content of hydrogen sulfide in the sulfide gas is 1-10%.
  • the vulcanization treatment is a mild vulcanization treatment.
  • the mild vulcanization treatment It refers to removing the low-coordinated sulfur atoms at the corner positions of the active phase after sulfide, while retaining the three-coordinated sulfur atoms in the active phase bulk phase.
  • the oxidation state hydrogenation catalyst of the present invention undergoes primary sulfurization and sulfidation treatment in sequence, so that the metal active phase that needs to be modified is in a specific sulfur loss and high activity state, and the outer layer of the active phase edge is the exposed active component, and at the same time, it can effectively retain
  • the internal three-coordinated sulfur atoms in the hydrogenation active phase and the stable A-B-S crystal structure are more conducive to the subsequent modification of the additive components to more effectively contact the outer layer of the active phase metal, so that the resulting hydrogenation catalyst is modified
  • the auxiliary component (represented by R) forms an R-A-B-S combined mixed active phase with active component A, active component B and S to achieve the purpose of improving the performance of the hydrogenation catalyst.
  • the temperature of the vulcanization treatment in step (2) is lower than the vulcanization temperature.
  • the temperature of the vulcanization treatment is 50-100°C lower than the vulcanization temperature.
  • the conditions for the vulcanization treatment include: temperature is 180-370°C, preferably 200-300°C; treatment time is 4-24 hours, preferably 6-16 hours, and total pressure is 2-18MPa, preferably 4-15MPa .
  • the desulfidation treatment is a mild desulfidation treatment, preferably carried out in the presence of hydrogen sulfide, and preferably carried out in at least one of the following ways:
  • the volume ratio of hydrogen sulfide and hydrogen is 200:1-800:1, preferably 300:1-600:1, and the total gas flow is 5-30mL ⁇ min -1 ⁇ g -1 oxidation state hydrogenation catalyst, preferably 10-20 mL ⁇ min -1 ⁇ g -1 oxidation state hydrogenation catalyst.
  • the sulfurization liquid includes a sulfur-containing compound and an organic solvent, wherein the sulfur-containing compound is selected from dimethyl disulfide, carbon disulfide, diethyl sulfide, ethyl mercaptan, n-butyl sulfide At least one of alcohol, di-tertiary polysulfide and dimethyl sulfoxide; the organic solvent is selected from at least one of cyclohexane, n-heptane, aviation kerosene and diesel.
  • the sulfur-containing compound is selected from dimethyl disulfide, carbon disulfide, diethyl sulfide, ethyl mercaptan, n-butyl sulfide At least one of alcohol, di-tertiary polysulfide and dimethyl sulfoxide
  • the organic solvent is selected from at least one of cyclohexane, n-heptane, aviation kerosene and diesel.
  • the mass fraction of sulfur-containing compounds in the sulfurization liquid is 0.1%-0.6%, such as 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, and these values. Any value in the range formed by any two of .
  • the flow rate of the sulfide liquid is 0.5-4.5 mL ⁇ h -1 ⁇ g -1 oxidation state hydrogenation catalyst, preferably 1-4 mL ⁇ h -1 ⁇ g -1 oxidation state hydrogenation catalyst.
  • the hydrogen flow rate is 5-30 mL ⁇ min -1 ⁇ g -1 oxidation state hydrogenation catalyst, preferably 10-20 mL ⁇ min -1 ⁇ g -1 oxidation state hydrogenation catalyst.
  • the selection range of the types of modification auxiliary components described in step (3) of the present invention can be the same as the selection range of the types of modification auxiliary components described in the first aspect above, and will not be described again here.
  • the present invention has a wide selection range for the type of precursor of the modification auxiliary component, as long as it can provide the modification auxiliary component through the contact reaction in step (3), preferably it contains a modification auxiliary agent.
  • Components of organic matter and/or hydrides are included in the modification auxiliary component.
  • the modification auxiliary component precursor is selected from the group consisting of gallium acetylacetonate, triethylgallium, silver stearate, silver acetylacetonate, silver cyclohexane butyrate, stearyl At least one of magnesium phosphate, dibutylmagnesium, magnesium pyruvate, magnesium L-aspartate, magnesium tetraphenylporphyrin, zinc naphthenate, zinc glycerol, diethyl selenium and hydrogen selenide.
  • the present invention has no particular limitation on the phase state of the material containing the precursor of the modification auxiliary component. It can be a liquid phase solution or a gas phase.
  • the material containing the precursor of the modifying auxiliary component is an organic solution containing the precursor of the modifying auxiliary component.
  • the mass content of the precursor of the modification auxiliary component is 0.5%-5%, for example, 0.5%, 1% , 2%, 3%, 4%, 4.5%, 5%, and any value in the range formed by any two of these values.
  • the solvent selection range in the organic solution containing the precursor of the modifying agent component is relatively wide, subject to achieving good compatibility with the precursor of the modifying agent component.
  • the solvent containing the precursor of the modifying agent component is selected from a wide range.
  • the solvent is selected from one or more of toluene, cyclohexane, decalin, tetralin and n-heptane.
  • the organic solution containing the modification auxiliary component precursor also contains a stabilizer, and the stabilizer is selected from organic alkaline nitrogen compounds.
  • the stabilizer can also be called a space-occupying agent, which is selected from organic alkaline nitrogen compounds with a certain basicity.
  • These organic alkaline nitrogen compounds can be adsorbed on the acidic center and active components of the carrier to prevent the modification of the auxiliary agent group. adsorption on the carrier.
  • Some of the organic alkaline nitrogen compounds adsorbed on the active components can be hydrogenated and converted into hydrocarbons and ammonia gas to be desorbed from the active phase, while the modification additive components can be attached to the metal active phase.
  • the stabilizer is selected from at least one of triethanolamine, diethanolamine, monoethanolamine, pyridine, quinoline and aniline.
  • the mass content of the stabilizer is 2%-8%, for example, 2%, 3%, 4%, 5%, 6%, 7%. , 8%, and any value in the range formed by any two of these values.
  • the conditions for the contact reaction in step (3) include: temperature is 80-220°C, preferably 100-200°C, pressure is 0.2-8MPa, preferably 0.5-6MPa, and reaction time is 2 -24 hours, preferably 4-20 hours; the hydrogen flow is 2-20mL ⁇ min -1 ⁇ g -1 oxidation state hydrogenation catalyst, preferably 5-15mL ⁇ min -1 ⁇ g -1 oxidation state hydrogenation catalyst; The flow rate of the material containing the modification auxiliary component precursor is 2-10 mL ⁇ h -1 ⁇ g -1 oxidation state hydrogenation catalyst, preferably 3-8 mL ⁇ h -1 ⁇ g -1 oxidation state hydrogenation catalyst.
  • the material containing the precursor of the modifying auxiliary component is an organic solution containing the precursor of the modifying auxiliary component.
  • This method is preferably used when the modification auxiliary component is at least one of Ag, Mg, Zn, and Ga.
  • the material containing the precursor of the modifying additive component is a mixed gas containing the precursor of the modifying additive component.
  • the material containing the precursor of the modifying auxiliary component is a mixed gas containing the precursor of the modifying auxiliary component, and the mixed gas also contains hydrogen.
  • the volume content of the precursor of the modifying auxiliary component is 1%-20%, preferably 3%-15%, and the volume content of hydrogen is 80%-80%. 99%, preferably 85%-97%.
  • the precursor of the modification auxiliary component is preferably hydrogen selenide.
  • the conditions for the contact reaction in step (3) preferably include: a temperature of 120-250°C, preferably 150-220°C, a reaction time of 1-8 hours, preferably 2-6 hours; reaction pressure is 2-12MPa, preferably 4-8MPa, and the flow rate of the mixed gas containing the modification aid component precursor is 5-40mL ⁇ min -1 ⁇ g -1 oxidation state hydrogenation catalyst, preferably 10-30mL ⁇ min -1 ⁇ g - 1 oxidation state hydrogenation catalyst.
  • the catalyst obtained in step (3) may also be optionally subjected to secondary sulfurization.
  • secondary sulfurization There are no special limitations on the conditions and methods of secondary vulcanization, and reference may be made to the vulcanization described in step (1).
  • wet vulcanization can be used for the secondary vulcanization.
  • the sulfurization liquid used for secondary vulcanization may include sulfur-containing compounds and organic solvents; the mass fraction of sulfur-containing compounds in the sulfurization liquid is preferably 1%-5%, preferably 1.5%-3.5%.
  • the sulfur compound is preferably one or more of diethyl sulfide, ethyl mercaptan, n-butyl mercaptan, di-tertiary polysulfide and dimethyl sulfoxide, and the organic solvent is preferably cyclohexane. , n-heptane, aviation kerosene, diesel, etc. at least one.
  • the conditions for the secondary vulcanization include: temperature is 250-350°C, preferably 280-320°C, time is 2-24h, preferably 4-16h; hydrogen pressure is 2-8MPa, preferably 2-6MPa, the flow rate of hydrogen is 2-15mL ⁇ min -1 ⁇ g -1 oxidation state hydrogenation catalyst, preferably 5-10mL ⁇ min -1 ⁇ g -1 oxidation state hydrogenation catalyst.
  • the flow rate of the sulfide liquid is 1-5 mL ⁇ h -1 ⁇ g -1 oxidation state hydrogenation catalyst, preferably 2-4 mL ⁇ h -1 ⁇ g -1 oxidation state hydrogenation catalyst.
  • the temperature of primary vulcanization is higher than the temperature of secondary vulcanization, preferably 20-100°C higher, and the temperature of secondary vulcanization is higher than the temperature of vulcanization treatment, preferably 20-80°C higher.
  • a third aspect of the present invention provides the application of the hydrogenation catalyst described in the first aspect or the hydrogenation catalyst prepared by the method described in the second aspect in the hydrogenation of oil products.
  • the catalyst provided by the invention When used in oil hydrogenation, it has better hydrogenation processing ability and stability.
  • the selection of different modification auxiliary components also gives the catalyst provided by the present invention additional advantages.
  • the catalyst is particularly suitable for hydrodenitrification of heavy oil products.
  • the modification auxiliary component in the hydrogenation catalyst is Ga, and the application is in the hydrodenitrification of heavy oil products.
  • it is used to treat heavy oil products with a nitrogen content of 1000 ⁇ g/g or more, further 1500-3000 ⁇ g/g, and a carbon residue mass content of 10 wt% or more, further 12 wt%-15 wt%.
  • the catalyst is particularly suitable for hydrodesulfurization of heavy oil products.
  • the modification auxiliary component in the hydrogenation catalyst is Zn, and the application is in the hydrodesulfurization of heavy oil products.
  • it is used to treat heavy oil products with a sulfur content of more than 2.0wt%, especially sulfur content of more than 3.0wt%.
  • the carbon residue content of heavy oil is preferably 8.0wt% or more, and more preferably 10wt%-15wt%.
  • the present invention has a wide selection range for the total content of metal nickel and vanadium in the above-mentioned heavy oil.
  • the metal content of the heavy oil is The total content of nickel and vanadium Ni+V is less than 100 ⁇ g/g, and more preferably 20-60 ⁇ g/g.
  • the heavy oil products include but are not limited to deasphalted oil.
  • the catalyst is particularly suitable for treating low-sulfur oil products.
  • the modification auxiliary component in the hydrogenation catalyst is Ag, and the application is in low-sulfur oil products.
  • Ag-modified hydrogenation catalysts are used to hydrogenate olefins, diolefins, aromatic hydrocarbons and other substances in saturated oil products, as well as perform hydrodeoxygenation, hydrodecarboxylation, etc., and have good hydrogenation saturation properties. Capacity and stable hydrodeoxygenation and hydrodeacidification capabilities, and has the advantage of high stability, especially suitable for long-term operation.
  • the sulfur content of the low-sulfur oil is less than 200 ⁇ g/g.
  • the low-sulfur oil products include but are not limited to at least one of biodiesel, Fischer-Tropsch synthetic oil, low-temperature coal tar, etc.
  • the catalyst is particularly suitable for selective hydrogenation and saturation of olefins in oil products.
  • the modification auxiliary component in the hydrogenation catalyst is Mg, and the application is in the selective hydrogenation and saturation of oil olefins.
  • it is used to process secondary processing feed oil with an olefin mass content of not less than 10%.
  • the secondary processing raw material oil may be at least one of coal-to-synthetic oil, coal tar, ebullated bed residual oil hydrogenation tail oil, ethylene tar, etc.
  • the catalyst is particularly suitable for the hydrogenation and decarbonization reaction of heavy feedstock oil.
  • the modification aid component in the hydrogenation catalyst is Se
  • the application is the application in the hydrogenation and decarbonization of heavy feedstock oil.
  • the heavy feedstock oil is a heavy feedstock oil with a residual carbon mass content of more than 10%, especially a heavy feedstock oil with a residual carbon mass content of more than 15%.
  • the heavy feedstock oil can be derived from inferior heavy oil and/or residual oil.
  • the application according to the present invention preferably includes reacting the oil product with the hydrogenation catalyst in the presence of hydrogen.
  • the reaction conditions include: reaction temperature is 200-420°C, preferably 250-400°C, hydrogen pressure is 4-25MPa, preferably 6-22MPa, and liquid hourly volume space velocity is 0.1-3h -1 , preferably 0.1- 2h -1 , the volume ratio of hydrogen to oil is 400:1-1500:1, preferably 400:1-1200:1.
  • the content of the modifying additive components distributed in the A-B-S active phase region accounts for the total content of the modifying additive components, and the sulfur content at the corners of the A-B-S active phase accounts for the proportion of the A-B-S active phase.
  • the total sulfur content was characterized by TEM-EDS (Transmission Electron Microscope-Energy Dispersive X-ray Spectroscopy), and the specific method was as described in the Specific Embodiments section.
  • the oxidation state hydrogenation catalysts used in the following Examples A1-A6 and Comparative Examples A1-A5 were all prepared using the following methods:
  • TQ-1 Take 1000g cyclohexane and 2.0g dimethyl disulfide, and the prepared sulfide liquid is marked as TQ-1.
  • the obtained catalyst was designated as ECT-1.
  • the obtained catalyst was designated as TCT-2.
  • the obtained catalyst was designated as ECT-2.
  • the obtained catalyst was designated as ECT-3.
  • the temperature of the reaction tube was lowered to 280°C, the reaction pressure was adjusted to 6.0 MPa, and a mixed gas of hydrogen and hydrogen sulfide was introduced into the reaction tube, the volume ratio of hydrogen to hydrogen sulfide was 400:1, the total flow rate of the mixed gas was 400 mL/min, and the treatment time was 12 hours.
  • the obtained catalyst was recorded as TCT-4.
  • the obtained catalyst was designated ECT-4.
  • the reaction tube Reduce the temperature of the reaction tube to 280°C, adjust the reaction pressure to 6.0MPa, and pass a mixed gas of hydrogen and hydrogen sulfide into the reaction tube.
  • the volume ratio of hydrogen to hydrogen sulfide is 500:1, and the total flow rate of the mixed gas is 500mL/ min, processing time is 12 hours.
  • the obtained catalyst was designated as TCT-5.
  • the obtained catalyst was designated as ECT-5.
  • catalyst DCT-1 The preparation process of catalyst DCT-1 is the same as that of Comparative Example A1.
  • the reaction tube containing SCT-0 was cooled to 110°C, the pressure was adjusted to 0.8MPa, the hydrogen flow was 120.0mL/min, GQ-1 was passed into the reaction tube, the flow was 120mL/h, and the treatment time was 8.0 hours.
  • the obtained catalyst was designated as DCT-3.
  • the obtained catalyst was designated as DTCT-4.
  • the obtained catalyst was designated DCT-4.
  • the hydrogenation catalyst was characterized by TEM-EDS, and the percentage of Ga content distributed in the Ni-Mo-S active phase region in the catalyst to the total Ga content and the percentage of sulfur content at the corners of the Ni-Mo-S active phase to the total sulfur content in the Ni-Mo-S active phase were obtained. See Table A2 for details.
  • the activity of the catalysts obtained in Examples A1-A6 was evaluated respectively.
  • the properties of the deasphalted oil are shown in Table A3.
  • a hydrogenation protective agent FZC-100B
  • the filling volume ratio of the protective agent to the hydrodenitrification catalyst obtained in the example is 1:4.
  • the operating conditions are: reaction temperature 390°C, reaction pressure 20.0MPa, hydrogen-oil volume ratio 1000:1, and liquid hourly volume space velocity 0.2h -1 .
  • the carbon residue value and sulfur content in the hydrogenated oil should not be lower than the 200°C fraction. and nitrogen content were analyzed, and the results are shown in Table A4.
  • the activity of the catalysts obtained in Comparative Examples A1-A5 was evaluated respectively, and the properties of the deasphalted oil are shown in Table A3.
  • a fixed bed process was adopted, and a hydrogenation protective agent (FZC-100B) was loaded before the above catalyst, and the loading volume ratio of the protective agent to the hydrodenitrogenation catalyst obtained in the comparative example was 1:4.
  • the operating conditions were: reaction temperature 390°C, reaction pressure 20.0MPa, hydrogen oil volume ratio 1000:1, and liquid hourly volume space velocity 0.2h -1 .
  • the residual carbon value, sulfur content and nitrogen content of the hydrogenation oil not less than 200°C fraction were analyzed, and the results are shown in Table A4.
  • the hydrogenation catalyst prepared by the present invention not only has good hydrodenitrification ability, but also has good aromatic hydrocarbon saturation ability and hydrodesulfurization ability.
  • oxidation state hydrogenation catalysts used in the following embodiments B1-B5 and comparative examples B1-B5 of the present invention are all prepared by the following methods:
  • TQ-1 Take 1000g cyclohexane and 2.0g dimethyl disulfide, and the prepared sulfide liquid is marked as TQ-1.
  • vulcanization temperature is 350°C
  • hydrogen pressure is 6.0MPa
  • hydrogen flow rate is 300.0mL/min
  • vulcanization liquid SQ-0 The flow rate is 40.0mL/h
  • the sulfidation time is 6 hours
  • the obtained sulfide hydrogenation catalyst is marked as SCT-0.
  • the obtained catalyst was designated as ECT-1.
  • the obtained catalyst was designated as TCT-2.
  • the obtained catalyst was designated as ECT-2.
  • the temperature of the reaction tube was lowered to 150°C, the hydrogen pressure was adjusted to 2.0 MPa, the hydrogen flow rate was 180.0 mL/min, YQ-3 was introduced into the reaction tube at a flow rate of 120.0 ml/h, and the treatment time was 15.0 hours.
  • the obtained catalyst was recorded as ECT-3.
  • the obtained catalyst was designated as TCT-4.
  • the obtained catalyst was designated ECT-4.
  • the obtained catalyst was designated as TCT-5.
  • catalyst DCT-1 The preparation process of catalyst DCT-1 is the same as that of Comparative Example B1.
  • catalyst DCT-1 The preparation process of catalyst DCT-1 is the same as that of comparative example B1.
  • the obtained catalyst was designated as DTCT-4.
  • composition of the above catalyst is shown in Table B1.
  • the hydrogenation catalysts obtained in each case were characterized by TEM-EDS to obtain the percentage of the Ag content distributed in the Ni-Mo-S active phase region of the catalyst to the total Ag content and the percentage of the sulfur content at the corners of the Ni-Mo-S active phase to the total sulfur content in the Ni-Mo-S active phase. See Table B2 for details.
  • the activity and stability of the catalysts ECT-1 to ECT-5 of Examples B1-B5 were investigated on a fixed-bed hydrogenation device.
  • the evaluation conditions were: reaction pressure 8.0MPa, hydrogen-to-oil volume ratio 500:1, temperature 300°C.
  • the volume space velocity is 2.0h -1 , and samples at two time points of 500 hours and 1500 hours of reaction are sampled and analyzed.
  • the raw material oil selected is Fischer-Tropsch synthetic oil, its properties are shown in Table B3, and the catalyst evaluation results are shown in Table B4.
  • oxidation state hydrogenation catalysts used in the following embodiments C1-C5 and comparative examples C1-C5 of the present invention are all prepared by the following method:
  • alumina dry glue powder add 10.0g of citric acid, and 50.0g of sesbania powder. After mixing evenly, add 900.0g of an aqueous solution containing 1.0% acetic acid mass fraction. After kneading for 20.0 minutes, use a clover hole with a diameter of 2.4mm. Extruded boards. After drying at 120°C for 6.0h, roasting at 750°C for 6.0h. The calcined carrier is marked as S-0 (after analysis and detection, the specific surface area of the carrier is 322m 2 /g, and the pore volume of the carrier is 0.9cm 3 /g).
  • the temperature of the reaction tube was lowered to 260°C, the hydrogen pressure was adjusted to 5.0 MPa, the flow rate of hydrogen was 200.0 mL/min, TQ-1 was introduced into the reaction tube at a flow rate of 30.0 mL/h, and the treatment time was 9 hours.
  • the obtained catalyst was recorded as TCT-1.
  • the temperature of the reaction tube was lowered to 110°C, the hydrogen pressure was adjusted to 0.4 MPa, the gas flow rate was 100.0 mL/min, MQ-1 was introduced into the reaction tube at a flow rate of 80.0 mL/h, and the treatment time was 10.0 hours.
  • the obtained catalyst was recorded as ECT-1.
  • the obtained catalyst was designated as TCT-2.
  • the obtained catalyst was designated as ECT-2.
  • the obtained catalyst was designated as ECT-3.
  • the obtained catalyst was designated as TCT-4.
  • the temperature of the reaction tube was lowered to 140°C, the pressure was adjusted to 0.6 MPa, the gas flow rate was 130.0 mL/min, MQ-4 was introduced into the reaction tube at a flow rate of 120.0 mL/h, and the treatment time was 12.0 hours.
  • the obtained catalyst was recorded as ECT-4.
  • the temperature of the reaction tube was lowered to 300°C, the reaction pressure was adjusted to 6.0 MPa, and a mixed gas of hydrogen and hydrogen sulfide was introduced into the reaction tube, the volume ratio of hydrogen to hydrogen sulfide was 550:1, the total flow rate of the mixed gas was 450 mL/min, and the treatment time was 12 hours.
  • the obtained catalyst was recorded as TCT-5.
  • the temperature of the reaction tube was lowered to 150°C, the pressure was adjusted to 0.6 MPa, the gas flow rate was 130.0 mL/min, MQ-5 was introduced into the reaction tube at a flow rate of 120.0 mL/h, and the treatment time was 14.0 hours.
  • the obtained catalyst was recorded as ECT-5.
  • catalyst DCT-1 The preparation process of catalyst DCT-1 is the same as that of Comparative Example C1.
  • the preparation process of the sulfide hydrogenation catalyst SCT-0 is the same as that of Example C1.
  • the obtained catalyst was designated as DCT-3.
  • catalyst DCT-1 The preparation process of catalyst DCT-1 is the same as that of Comparative Example C1.
  • the obtained catalyst was designated as DTCT-4.
  • the temperature of the reaction tube was lowered to 110°C, the pressure was adjusted to 0.4 MPa, the gas flow rate was 100.0 mL/min, DGQ-4 was introduced into the reaction tube at a flow rate of 80.0 mL/h, and the treatment time was 10.0 hours.
  • the obtained catalyst was recorded as DCT-4.
  • composition of the above catalyst is shown in Table C1.
  • the activity of the catalysts obtained in Examples C1-C5 was evaluated respectively, wherein the properties of the feed oil are shown in Table C3.
  • the feed oil was hydrogenated and the evaluation conditions were: reaction temperature 320°C, reaction pressure 8.0 MPa, liquid hourly volume space velocity 2.5 h -1 , hydrogen to oil volume ratio 800:1. After the catalyst was evaluated for 1000 hours, the evaluation results are shown in Table C4.
  • the activity of the catalysts obtained in Comparative Examples C1-C5 was evaluated respectively.
  • the properties of the raw material oil are as shown in Table C3.
  • the raw materials were hydrogenated and evaluated.
  • the evaluation conditions were: reaction temperature 320°C, reaction pressure 8.0MPa, liquid hour volume The space velocity was 2.5h -1 , the hydrogen-to-oil volume ratio was 800:1, and the catalyst was evaluated for 1000 hours.
  • the evaluation results obtained are shown in Table C4.
  • the Mg-modified hydrogenation catalyst prepared by the method of the present invention not only has good hydrogenation activity, but also has good hydrogenation saturation performance for olefins, and the catalyst stability is good.
  • oxidation state hydrogenation catalysts used in the following embodiments D1-D5 and comparative examples D1-D5 of the present invention are all prepared by the following methods:
  • alumina dry rubber powder add 10.0g of citric acid and 30.0g of sesbania powder. After mixing evenly, add 1000.0g of an aqueous solution containing 0.5% nitric acid mass fraction. After rolling for 10.0 minutes, use a clover with a diameter of 2.0mm. Orifice plate extrusion strip. After drying at 120°C for 6.0h, it was roasted at 800°C for 6.0h.
  • the calcined carrier is marked as S-0 (after analysis and detection, the specific surface area of the carrier is 271 m 2 /g, and the pore volume of the carrier is 0.93 cm 3 /g).
  • TQ-1 Take 1000g cyclohexane and 2.0g dimethyl disulfide, and the prepared sulfide liquid is marked as TQ-1.
  • the temperature of the reaction tube was lowered to 140°C, the hydrogen pressure was adjusted to 3.0 MPa, the gas flow rate was 120.0 mL/min, ZQ-1 was introduced into the reaction tube at a flow rate of 80.0 mL/h, and the treatment time was 3.0 hours.
  • the obtained catalyst was recorded as ECT-1.
  • the obtained catalyst was designated as TCT-2.
  • the obtained catalyst was designated as ECT-2.
  • the obtained catalyst was designated as ECT-3.
  • the obtained catalyst was designated as TCT-4.
  • the obtained catalyst was designated ECT-4.
  • the reaction tube Reduce the temperature of the reaction tube to 300°C, adjust the reaction pressure to 6.0MPa, and pass a mixed gas of hydrogen and hydrogen sulfide into the reaction tube.
  • the volume ratio of hydrogen to hydrogen sulfide is 450:1, and the total flow rate of the mixed gas is 450mL/ min, processing time is 12 hours.
  • the obtained catalyst was designated as TCT-5.
  • the obtained catalyst was designated as ECT-5.
  • catalyst DCT-1 The preparation process of catalyst DCT-1 is the same as that of Comparative Example D1.
  • the obtained catalyst was designated as DCT-3.
  • catalyst DCT-1 The preparation process of catalyst DCT-1 is the same as that of Comparative Example D1.
  • the obtained catalyst was designated as DTCT-4.
  • the obtained catalyst was designated DCT-4.
  • composition of the above catalyst is shown in Table D1.
  • the Zn-modified hydrodesulfurization catalyst was characterized by TEM-EDS, and it was found that the Zn content distributed in the Ni-Mo-S active phase region in the catalyst accounted for the percentage of the total Zn content and the corner positions of the Ni-Mo-S active phase.
  • the sulfur content accounts for the percentage of the total sulfur content in the Ni-Mo-S active phase. See Table D2 for details.
  • the activity of the catalysts obtained in Examples D1-D5 was evaluated respectively.
  • the properties of the deasphalted oil are shown in Table D3.
  • a hydrogenation protective agent FZC-100B
  • the filling volume ratio of the protective agent to the hydrodesulfurization catalyst obtained in the example is 1:4.
  • the operating conditions are: reaction temperature 385°C, reaction pressure 18.0MPa, hydrogen-oil volume ratio 800:1, and liquid hourly volume space velocity 0.15h -1 .
  • the carbon residue value, sulfur content and nitrogen content in the hydrogenated oil fraction not lower than 200°C were analyzed. The results are shown in Table D4.
  • the activity of the catalysts obtained in Comparative Examples D1-D5 was evaluated respectively.
  • the properties of the deasphalted oil are shown in Table D3.
  • a hydrogenation protective agent FZC-100B
  • the filling volume ratio of the protective agent to the hydrodesulfurization catalyst obtained in the example is 1:4.
  • the operating conditions are: reaction temperature 385°C, reaction pressure 18.0MPa, hydrogen-oil volume ratio 800:1, and liquid hourly volume space velocity 0.15h -1 .
  • the carbon residue value, sulfur content and nitrogen content in the hydrogenated oil fraction not lower than 200°C were analyzed. The results are shown in Table D4.
  • the hydrodesulfurization catalyst of the present invention not only has good hydrodesulfurization capabilities, but also has good hydrodenitrification capabilities and hydrodecarbonization capabilities.
  • oxidation state hydrogenation catalysts used in the following examples E1-E5 and comparative examples E1-E5 of the present invention are all prepared by the following methods:
  • alumina dry glue powder add 20.0g of citric acid and 20.0g of sesbania powder. After mixing evenly, add 1000.0g of an aqueous solution containing 1.0% nitric acid mass fraction. After rolling for 20.0 minutes, use a clover with a diameter of 1.8mm. Orifice plate extrusion strip. After drying at 120°C for 6.0h, it was roasted at 700°C for 6.0h.
  • the calcined carrier is marked as S-0 (after analysis, the properties of the carrier are as follows: specific surface area is 270m 2 /g, pore volume is 0.9cm 3 /g).
  • TQ-1 Take 1000g cyclohexane and 2.0g dimethyl disulfide, and the prepared sulfide liquid is marked as TQ-1.
  • the pressure of hydrogen is 6.0MPa
  • the flow rate of hydrogen is 300.0mL/min
  • the flow rate of vulcanization liquid SQ-0 is 40.0mL.
  • the sulfurization temperature is 350°C
  • the sulfurization time is 6 hours
  • the obtained sulfurized hydrogenation catalyst is marked as SCT-0.
  • the obtained catalyst was designated as TCT-1.
  • the obtained catalyst was designated as ECT-1.
  • the reaction tube Reduce the temperature of the reaction tube to 180°C, adjust the pressure to 8.0MPa, and pass a mixed gas of hydrogen and hydrogen selenide into the reaction tube.
  • the volume fraction of hydrogen is 93% and the volume fraction of hydrogen selenide is 7%.
  • Mix The gas flow rate is 400.0mL/min, and the processing time is 4.0 hours.
  • the obtained catalyst was designated as ECT-2.
  • the obtained catalyst was designated as TCT-3.
  • the reaction tube reduces the temperature of the reaction tube to 200°C, adjust the pressure to 7.0MPa, and pass a mixed gas of hydrogen and hydrogen selenide into the reaction tube.
  • the volume fraction of hydrogen is 90% and the volume fraction of hydrogen selenide is 10%.
  • Mix The gas flow rate is 500.0mL/min, and the processing time is 5.0 hours.
  • the obtained catalyst was designated as ECT-3.
  • the reaction tube equipped with the sulfide hydrogenation catalyst SCT-0 to 270°C adjust the reaction pressure to 6.0MPa, and introduce a mixed gas of hydrogen and hydrogen sulfide at the same time.
  • the partial pressure ratio of hydrogen and hydrogen sulfide is 400:1.
  • the mixed gas flow rate is 400.0mL/min
  • the processing time is 12 hours.
  • the obtained catalyst was designated as TCT-4.
  • the temperature of the reaction tube was lowered to 180°C, the pressure was adjusted to 8.0 MPa, and a mixed gas of hydrogen and hydrogen selenide was introduced into the reaction tube, wherein the volume fraction of hydrogen gas was 93%, the volume fraction of hydrogen selenide was 7%, the flow rate of the mixed gas was 500.0 mL/min, and the treatment time was 4.0 hours.
  • the obtained catalyst was recorded as ECT-4.
  • the obtained catalyst was designated as TCT-5.
  • the reaction tube reduces the temperature of the reaction tube to 210°C, adjust the pressure to 7.0MPa, and pass a mixed gas of hydrogen and hydrogen selenide into the reaction tube.
  • the volume fraction of hydrogen is 88% and the volume fraction of hydrogen selenide is 12%.
  • Mix The gas flow rate is 300.0mL/min, and the processing time is 5.0 hours.
  • the obtained catalyst was designated as ECT-5.
  • catalyst DCT-1 The preparation process of catalyst DCT-1 is the same as that of comparative example E1.
  • the obtained catalyst was designated as DCT-2.
  • the reaction tube containing SCT-0 to 180°C adjust the hydrogen pressure to 8.0MPa, and pass a mixed gas of hydrogen and hydrogen selenide into the reaction tube.
  • the volume fraction of hydrogen is 93%, and the volume of hydrogen selenide is 93%.
  • the fraction was 7%, the gas flow rate was 400.0 mL/min, and the treatment time was 4.0 hours.
  • the obtained catalyst was designated as DCT-3.
  • catalyst DCT-1 The preparation process of catalyst DCT-1 is the same as that of Comparative Example E1.
  • the obtained catalyst was designated as DTCT-4.
  • the reaction tube reduces the temperature of the reaction tube to 160°C, adjust the pressure to 5.0MPa, and pass a mixed gas of hydrogen and hydrogen selenide into the reaction tube.
  • the volume fraction of hydrogen is 95% and the volume fraction of hydrogen selenide is 5%.
  • Mix The gas flow rate is 300.0mL/min, and the processing time is 3.0 hours.
  • the obtained catalyst was designated DCT-4.
  • the obtained catalyst was designated DCT-5.
  • composition of the above catalyst is shown in Table E1.
  • TEM-EDS was used to characterize the hydrogenation and decarbonization catalyst, and it was found that the Se content distributed in the Ni-Mo-S active phase area in the catalyst accounted for the percentage of the total Se content and the sulfur at the corners of the Ni-Mo-S active phase. The content accounts for the percentage of the total sulfur content in the Ni-Mo-S active phase. See Table E2 for details.
  • the activity of the catalysts obtained in Examples E1-E5 was evaluated respectively.
  • the properties of the residual oil raw materials are shown in Table E3.
  • a hydrogenation protective agent FZC-100B
  • a hydrodemetallization catalyst FZC-204A
  • a hydrodesulfurization catalyst FZC-33B
  • the filling volume ratio of the catalyst, the hydrodesulfurization catalyst, and the catalyst obtained in the example is 1.5:2.0:2.0:4.5.
  • the operating conditions are: reaction temperature 380°C, reaction pressure 16.0MPa, hydrogen-oil volume ratio 1200:1, and liquid hourly volume space velocity 0.2h -1 .
  • the carbon residue value, saturation fraction and nitrogen content in the hydrogenated oil fraction not lower than 200°C were analyzed. The results are shown in Table E4.
  • the activity of the catalysts obtained in Comparative Examples E1-E5 was evaluated respectively, and the properties of the residual oil raw materials are shown in Table E3.
  • a fixed bed process was adopted, and a hydrogenation protective agent (FZC-100B), a hydrodemetallization catalyst (FZC-204A), and a hydrodesulfurization catalyst (FZC-33B) were loaded before the above catalysts.
  • the loading volume ratio of the protective agent, the hydrodemetallization catalyst, the hydrodesulfurization catalyst, and the catalyst obtained in the comparative example was 1.5:2.0:2.0:4.5.
  • the operating conditions were: reaction temperature 380°C, reaction pressure 16.0MPa, hydrogen oil volume ratio 1200:1, and liquid hourly volume space velocity 0.2h -1 . After 2000h of reaction evaluation, the residual carbon value, saturated fraction and nitrogen content of the hydrogenation generated oil not lower than 200°C fraction were analyzed, and the results are shown in Table E4.
  • the catalyst of the present invention has good hydrogenation and carbon residue removal, hydrogenation saturation capabilities and good hydrodenitrification capabilities.

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Abstract

本发明公开了一种加氢催化剂及其制备方法和应用，所述加氢催化剂为硫化态加氢催化剂，包括载体以及活性组分A、活性组分B和改性助剂组分，所述活性组分A选自第VIII族金属元素中的至少一种，所述活性组分B选自第VIB族金属元素中的至少一种，所述改性助剂组分选自IB、IIA、IIB、IIIA和VIA族元素中的至少一种；其中，所述加氢催化剂采用TEM-EDS方法表征，分布在A-B-S活性相区域内的改性助剂组分含量占总改性助剂组分含量的60％-98％。本发明提供的加氢催化剂具有较好的加氢处理能力以及稳定性。

Description

加氢催化剂及其制备方法和应用
相关申请的交叉引用
本申请要求2022年9月19日提交的中国专利申请202211136689.1的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明属于加氢催化剂领域，涉及一种加氢催化剂及其制备方法和应用。
背景技术
目前渣油加氢处理使用的活性相主要以Co(Ni)-Mo(W)-S类型为主，为了更好的应对不用的需求，在催化剂制备过程中可以对活性相进行杂原子改性，来提高催化剂的使用性能。
CN101722039A公开一种加氢催化剂及其制备方法，在催化剂制备过程中引入镓和稀土金属元素，对催化剂进行改性处理。此种改性方法助剂以改性载体为主，提升效果有限而且会导致在加工重油过程中，活性金属的迁移现象严重。
CN113559875A公开一种加氢催化剂及其制备方法，在载体的制备过程中，引入助剂磷和镁，起到了调节孔道结构的作用和催化剂的孔道扩散作用。这种方法仍然以载体改性为主，没有对活性相进行有针对性的修饰，对一些非常规劣质原料的加氢处理缺乏适应性。
CN101844081A公开一种选择加氢催化剂的制备方法，在活性金属浸渍过程中，引入锌助剂，来提高催化剂加氢脱硫效果。此种改性方法，锌和镍难以同步硫化，而导致很多没有被Zn修饰的活性相，对处理劣质油品，尤其是硫含量较高的渣油时，脱硫活性不足。
发明内容
为了克服现有技术加氢催化剂加氢处理能力、原料油适应性以及稳定性有待进一步提高的问题，本发明提供一种加氢催化剂及其制备方法和应用，本发明提供的加氢催化剂具有较好的加氢处理能力以及稳定性，适合多种类型原料油的处理。
本发明第一方面提供一种加氢催化剂，所述加氢催化剂为硫化态加氢催化剂，包括载体以及活性组分A、活性组分B和改性助剂组分，所述活性组分A选自第VIII族金属元素中的至少一种，所述活性组分B选自第VIB族金属元素中的至少一种，所述改性助剂组分选自IB、IIA、IIB、IIIA和VIA族元素中的至少一种；
其中，所述加氢催化剂采用TEM-EDS方法表征，分布在A-B-S活性相区域内的改性助剂组分含量占总改性助剂组分含量的60％-95％，优选为75％-90％。
本发明提供的加氢催化剂中，分布在A-B-S活性相区域内的改性助剂组分含量较高，使得改性助剂组分能够更好的发挥作用，与A-B-S活性相有效结合。
本发明的发明人在研究过程中发现，现有技术大多重点强调在氧化态加氢催化剂中引入助剂金属的问题，但本发明的发明人发现这种改性没有定位化，缺乏针对性，存在效果欠佳，油品适应性和稳定性不足等问题。
本发明第二方面提供一种加氢催化剂的制备方法，该方法包括以下步骤：
(1)对氧化态加氢催化剂进行硫化，得到硫化态加氢催化剂；
(2)将所述硫化态加氢催化剂进行失硫化处理；
(3)将步骤(2)得到的处理后的催化剂与含有改性助剂组分前驱物的物料进行接触反应；
其中，所述改性助剂组分选自IB、IIA、IIB、IIIA和VIA族元素中的至少一种。
本发明提供的加氢催化剂的制备方法中先对氧化态加氢催化剂进行硫化，然后进行失硫化，使需要改性的金属活性相处于特定的失硫高活性状态，活性相边缘外层为暴露的活性金属，同时可以有效保留加氢活性相中内部的三配位硫原子以及稳定的A-B-S晶体结构，改性助剂组分可以更有效的与活性相外层金属相接触，使所得加氢催化剂中，改性助剂组分(以R表示)与A、B和S形成了R-A-B-S组合混合活性相，实现改性的目的。
本发明第三方面提供第一方面所述加氢催化剂或者第二方面所述方法制备的加氢催化剂在油品加氢中的应用。
将本发明提供的催化剂应用于油品加氢中，具有较好的加氢处理能力以及稳定性。不同改性助剂组分的选择，还使得本发明提供的催化剂具有额外的优势，例如选择性。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明中，除非另有其他明确说明，否则百分比、百分含量均以质量计。
本发明第一方面提供一种加氢催化剂，所述加氢催化剂为硫化态加氢催化剂，包括载体以及活性组分A、活性组分B和改性助剂组分，所述活性组分A选自第VIII族金属元素中的至少一种，所述活性组分B选自第VIB族金属元素中的至少一种，所述改性助剂组分选自IB、IIA、IIB、 IIIA和VIA族元素中的至少一种；
其中，所述加氢催化剂采用TEM-EDS方法表征，分布在A-B-S活性相区域内的改性助剂组分含量占总改性助剂组分含量的60％-98％。
根据本发明，所述A-B-S活性相具有加氢催化剂领域的常规释义，A-B-S活性相是指加氢催化剂的有效活性中心，该概念由Haldor Topsoe公司于1984年提出。
在本发明中，分布在A-B-S活性相区域内的改性助剂组分含量占总改性助剂组分含量以R-A-B-S/R总表示，其中，R表示改性助剂组分，R-A-B-S表示分布在A-B-S活性相区域内的改性助剂组分含量，R总表示催化剂中改性助剂组分的总含量。本发明R-A-B-S/R总通过TEM-EDS(透射电镜-能量弥散X射线谱)方法表征得到，采用的仪器型号为，日本JEOL JEM2200FS型发射透射电子显微镜，配有扫描透射附件和美国EDAX公司X射线能谱附件。电镜加速电压200KV,STEM模式中，聚光镜光阑取2，Spote size为0.5nm。测定过程如下：将催化剂颗粒磨碎，采用悬浮法制样，将0.1g催化剂样品放入2mL容器中，用无水乙醇超声分散，取上清液，用滴管取二-三滴，滴在直径3mm样品网上，经干燥得到待测样品，然后采用TEM对待测样品进行观察分析，然后结合EDS对TEM观察到活性的区域内的改性助剂组分的含量分布进行统计，以改性助剂组分的相应峰面积计，得出分布在A-B-S活性相区域内的改性助剂组分含量与总改性助剂组分含量的比值(用R-A-B-S/R总表示)，本发明R-A-B-S/R总是通过选择40张TEM图像结合EDS分析得到的数据取平均值得到。
根据本发明的一种优选实施方式，分布在A-B-S活性相区域内的改性助剂组分含量占总改性助剂组分含量的75％-98％，例如为75％、78％、80％、82％、84％、86％、88％、90％，以及这些数值中的任意两个所构成的范围中的任意值。
现有技术中，改性助剂组分往往在氧化态催化剂中引入，然后进行硫化，现有技术采用先结合后形成活性相的方式，真正发挥有效作用的改性助剂组分占比相对较小，本发明的发明人在研究后发现，现有技术分布在Ni-Mo-S活性相区域内的改性助剂组分含量与总改性助剂组分含量的比值一般在30％以下。
根据本发明的一种优选实施方式，所述加氢催化剂采用TEM-EDS方法表征，A-B-S活性相边角位的硫含量占A-B-S活性相中总硫含量的6.0％以下，优选为0.5％-4.5％，例如为0.5％、1％、2％、3％、4％、4.5％，以及这些数值中的任意两个所构成的范围中的任意值。采用该种优选实施方式，使活性相边角位硫含量适度降低，有利于活性组分原子的空轨道暴露在外，强化金属修饰过程中，活性相对改性助剂组分有机物的吸附，使改性助剂组分更好的固定在活性相的边角位上。
A-B-S活性相边角位的硫含量占A-B-S活性相中总硫含量以S边角位/S总表示，其中，S边角位表示A-B-S活性相边角位的硫含量，S总表示A-B-S活性相中总硫含量。本发明S边角位/S总通过TEM- EDS(透射电镜-能量弥散X射线谱)方法表征得到，采用的仪器型号同上。测定过程如下：将催化剂颗粒磨碎，采用悬浮法制样，将0.1g催化剂样品放入2mL容器中，用无水乙醇超声分散，取上清液，用滴管取二-三滴，滴在直径3mm样品网上，经干燥得到待测样品，采用TEM对待测样品进行观察分析，然后结合EDS对TEM观察到活性相区域内的S的含量分布进行统计。本发明定义距离活性相边缘端点小于1nm处为活性相的边角位。选取任意一个TEM电镜下观察得到的活性相，再结合EDS对活性相距离边缘端点小于1nm处的硫含量以及活性相中的硫含量进行统计分析，以硫的相应峰面积计，得到A-B-S活性相边角位的硫含量占A-B-S活性相中总硫含量，(用S边角位/S总表示)。本发明S边角位/S总是通过选择40张TEM图像结合EDS分析得到的数据取平均值得到。
现有技术中对Ni-Mo-S型加氢活性相的改性方法中，助剂元素在活性金属为氧化物前驱体状态时便已经引入，在活性金属发生硫化时，助剂元素很难高选择性负载在活性相上，直接修饰效果较差。且现有技术中提供的硫化态催化剂，S边角位/S总的值较大。
根据本发明，优选地，以加氢催化剂的质量为基准，以元素计，活性组分A的含量为1-10％，优选1.5％-6％，例如为1.5％、2％、2.5％、3％、3.5％、4％、4.5％、5％、5.5％、6％，以及这些数值中的任意两个所构成的范围中的任意值；以元素计，活性组分B的含量为6％-24％，优选8％-18％，例如为8％、9％、10％、12％、14％、16％、18％，以及这些数值中的任意两个所构成的范围中的任意值。
根据本发明，优选地，以加氢催化剂的质量为基准，以元素计，改性助剂组分的含量为0.2％-4％，优选0.8％-4％，例如为0.8％、1％、1.5％、2％、2.5％、3％、3.5％、4％，以及这些数值中的任意两个所构成的范围中的任意值。本发明采用较少的改性助剂组分即可有效改善加氢催化剂的性能。
根据本发明，优选地，以加氢催化剂的质量为基准，硫元素的含量为3％-20％，优选4％-15％，例如为4％、5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、15％，以及这些数值中的任意两个所构成的范围中的任意值。
在本发明中，加氢催化剂中，活性组分A、活性组分B、改性助剂组分以及硫元素的含量通过ICP测得，所用设备为PE公司生产OPTIMA 7000DV型原子发射光谱仪。将0.1g样品溶解在体积比为3HCl:1HNO3:0.5HF的混合溶液中，后将混合溶液用去离子水稀释至某一体积，使溶液中待测元素的含量在1-10ppm之间，然后进行测定。
根据本发明的一种特别优选实施方式，以加氢催化剂的质量为基准，以元素计，活性组分A的含量为1-10％，优选1.5％-6％；以元素计，活性组分B的含量为6％-24％，优选8％-18％，以元素计，改性助剂组分的含量为0.2％-4％，优选0.8％-4％，硫元素的含量为3％-20％，优选4％- 15％，载体的含量为42-89％，优选57-85％。
根据本发明提供的加氢催化剂，其中还可以含有其他组分，可以知晓的是，加氢催化剂中所有组分含量之和为100％。
根据本发明的一种优选实施方式，所述活性组分A为Co和/或Ni，所述活性组分B为Mo和/或W。
根据本发明，优选地，所述活性组分A为Ni，所述活性组分B为Mo。采用该种优选实施方式的催化剂更有利于重质油的加氢处理。
本发明对所述改性助剂组分的具体种类选择范围较宽，上述种类均可以实现本发明提高加氢催化剂加氢处理能力以及稳定性的目的。另外，选自特定改性助剂组分种类可以使得加氢催化剂具有额外的优势，更加适用于特定油品的处理。
优选地，所述改性助剂组分选自Cu、Ag、Au、Mg、Ca、Zn、Cd、Ga和Se中的至少一种，更优选为Ag、Mg、Zn、Ga和Se中的至少一种。
本发明的发明人在研究过程中发现，改性助剂组分选用Ag时，在低硫环境下，仍具有较好稳定性，特别适用于长期加工低硫或无硫的原料(包括但不限于生物柴油、费托合成油、低温煤焦油等中的至少一种)，且催化剂具有较好的芳烃等加氢饱和选择性。
本发明的发明人在研究过程中发现，改性助剂组分选用Mg时，催化剂烯烃加氢选择性较好，特别适用于处理烯烃较多的原料油，例如为煤制合成油、煤焦油、沸腾床渣油加氢尾油、乙烯焦油等中的至少一种。
本发明的发明人在研究过程中发现，改性助剂组分选用Zn时，催化剂的加氢脱硫选择性较好，特别适用于处理重质油如脱沥青油的加氢脱硫处理。
本发明的发明人在研究过程中发现，改性助剂组分选用Ga时，催化剂的加氢脱氮选择性较好，特别适用于处理重质油如脱沥青油的加氢脱氮处理。
本发明的发明人在研究过程中发现，改性助剂组分选用Se时，催化剂的加氢脱残炭选择性较好，特别适用于残炭含量较高的重质原料油如劣质重油或渣油的处理。
本发明对所述载体没有特别的限定，可以为本领域常规使用的各种载体，可以是市售的商品也可由现有技术中任意一种方法制备，例如所述载体可以为无机耐熔氧化物。优选地，所述载体选自氧化铝、氧化硅和无定形硅铝中的至少一种。
本发明对载体的比表面积以及孔容选择范围较宽，优选地，所述载体的比表面积为200-500m2/g，优选250-400m2/g，孔容为0.4-1.0cm3/g，优选为0.6-0.8cm3/g。
本发明中，所述载体中还可以含有掺杂元素，所述掺杂元素例如可以为磷、硅、硼、氟、钠等元素中的一种或几种。所述掺杂元素的添加量可以为常规添加量，优选占载体质量的0.5％-6％。
本发明第二方面提供一种加氢催化剂的制备方法，该方法包括以下步骤：
(1)对氧化态加氢催化剂进行硫化，得到硫化态加氢催化剂；
(2)将所述硫化态加氢催化剂进行失硫化处理；
(3)将步骤(2)得到的处理后的催化剂与含有改性助剂组分前驱物的物料进行接触反应；
其中，所述改性助剂组分选自IB、IIA、IIB、IIIA和VIA族元素中的至少一种。
在本发明提供的制备方法中，所述氧化态加氢催化剂为本领域常规使用的各种氧化态加氢催化剂，对其没有特别的限定。可采用本领域的常规方式进行制备或为购买的商业化催化剂。优选情况下，所述氧化态加氢催化剂为具有重油加氢功能的氧化态加氢催化剂。
根据本发明的一种优选实施方式，所述氧化态加氢催化剂包括载体以及活性组分A和活性组分B，所述活性组分A选自第VIII族金属元素中的至少一种，所述活性组分B选自第VIB族金属元素中的至少一种。载体以及活性组分A和活性组分B的选择范围可以与上述第一方面所述的选择范围相同，在此不再赘述。
优选地，以氧化态加氢催化剂的重量为基准，载体的含量为50％-90％，以氧化物计的活性组分B的含量为10％-35％，以氧化物计的活性组分A的含量为2％-8％。
本发明对步骤(1)所述硫化没有特别的限定，可以采用本领域常规方法进行，优选步骤(1)所述硫化为充分硫化，即使氧化态加氢催化剂中的活性金属达到完全硫化的程度，可采用公知的硫化方法，优选所述硫化包括干法硫化和/或湿法硫化。本发明所述干法硫化、湿法硫化具有本领域常规释义。
优选地，所述硫化的条件包括：硫化温度为240-400℃，硫化时间为2-10h，氢气的压力为2-12MPa，氢气的流量为2-25mL·min-1·g-1氧化态加氢催化剂，进一步优选地，硫化温度为280-380℃，硫化时间为3-8h，氢气的压力为3-10MPa，氢气的流量为3-20mL·min-1·g-1氧化态加氢催化剂。
根据本发明的一种优选实施方式，所述湿法硫化采用的硫化液包括含硫化合物和有机溶剂。优选地，所述含硫化合物选自二甲基二硫、二硫化碳、二乙基硫、乙硫醇、正丁硫醇、二叔任基多硫化物和二甲基亚砜中的至少一种。优选地，所述有机溶剂选自环己烷、正庚烷、航空煤油和柴油中的至少一种。
对所述硫化液中含硫化合物的质量分数选择范围较宽，优选为2％-7％，更优选为4％-6％。优选硫化液的流量为0.5-5mL·h-1·g-1氧化态加氢催化剂，优选1-4mL·h-1·g-1氧化态加氢催化剂。
根据本发明的一种优选实施方式，所述干法硫化采用的硫化气包括硫化氢和氢气。优选地，硫化气中，硫化氢的体积含量为1-10％。
根据本发明的一种优选实施方式，所述失硫化处理为轻度失硫化处理。所述轻度失硫化处理 指的是将硫化后活性相边角位上低配位的硫原子移除，而保留活性相体相中三配位的硫原子。
本发明的氧化态加氢催化剂依次经过初次硫化和失硫化处理，使需要改性的金属活性相处于特定的失硫高活性状态，活性相边缘外层为暴露的活性组分，同时可以有效保留加氢活性相中内部的三配位硫原子以及稳定的A-B-S晶体结构，更有利于后续改性助剂组分更有效的与活性相外层金属相接触，使所得加氢催化剂中，改性助剂组分(以R表示)与活性组分A，活性组分B和S形成R-A-B-S组合混合活性相，实现提升加氢催化剂性能的目的。
优选地，步骤(2)所述失硫化处理的温度低于所述硫化的温度，优选所述失硫化处理的温度比所述硫化的温度低50-100℃。
优选地，所述失硫化处理的条件包括：温度为180-370℃，优选200-300℃；处理时间为4-24小时，优选6-16小时，总压力为2-18MPa，优选4-15MPa。
根据本发明，步骤(2)中，所述失硫化处理为轻度失硫化处理，优选在硫化氢存在下进行，优选采用如下至少一种方式进行：
(a)用含有硫化氢的氢气对所述硫化态加氢催化剂进行失硫化处理；
(b)在氢气存在下，用硫化液对所述硫化态加氢催化剂进行失硫化处理。
根据本发明，优选地，方式(a)中，硫化氢与氢气的体积比为200:1-800:1，优选300:1-600:1，总气体流量为5-30mL·min-1·g-1氧化态加氢催化剂，优选10-20mL·min-1·g-1氧化态加氢催化剂。
根据本发明，优选地，方式(b)中，硫化液包括含硫化合物和有机溶剂，其中，含硫化合物选自二甲基二硫、二硫化碳、二乙基硫、乙硫醇、正丁硫醇、二叔任基多硫化物和二甲基亚砜中的至少一种；有机溶剂选自环己烷、正庚烷、航空煤油和柴油中的至少一种。
优选地，方式(b)中，所述硫化液中含硫化合物的质量分数为0.1％-0.6％，例如为0.1％、0.2％、0.3％、0.4％、0.5％、0.6％，以及这些数值中的任意两个所构成的范围中的任意值。
优选地，失硫化处理过程中，硫化液的流量为0.5-4.5mL·h-1·g-1氧化态加氢催化剂，优选1-4mL·h-1·g-1氧化态加氢催化剂。
优选地，失硫化处理过程中，氢气流量为5-30mL·min-1·g-1氧化态加氢催化剂，优选10-20mL·min-1·g-1氧化态加氢催化剂。
本发明步骤(3)所述改性助剂组分种类的选择范围可以同上述第一方面所述改性助剂组分种类的选择范围相同，在此不再赘述。
本发明对所述改性助剂组分前驱物的种类选择范围较宽，只要能够通过步骤(3)所述接触反应提供所述改性助剂组分即可，优选为含有改性助剂组分的有机物和/或氢化物。优选地，所述改性助剂组分前驱物选自乙酰丙酮镓、三乙基镓、硬脂酸银、乙酰丙酮银、环己烷丁酸银、硬脂 酸镁、二丁基镁、丙酮酸镁、L-天门冬氨酸镁、四苯基卟啉镁中、环烷酸锌、甘油锌、二乙基硒和硒化氢中的至少一种。
本发明对所述含有改性助剂组分前驱物的物料的相态没有特别的限定，可以为液相的溶液，也可以为气相的气体。
根据本发明的一种优选实施方式，所述含有改性助剂组分前驱物的物料为含有改性助剂组分前驱物的有机溶液。
在该种优选实施方式下，优选地，含有改性助剂组分前驱物的有机溶液中，改性助剂组分前驱物的质量含量为0.5％-5％，例如为0.5％、1％、2％、3％、4％、4.5％、5％，以及这些数值中的任意两个所构成的范围中的任意值。
对所述含有改性助剂组分前驱物的有机溶液中溶剂选择范围较宽，以能够与所述改性助剂组分前驱物实现较好相容为准，优选地，含有改性助剂组分前驱物的有机溶液中，溶剂选自甲苯、环己烷、十氢萘、四氢萘和正庚烷中的一种或几种。
为了更进一步提高制得的加氢催化剂的性能，优选地，所述含有改性助剂组分前驱物的有机溶液中还含有稳定剂，所述稳定剂选自有机碱性氮化物。所述稳定剂也可称为占位剂，选自具有一定碱性的有机碱性氮化物，这些有机碱性氮化物可以吸附在载体的酸性中心和活性组分上，防止改性助剂组分在载体上的吸附。而吸附在活性组分上的部分有机碱性氮化物可以被加氢转化为烃类和氨气从活性相上脱附，而改性助剂组分可以附着在金属活性相上。
优选地，所述稳定剂选自三乙醇胺、二乙醇胺、一乙醇胺、吡啶、喹啉和苯胺中的至少一种。
优选地，所述含有改性助剂组分前驱物的有机溶液中，稳定剂的质量含量为2％-8％，例如为2％、3％、4％、5％、6％、7％、8％，以及这些数值中的任意两个所构成的范围中的任意值。
根据本发明的一种优选实施方式，步骤(3)所述接触反应的条件包括：温度为80-220℃，优选100-200℃，压力为0.2-8MPa，优选0.5-6MPa，反应时间为2-24小时，优选4-20小时；氢气的用流为2-20mL·min-1·g-1氧化态加氢催化剂，优选5-15mL·min-1·g-1氧化态加氢催化剂；含有改性助剂组分前驱物的物料的流量为2-10mL·h-1·g-1氧化态加氢催化剂，优选3-8mL·h-1·g-1氧化态加氢催化剂。
以上详述了含有改性助剂组分前驱物的物料为含有改性助剂组分前驱物的有机溶液的情况下的一些优选实施方式。改性助剂组分为Ag、Mg、Zn、和Ga中的至少一种时优选采用该种方式进行。
以下详细说明所述含有改性助剂组分前驱物的物料为含有改性助剂组分前驱物的混合气体的情况。优选地，所述含有改性助剂组分前驱物的物料为含有改性助剂组分前驱物的混合气体，所述混合气体中还含有氢气。
优选地，含有改性助剂组分前驱物的混合气体中，改性助剂组分前驱物的体积含量为1％-20％，优选3％-15％，氢气的体积含量为80％-99％，优选85％-97％。
在该种优选实施方式下，所述改性助剂组分前驱物优选为硒化氢。
在该种优选实施方式下，步骤(3)所述接触反应的条件优选包括：温度为120-250℃，优选150-220℃，反应时间为1-8小时，优选2-6小时；反应压力为2-12MPa，优选4-8MPa，含有改性助剂组分前驱物的混合气体的流量为5-40mL·min-1·g-1氧化态加氢催化剂，优选10-30mL·min-1·g- 1氧化态加氢催化剂。
根据本发明，还任选包括对步骤(3)得到的催化剂进行二次硫化。对二次硫化的条件以及方式没有特别的限定，可以参考步骤(1)所述硫化。优选地，所述二次硫化可以选用湿法硫化。二次硫化所采用的硫化液可以包括含硫化合物和有机溶剂；所述硫化液中含硫化合物的质量分数优选为1％-5％，优选1.5％-3.5％。所述硫化合物优选为二乙基硫、乙硫醇、正丁硫醇、二叔任基多硫化物和二甲基亚砜中的一种或几种，所述有机溶剂优选为环己烷、正庚烷、航空煤油和柴油等中的至少一种。
进一步地，步骤(4)中，所述二次硫化的条件包括：温度为250-350℃，优选280-320℃，时间为2-24h，优选4-16h；氢气压力为2-8MPa，优选2-6MPa，氢气的流量为2-15mL·min-1·g-1氧化态加氢催化剂，优选5-10mL·min-1·g-1氧化态加氢催化剂。所述硫化液的流量为1-5mL·h-1·g-1氧化态加氢催化剂，优选2-4mL·h-1·g-1氧化态加氢催化剂。
进一步优选地，初次硫化的温度高于二次硫化的温度，优选高20-100℃，二次硫化的温度高于失硫化处理的温度，优选高20-80℃。
本发明第三方面提供第一方面所述加氢催化剂或者第二方面所述方法制备的加氢催化剂在油品加氢中的应用。将本发明提供的催化剂应用于油品加氢中，具有较好的加氢处理能力以及稳定性。不同改性助剂组分的选择，还使得本发明提供的催化剂具有额外的优势。
本发明的发明人在研究过程中发现，当改性助剂组分为Ga时，所述催化剂特别适用于重质油品的加氢脱氮。优选地，所述加氢催化剂中改性助剂组分为Ga，所述应用为在重质油品加氢脱氮中的应用。优选地，用于处理氮含量为1000μg/g以上，进一步为1500-3000μg/g，残炭质量含量为10wt％以上，进一步为12wt％-15wt％的重质油品。
本发明的发明人在研究过程中发现，当改性助剂组分为Zn时，所述催化剂特别适用于重质油品的加氢脱硫。优选地，所述加氢催化剂中改性助剂组分为Zn，所述应用为在重质油品加氢脱硫中的应用。优选地，用于处理硫含量为2.0wt％以上，尤其是硫含量在3.0wt％以上的重质油品。优选重质油品残炭含量为8.0wt％以上，进一步优选为10wt％-15wt％。
本发明对上述重质油品中金属镍和钒的总含量选择范围较宽，优选地，所述重质油品的金属 镍和钒的总含量Ni+V小于100μg/g，进一步优选为20-60μg/g。所述重质油品包括但不限于脱沥青油。
本发明的发明人在研究过程中发现，当改性助剂组分为Ag时，所述催化剂特别适用于低硫油品的处理。优选地，所述加氢催化剂中改性助剂组分为Ag，所述应用为在低硫油品中的应用。采用Ag改性加氢催化剂在加工低硫油品时，用来加氢饱和油品中的烯烃、二烯烃和芳烃等物质，以及进行加氢脱氧，加氢脱羧等，具有良好的加氢饱和能力以及稳定的加氢脱氧，加氢脱酸能力，且具有稳定性高的优点，特别适合长周期运行。优选所述低硫油品的硫含量低于200μg/g。所述低硫油品包括但不限于生物柴油、费托合成油、低温煤焦油等中的至少一种。
本发明的发明人在研究过程中发现，当改性助剂组分为Mg时，所述催化剂特别适用于油品的烯烃选择性加氢饱和。优选地，所述加氢催化剂中改性助剂组分为Mg，所述应用为在油品烯烃选择性加氢饱和中的应用。优选地，用于处理烯烃质量含量不小于10％的二次加工原料油。所述二次加工原料油可以为煤制合成油、煤焦油，沸腾床渣油加氢尾油，乙烯焦油等中的至少一种。
本发明的发明人在研究过程中发现，当改性助剂组分为Se时，所述催化剂特别适用于重质原料油的加氢脱残炭反应。优选地，所述加氢催化剂中改性助剂组分为Se，所述应用为在重质原料油加氢脱残炭中的应用。优选地，所述重质原料油为残炭质量含量在10％以上的重质原料油，尤其是残炭质量含量在15％以上的重质原料油。所述重质原料油可以来源于劣质重油和/或渣油。
根据本发明的应用，优选包括在氢气存在下，将所述油品与所述加氢催化剂进行反应。优选地，所述反应条件包括：反应温度为200-420℃，优选250-400℃，氢气压力为4-25MPa，优选6-22MPa，液时体积空速为0.1-3h-1，优选0.1-2h-1，氢油体积比为400:1-1500:1，优选400:1-1200:1。
下面结合实施例及对比例来进一步说明本发明方法的制备过程和产品性能，但以下实施例不构成对本发明方法的限制。
以下实施例和对比例加氢催化剂中，分布在A-B-S活性相区域内的改性助剂组分含量占总改性助剂组分含量、A-B-S活性相边角位的硫含量占A-B-S活性相中总硫含量采用TEM-EDS(透射电镜-能量弥散X射线谱)表征，具体方法如具体实施方式部分所述。
以下实施例A1-A6和对比例A1-A5所采用的氧化态加氢催化剂，均采用以下方法制备而得：
称取氧化铝干胶粉1000.0g，加入柠檬酸30.0g，田菁粉10.0g，混合均匀后，加入含硝酸质量分数2.0％的水溶液900.0g，碾压30.0min后，用直径1.6mm的三叶草孔板挤条。经120℃干燥6.0h后600℃焙烧6.0h。焙烧后的载体记为S-0(载体的比表面积为304m2/g，孔容为0.75cm3/g)。称取120.0g四水合七钼酸铵，80.0g六水合硝酸镍，120.0g去离子水，在80℃下，充 分搅拌30min后，冷却至室温，再用去离子水定容到180.0mL，得到的溶液记为Q-0。
取200g载体S-0，使用Q-0浸渍，自然晾干24小时，后120℃干燥4小时，后在420℃下焙烧4.0小时，得到的氧化态加氢催化剂记为CT-0(以催化剂的重量计，载体的含量为68.4％，钼以氧化物计的含量为26.5％，镍以氧化物计的含量为5.1％)。
实施例A1
取1000g环己烷，50.0g二甲基二硫，配制成的硫化液记为SQ-0。
取1000g环己烷，2.0g二甲基二硫，配制成的硫化液记为TQ-1。
取1000g甲苯，25.0g乙酰丙酮镓，40.0g三乙醇胺，配制成含有镓的有机溶液，记为GQ-1。
取20.0g CT-0装入反应管中，使用SQ-0进行硫化，硫化过程中，氢气的压力为6.0MPa，氢气的流量为300.0mL/min，硫化液SQ-0的流量为40.0mL/h，硫化温度为350℃，硫化时间为6小时，得到的硫化态加氢催化剂记为SCT-0。
将反应管温度降低至260℃，氢气压力调整至5.0MPa，氢气的流量为200.0mL/min，向反应管中通入TQ-1，流量为30.0mL/h，处理时间为9小时。得到的催化剂记为TCT-1。
将反应管温度降低至110℃，氢气压力调整至0.8MPa，氢气流量为120.0mL/min，向反应管中通入GQ-1，流量为120.0mL/h，处理时间为8.0小时。得到的催化剂记为ECT-1。
实施例A2
硫化态加氢催化剂SCT-0的制备过程同实施例A1。
取1000g环己烷，3.0g二甲基二硫，配制成的硫化液记为TQ-2。
取1000g甲苯，15.0g三乙基镓，50.0g三乙醇胺，配制成含有镓的有机溶液，记为GQ-2。
将反应管温度降低至280℃，氢气压力调整至6.0MPa，氢气的流量为300.0mL/min，向反应管中通入TQ-2，流量为40.0mL/h，处理时间为12小时。得到的催化剂记为TCT-2。
将反应管温度降低至130℃，压力调整至1.2MPa，氢气流量为150.0mL/min，向反应管中通入GQ-2，流量为120.0mL/h，处理时间为8.0小时。得到的催化剂记为ECT-2。
实施例A3
硫化态加氢催化剂SCT-0的制备过程同实施例A1。
取1000g环己烷，4.0g二甲基二硫，配制成的硫化液记为TQ-3。
取1000g甲苯，10.0g三乙基镓，20.0g乙酰丙酮镓，60.0g三乙醇胺，配制成含有镓的有 机溶液，记为GQ-3。
将反应管温度降低至300℃，氢气压力调整至10.0MPa，氢气的流量为400.0mL/min，向反应管中通入TQ-3，流量为40.0mL/h，处理时间为12小时。得到的催化剂记为TCT-3。
将反应管温度降低至150℃，压力调整至1.8MPa，氢气流量为180.0mL/min，向反应管中通入GQ-3，流量为120.0mL/h，处理时间为8.0小时。得到的催化剂记为ECT-3。
实施例A4
载体S-0，溶液Q-0，氧化态加氢催化剂CT-0，硫化液SQ-0，硫化催化剂SCT-0的制备过程同实施例A1。
将反应管温度降低至280℃，反应压力调整至6.0MPa，向反应管中通入氢气和硫化氢的混合气体，氢气与硫化氢的体积比为400:1，混合气体的总流量为400mL/min，处理时间为12小时。得到的催化剂记为TCT-4。
取1000g甲苯，15.0g三乙基镓，15.0g乙酰丙酮镓，60.0g三乙醇胺，配制成含有镓的有机溶液，记为GQ-4。
将反应管温度降低至150℃，压力调整至0.6MPa，氢气流量为150.0mL/min，向反应管中通入GQ-4，流量为120.0mL/h，处理时间为8.0小时。得到的催化剂记为ECT-4。
实施例A5
载体S-0，溶液Q-0，氧化态加氢催化剂CT-0，硫化液SQ-0，硫化催化剂SCT-0的制备过程同实施例A1。
将反应管温度降低至280℃，反应压力调整至6.0MPa，向反应管中通入氢气和硫化氢的混合气体，氢气与硫化氢的体积比为500:1，混合气体的总流量为500mL/min，处理时间为12小时。得到的催化剂记为TCT-5。
取1000g甲苯，10.0g三乙基镓，20.0g乙酰丙酮镓，60.0g三乙醇胺，配置成含有镓的有机溶液，记为GQ-5。
将反应管温度降低至150℃，压力调整至0.6MPa，氢气流量为150.0mL/min，向反应管中通入GQ-5，流量为120.0mL/h，处理时间为8.0小时。得到的催化剂记为ECT-5。
实施例A6
按照实施例A1的方法，不同的是，GQ-1中不加入三乙醇胺。得到的催化剂记为ECT-6。
对比例A1
取20.0g CT-0装入反应管中，使用SQ-0进行硫化，硫化过程中，氢气的压力为6.0MPa，氢气的流量为300.0mL/min，硫化液SQ-0的流量为40.0mL/h，硫化温度为350℃，硫化时间为6小时，硫化后的催化剂记为DCT-1。
对比例A2
催化剂DCT-1的制备过程同对比例A1。
将装有DCT-1的反应管降温至260℃，氢气压力调整至5.0MPa，氢气的流量为200.0mL/min，向反应管中通入TQ-1，流量为30.0mL/h，处理时间为9小时。得到的催化剂记为DCT-2。
对比例A3
硫化态加氢催化剂SCT-0的制备过程同实施例A1。
将装有SCT-0的反应管降温至110℃，压力调整至0.8MPa，氢气流量为120.0mL/min，向反应管中通入GQ-1，流量为120mL/h，处理时间为8.0小时。得到的催化剂记为DCT-3。
对比例A4
硫化态加氢催化剂SCT-0的制备过程同实施例A1。
将装有SCT-0的反应管降温至260℃，氢气压力调整至5.0MPa，氢气的流量为240.0mL/min，处理时间为9小时。得到的催化剂记为DTCT-4。
将反应管温度降低至110℃，压力调整至0.8MPa，氢气流量为120.0mL/min，向反应管中通入GQ-1，流量为120L/h，处理时间为8.0小时。得到的催化剂记为DCT-4。
对比例A5
称取氧化铝干胶粉1000.0g，加入柠檬酸30.0g，田菁粉10.0g，混合均匀后，加入含硝酸质量分数2.0％的水溶液900.0g，碾压30.0min后，用直径1.6mm的三叶草孔板挤条。经120℃干燥6.0h后600℃焙烧6.0h。焙烧后的载体记为S-0。
称取120.0g四水合七钼酸铵，80.0g六水合硝酸镍，12.0g无水硝酸镓，120.0g去离子水，在80℃下，充分搅拌30min后，冷却至室温，再用去离子水定容到180.0mL，得到的溶液记为DQ-5。
取200g载体S-0，使用DQ-5浸渍，自然晾干24小时，后120℃干燥4小时，后在420℃下 焙烧4.0小时，得到的氧化态加氢催化剂记为DCT-0。
取20.0g DCT-0装入反应管中，使用SQ-0(同实施例A1)进行硫化，硫化过程中，氢气的压力为6.0MPa，氢气的流量为300.0mL/min，硫化液SQ-0的流量为40.0mL/h，硫化温度为350℃，硫化时间为6小时，得到的硫化态加氢催化剂记为DCT-5。
以上催化剂的物化组成如表A1所示。
表A1催化剂的物化组成
对加氢催化剂进行TEM-EDS表征，得出催化剂中分布在Ni-Mo-S活性相区域内的Ga含量占总Ga含量的百分数以及Ni-Mo-S活性相边角位的硫含量占Ni-Mo-S活性相中总硫含量的百分数。具体见表A2。
表A2
测试例A1
分别对实施例A1-A6所得的催化剂进行活性评价，脱沥青油的性质见表A3。采用固定床工艺，在上述催化剂之前装填加氢保护剂(FZC-100B)，所述保护剂与实施例所得加氢脱氮催化剂的装填体积比为1:4。操作条件为：反应温度390℃，反应压力20.0MPa，氢油体积比1000：1，液时体积空速为0.2h-1。反应评价2000h后针对加氢生成油不低于200℃馏分中，残炭值，硫含量 和氮含量进行分析，结果如表A4所示。
对比测试例A1
分别对对比例A1-A5所得的催化剂进行活性评价，脱沥青油的性质见表A3。采用固定床工艺，在上述催化剂之前装填加氢保护剂(FZC-100B)，所述保护剂与对比例所得加氢脱氮催化剂的装填体积比为1:4。操作条件为：反应温度390℃，反应压力20.0MPa，氢油体积比1000：1，液时体积空速为0.2h-1。反应评价2000h后针对加氢生成油不低于200℃馏分中，残炭值，硫含量和氮含量进行分析，结果如表A4所示。
表A3脱沥青油的性质
表A4催化剂2000h加氢评价结果

从表A4的评价结果中可以看出，本发明制备的加氢催化剂，不仅有很好的加氢脱氮能力，而且也具有良好的芳烃饱和能力和加氢脱硫能力。
本发明中以下实施例B1-B5和对比例B1-B5所采用的氧化态加氢催化剂，均采用以下方法制备而得：
称取氧化铝干胶粉1000.0g，加入柠檬酸30.0g，田菁粉10.0g，混合均匀后，加入含硝酸质量分数2.0％的水溶液900.0g，碾压30.0min后，用直径1.6mm的三叶草孔板挤条。经120℃干燥6.0h后600℃焙烧6.0h。焙烧后的载体记为S-0(载体的比表面积为304m2/g，孔容为0.75cm3/g)。称取100.0g四水合七钼酸铵，60.0g六水合硝酸镍，120.0g去离子水，在80℃下，充分搅拌30min后，冷却至室温，再用去离子水定容到180.0mL，得到的溶液记为Q-0。取200g载体S-0，使用Q-0浸渍，自然晾干24小时，后120℃干燥4小时，后在420℃下焙烧4.0小时，得到的氧化态加氢催化剂记为CT-0(以催化剂的质量为基准，载体的含量为70.2％，钼以氧化物计的含量为25.0％，镍以氧化物计的含量为4.8％)。
实施例B1
取1000g环己烷，50.0g二甲基二硫，配制成的硫化液记为SQ-0。
取1000g环己烷，2.0g二甲基二硫，配制成的硫化液记为TQ-1。
取2000g甲苯，70.0g硬脂酸银，80.0g苯胺，配制成含有银的有机溶液，记为YQ-1。
取20.0g CT-0装入反应管中，使用SQ-0进行初次硫化，条件为：硫化温度为350℃，氢气的压力为6.0MPa，氢气的流量为300.0mL/min，硫化液SQ-0的流量为40.0mL/h，硫化时间为6小时，得到的硫化态加氢催化剂记为SCT-0。
将反应管温度降低至260℃，氢气压力调整至5.0MPa，氢气的流量为200.0mL/min，向反应管中通入TQ-1，流量为30.0mL/h，处理时间为9小时。得到的催化剂记为TCT-1。
将反应管温度降低至110℃，氢气压力调整至1.0MPa，氢气流量为120.0mL/min，向反应管中通入YQ-1，流量为80.0mL/h，处理时间为9.0小时。得到的催化剂记为ECT-1。
实施例B2
硫化态加氢催化剂SCT-0的制备过程同实施例B1。
取1000g环己烷，3.0g二硫化碳，配制成的硫化液记为TQ-2。
取2000g甲苯，80.0g乙酰丙酮银，80.0g苯胺，配制成含有银的有机溶液，记为YQ-2。
取1000g环己烷，30.0g二硫化碳，配制成的硫化液记为RQ-2。
将反应管温度降低至280℃，氢气压力调整至6.0MPa，氢气的流量为300.0mL/min，向反应管中通入TQ-2，流量为40.0mL/h，处理时间为12小时。得到的催化剂记为TCT-2。
将反应管温度降低至130℃，氢气压力调整至1.5MPa，氢气流量为150.0mL/min，向反应管中通入YQ-2，流量为100.0mL/h，处理时间为12.0小时。得到的催化剂记为ECT-2。
实施例B3
硫化态加氢催化剂SCT-0的制备过程同实施例B1。
取1000g环己烷，4.0g二甲基二硫，配制成的硫化液记为TQ-3。
取2000g甲苯，90.0g环己烷丁酸银，80.0g苯胺，配制成含有银的有机溶液，记为YQ-3。
将反应管温度降低至300℃，氢气压力调整至10.0MPa，氢气的流量为400.0mL/min，向反应管中通入TQ-3，流量为40.0mL/h，处理时间为12小时。得到的催化剂记为TCT-3。
将反应管温度降低至150℃，氢气压力调整至2.0MPa，氢气流量为180.0mL/min，向反应管中通入YQ-3，流量为120.0ml/h，处理时间为15.0小时。得到的催化剂记为ECT-3。
实施例B4
硫化态加氢催化剂SCT-0的制备过程同实施例B1。
取2000g甲苯，100.0g硬脂酸银，80.0g苯胺，配制成含有银的有机溶液，记为YQ-4。
将反应管温度降低至260℃，反应压力调整至4.0MPa，同时通入氢气和硫化氢的混合气体，氢气与硫化氢的分压比例为300:1，混合气体流量为300.0mL/min，处理时间为12小时。得到的催化剂记为TCT-4。
将反应管温度降低至140℃，氢气压力调整至2.5MPa，氢气流量为150.0mL/min，向反应管中通入YQ-4，流量为100.0ml/h，处理时间为12.0小时。得到的催化剂记为ECT-4。
实施例B5
硫化态加氢催化剂SCT-0的制备过程同实施例B1。
取2000g甲苯，60.0g乙酰丙酮银，80.0g苯胺，配制成含有银的有机溶液，记为YQ-5。
将反应管温度降低至260℃，反应压力调整至4.0MPa，同时通入氢气和硫化氢的混合气体， 氢气与硫化氢的分压比例为250:1，混合气体流量为350.0mL/min，处理时间为12小时。得到的催化剂记为TCT-5。
将反应管温度降低至160℃，氢气压力调整至3.0MPa，氢气流量为160.0mL/min，向反应管中通入YQ-5，流量为100.0mL/h，处理时间为12.0小时。得到的催化剂记为ECT-5。
对比例B1
取20.0g CT-0装入反应管中，使用SQ-0进行硫化，硫化过程中，氢气的压力为6.0MPa，氢气的流量为300.0mL/min，硫化液SQ-0的流量为40.0mL/h，硫化温度为350℃，硫化时间为6.0小时，硫化后的催化剂记为DCT-1。
对比例B2
催化剂DCT-1的制备过程同对比例B1。
将装有DCT-1的反应管降温至260℃，氢气压力调整至5.0MPa，氢气的流量为200.0mL/min，向反应管中通入TQ-1，流量为30.0mL/h，处理时间为9小时。得到的催化剂记为DCT-2。
对比例B3
硫化态加氢催化剂SCT-0的制备过程同实施例B1。
取2000g甲苯，环己烷丁酸银90.0g，80.0g苯胺，配制成含有银的有机溶液，记为DYQ-3。
将装有SCT-0的反应管降温至150℃，氢气压力调整至2.0MPa，氢气流量为180.0mL/min，向反应管中通入DYQ-3，流量为120.0mL/h，处理时间为15.0小时。得到的催化剂记为DCT-3。
对比例B4
催化剂DCT-1的制备过程同对比例B1。
取2000g甲苯，90.0g环己烷丁酸银，80.0g苯胺，配制成含有银的有机溶液，记为DYQ-4。
将装有DCT-1的反应管降温至300℃，氢气压力调整至10.0MPa，氢气的流量为400.0mL/min，处理时间为12小时。得到的催化剂记为DTCT-4。
将装有DTCT-4反应管温度降低至150℃，氢气压力调整至2.0MPa，氢气流量为180.0mL/min，向反应管中通入DYQ-4，流量为120.0mL/h，处理时间为15.0小时。得到的催化剂记为DCT-4。
对比例B5
称取氧化铝干胶粉1000.0g，加入柠檬酸30.0g，田菁粉10.0g，混合均匀后，加入含硝酸质量分数2.0％的水溶液900.0g，碾压30.0min后，用直径1.6mm的三叶草孔板挤条。经120℃干燥6.0h后600℃焙烧6.0h。焙烧后的载体记为S-0。
称取100.0g四水合七钼酸铵，60.0g六水合硝酸镍，7.5g硝酸银，120.0g去离子水，在80℃下，充分搅拌30min后，冷却至室温，再用去离子水定容到180.0mL，得到的溶液记为DQ-5。
取200g载体S-0，使用DQ-5浸渍，自然晾干24小时，后120℃干燥4小时，后在420℃下焙烧4.0小时，得到的氧化态加氢催化剂记为DCT-0。
取20.0g DCT-0装入反应管中，使用SQ-0进行初次硫化，硫化过程中，氢气的压力为6.0MPa，氢气的流量为300.0mL/min，硫化液SQ-0的流量为40.0mL/h，硫化温度为350℃，硫化时间为6小时，得到的硫化态加氢催化剂记为DCT-5。
以上催化剂的组成如表B1所示。
表B1各例所得催化剂的组成
对各例所得加氢催化剂进行TEM-EDS表征，得出催化剂中分布在Ni-Mo-S活性相区域内的Ag含量占总Ag含量的百分数以及Ni-Mo-S活性相边角位的硫含量占Ni-Mo-S活性相中总硫含量的百分数。具体见表B2。
表B2

测试例B1
在固定床加氢装置上对实施例B1-B5催化剂ECT-1至ECT-5的活性和稳定性进行考察，评价条件为：反应压力8.0MPa，氢油体积比500:1，温度300℃，体积空速2.0h-1，对反应500小时和1500小时两个时间点的样品进行取样分析。其中选用的原料油为费托合成油，其性质如表B3所示，催化剂评价结果如表B4所示。
对比测试例B1
在固定床加氢装置上对对比例B1-B5催化剂DCT-1至DCT-5的活性和稳定性进行考察，评价条件同测试例B1。
表B3原料油性质
表B4催化剂评价结果

从表B4评价结果中可以看出，使用本发明加氢催化剂，在加工处理低硫的费托合成油时，在长周期运行的情况下，仍具有良好的加氢脱酸，加氢饱和性能，保持了良好的活性稳定性。
本发明中以下实施例C1-C5和对比例C1-C5所采用的氧化态加氢催化剂，均采用以下方法制备而得：
称取氧化铝干胶粉1000.0g，加入柠檬酸10.0g，田菁粉50.0g，混合均匀后，加入含乙酸质量分数1.0％的水溶液900.0g，混捏20.0min后，用直径2.4mm的三叶草孔板挤条。经120℃干燥6.0h后750℃焙烧6.0h。焙烧后的载体记为S-0(经分析检测，载体的比表面积为322m2/g，载体的孔容为0.9cm3/g)。称取40.0g四水合七钼酸铵，25.0g六水合硝酸镍，150.0g去离子水，在80℃下，充分搅拌30min后，冷却至室温，再用去离子水定容到210.0mL，得到的溶液记为Q-0。
取200g载体S-0，使用Q-0浸渍，自然晾干24小时，后120℃干燥4小时，后在420℃下焙烧4.0小时，得到的氧化态加氢催化剂记为CT-0(以催化剂的重量计，载体的含量为84.1％，钼以氧化物计的含量为13.2％，镍以氧化物计的含量为2.7％)。
实施例C1
取1000g环己烷，50.0g二甲基二硫，配制成的硫化液记为SQ-0。
取1000g环己烷，2.0g二甲基二硫，配制成的硫化液记为TQ-1。
取2000g甲苯，35.0g四苯基卟啉镁，50.0g二乙醇胺，配置成含有镁的有机溶液，记为MQ-1。
取20.0g CT-0装入反应管中，使用SQ-0进行硫化，硫化过程中，氢气的压力为6.0MPa， 氢气的流量为300.0mL/min，硫化液SQ-0的流量为40.0mL/h，硫化温度为350℃，硫化时间为6小时，硫化后的催化剂记为SCT-0。
将反应管温度降低至260℃，氢气压力调整至5.0MPa，氢气的流量为200.0mL/min，向反应管中通入TQ-1，流量为30.0mL/h，处理时间为9小时。得到的催化剂记为TCT-1。
将反应管温度降低至110℃，氢气压力调整至0.4MPa，气体流量为100.0mL/min，向反应管中通入MQ-1，流量为80.0mL/h，处理时间为10.0小时。得到的催化剂记为ECT-1。
实施例C2
载体S-0，溶液Q-0，氧化态加氢催化剂CT-0，硫化液SQ-0，硫化催化剂SCT-0的制备过程同实施例C1。
取1000g环己烷，3.0g二甲基二硫，配制成的硫化液记为TQ-2。
取2000g甲苯，16.0g L-天门冬氨酸镁，50.0g二乙醇胺，配置成含有镁的有机溶液，记为MQ-2。
将反应管温度降低至280℃，氢气压力调整至6.0MPa，氢气的流量为300.0mL/min，向反应管中通入TQ-2，流量为40.0mL/h，处理时间为12小时。得到的催化剂记为TCT-2。
将反应管温度降低至130℃，压力调整至0.6MPa，气体流量为120.0mL/min，向反应管中通入MQ-2，流量为100.0mL/h，处理时间为12.0小时。得到的催化剂记为ECT-2。
实施例C3
载体S-0，溶液Q-0，氧化态加氢催化剂CT-0，硫化液SQ-0，硫化催化剂SCT-0的制备过程同实施例C1。
取1000g环己烷，4.0g二甲基二硫，配制成的硫化液记为TQ-3。
取2000g环己烷，12.0g二正丁基镁，50.0g二乙醇胺，配置成含有镁的有机溶液，记为MQ-3。
将反应管温度降低至300℃，氢气压力调整至8.0MPa，氢气的流量为400.0mL/min，向反应管中通入TQ-3，流量为40.0mL/h，处理时间为12小时。得到的催化剂记为TCT-3。
将反应管温度降低至150℃，压力调整至0.8MPa，气体流量为140.0mL/min，向反应管中通入MQ-3，流量为120.0mL/h，处理时间为10.0小时。得到的催化剂记为ECT-3。
实施例C4
硫化催化剂SCT-0的制备过程同实施例C1。
将反应管温度降低至280℃，反应压力调整至6.0MPa，向反应管中通入氢气和硫化氢的混合气体，氢气与硫化氢的体积比为350:1，混合气体的总流量为350mL/min，处理时间为12小时。得到的催化剂记为TCT-4。
取2000.0g甲苯与12.0g丙酮酸镁，50.0g二乙醇胺，配置成含有镁的有机溶液，记为MQ-4。
将反应管温度降低至140℃，压力调整至0.6MPa，气体流量为130.0mL/min，向反应管中通入MQ-4，流量为120.0mL/h，处理时间为12.0小时。得到的催化剂记为ECT-4。
实施例C5
硫化催化剂SCT-0的制备过程同实施例C1。
将反应管温度降低至300℃，反应压力调整至6.0MPa，向反应管中通入氢气和硫化氢的混合气体，氢气与硫化氢的体积比为550:1，混合气体的总流量为450mL/min，处理时间为12小时。得到的催化剂记为TCT-5。
取2000.0g正辛烷与30.0g硬脂酸镁，50.0g二乙醇胺，配置成含有镁的有机溶液，记为MQ-5。
将反应管温度降低至150℃，压力调整至0.6MPa，气体流量为130.0mL/min，向反应管中通入MQ-5，流量为120.0mL/h，处理时间为14.0小时。得到的催化剂记为ECT-5。
对比例C1
取20.0g CT-0装入反应管中，使用SQ-0进行硫化，硫化过程中，氢气的压力为6.0MPa，氢气的流量为300.0mL/min，硫化液SQ-0的流量为40.0mL/h，硫化温度为350℃，硫化时间为6.0小时，硫化后的催化剂记为DCT-1。
对比例C2
催化剂DCT-1的制备过程同对比例C1。
将装有DCT-1的反应管降温至260℃，氢气压力调整至5.0MPa，氢气的流量为200.0mL/min，向反应管中通入TQ-1，流量为30.0mL/h，处理时间为9小时。得到的催化剂记为DCT-2。
对比例C3
硫化态加氢催化剂SCT-0的制备过程同实施例C1。
取2000g甲苯，35.0g四苯基卟啉镁，50.0g二乙醇胺，配置成含有镁的有机溶液，记为 DGQ-3。
将装有SCT-0的反应管降温至110℃，压力调整至0.4MPa，气体流量为100.0mL/min，向反应管中通入DGQ-3，流量为80.0mL/h，处理时间为10.0小时。得到的催化剂记为DCT-3。
对比例C4
催化剂DCT-1的制备过程同对比例C1。
取2000g甲苯，35.0g四苯基卟啉镁，50.0g二乙醇胺，配置成含有镁的有机溶液，记为DGQ-4。
将装有DCT-1的反应管降温至260℃，氢气压力调整至5.0MPa，氢气的流量为200.0mL/min，处理时间为9小时。得到的催化剂记为DTCT-4。
将反应管温度降低至110℃，压力调整至0.4MPa，气体流量为100.0mL/min，向反应管中通入DGQ-4，流量为80.0mL/h，处理时间为10.0小时。得到的催化剂记为DCT-4。
对比例C5
载体S-0的制备过程同实施例C1。
称取40.0g四水合七钼酸铵，25.0g六水合硝酸镍，15.0g无水硝酸镁，150.0g去离子水，在80℃下，充分搅拌30min后，冷却至室温，再用去离子水定容到210.0mL，得到的溶液记为DQ-5。
取200g载体S-0，使用DQ-5浸渍，自然晾干24小时，后120℃干燥4小时，后在420℃下焙烧4.0小时，得到的氧化态加氢催化剂记为DCT-0。
取20.0g DCT-0装入反应管中，使用SQ-0(同实施例1)进行硫化，硫化过程中，氢气的压力为6.0MPa，氢气的流量为300.0mL/min，硫化液SQ-0的流量为40.0mL/h，硫化温度为350℃，硫化时间为6小时，得到的硫化态加氢催化剂记为DCT-5。
以上催化剂的组成如表C1所示。
表C1各例所得催化剂的物化组成

对Mg改性加氢催化剂进行TEM-EDS表征，得出催化剂中分布在Ni-Mo-S活性相区域内的Mg含量占总Mg含量的百分数以及Ni-Mo-S活性相边角位的硫含量占Ni-Mo-S活性相中总硫含量的百分数。具体见表C2。
表C2
测试例C1
分别对实施例C1-C5所得的催化剂进行活性评价，其中，原料油的性质如表C3所示，对原料进行加氢评价，评价条件为：反应温度320℃，反应压力8.0MPa，液时体积空速2.5h-1，氢油体积比800:1，对催化剂进行1000小时评价后，得到的评价结果如表C4所示。
对比测试例C1
分别对对比例C1-C5所得的催化剂进行活性评价，其中，原料油的性质如表C3所示，对原料进行加氢评价，评价条件为：反应温度320℃，反应压力8.0MPa，液时体积空速2.5h-1，氢油体积比800:1，对催化剂进行1000小时评价后，得到的评价结果如表C4所示。
表C3煤制合成油的性质

表C4评价结果
从表C4评价结果中可以看出，本发明方法制备的Mg改性加氢催化剂，不仅具有较好的加氢活性，而且对烯烃具有很好的加氢饱和性能，且催化剂稳定性良好。
本发明中以下实施例D1-D5和对比例D1-D5所采用的氧化态加氢催化剂，均采用以下方法制备而得：
称取氧化铝干胶粉1000.0g，加入柠檬酸10.0g，田菁粉30.0g，混合均匀后，加入含硝酸质量分数0.5％的水溶液1000.0g，碾压10.0min后，用直径2.0mm的三叶草孔板挤条。经120℃干燥6.0h后800℃焙烧6.0h。焙烧后的载体记为S-0(经分析检测，载体的比表面积为271m2/g，载体的孔容为0.93cm3/g)。
称取50.0g四水合七钼酸铵，30.0g六水合硝酸镍，150.0g去离子水，在60℃下，充分搅拌30min后，冷却至室温，再用去离子水定容到200.0mL，得到的溶液记为Q-0。
取200g载体S-0，使用Q-0浸渍，自然晾干24小时，后120℃干燥4小时，后在480℃下焙烧4.0小时，得到的氧化态加氢催化剂记为CT-0(以催化剂的重量计，载体的含量为72.1％，钼以氧化物计的含量为24.9％，镍以氧化物计的含量为3.0％)。
实施例D1
取1000g环己烷，50.0g二甲基二硫，配制成的硫化液记为SQ-0。
取1000g环己烷，2.0g二甲基二硫，配制成的硫化液记为TQ-1。
取1000g环己烷，25.0g甘油锌，60.0g一乙醇胺，配制成含有锌的有机溶液，记为ZQ-1。
取20.0g CT-0装入反应管中，使用SQ-0进行硫化，硫化过程中，氢气的压力为6.0MPa，氢气的流量为300.0mL/min，硫化液SQ-0的流量为40.0mL/h，硫化温度为350℃，硫化时间为6小时，硫化后的催化剂记为SCT-0。
将反应管温度降低至260℃，氢气压力调整至5.0MPa，氢气的流量为200.0mL/min，向反应管中通入TQ-1，流量为30.0mL/h，处理时间为9小时。得到的催化剂记为TCT-1。
将反应管温度降低至140℃，氢气压力调整至3.0MPa，气体流量为120.0mL/min，向反应管中通入ZQ-1，流量为80.0mL/h，处理时间为3.0小时。得到的催化剂记为ECT-1。
实施例D2
载体S-0，溶液Q-0，氧化态加氢催化剂CT-0，硫化液SQ-0，硫化催化剂SCT-0的制备过程同实施例D1。
取1000g环己烷，3.0g二甲基二硫，配制成的硫化液记为TQ-2。
取1000g甲苯，30.0g甘油锌，60.0g一乙醇胺，配制成含有锌的有机溶液，记为ZQ-2。
将反应管温度降低至280℃，氢气压力调整至6.0MPa，氢气的流量为300.0mL/min，向反应管中通入TQ-2，流量为40.0mL/h，处理时间为12小时。得到的催化剂记为TCT-2。
将反应管温度降低至160℃，压力调整至4.0MPa，气体流量为150.0mL/min，向反应管中通入ZQ-2，流量为100.0mL/h，处理时间为4.0小时。得到的催化剂记为ECT-2。
实施例D3
载体S-0，溶液Q-0，氧化态加氢催化剂CT-0，硫化液SQ-0，硫化催化剂SCT-0的制备过程同实施例D1。
取1000g环己烷，4.0g二甲基二硫，配制成的硫化液记为TQ-3。
取1000g甲苯，40.0g甘油锌，60.0g一乙醇胺，配制成含有锌的有机溶液，记为ZQ-3。
将反应管温度降低至300℃，氢气压力调整至10.0MPa，氢气的流量为400.0mL/min，向反应管中通入TQ-3，流量为40.0mL/h，处理时间为12小时。得到的催化剂记为TCT-3。
将反应管温度降低至190℃，压力调整至5.0MPa，气体流量为180.0mL/min，向反应管中通入ZQ-3，流量为120.0mL/h，处理时间为5.0小时。得到的催化剂记为ECT-3。
实施例D4
载体S-0，溶液Q-0，氧化态加氢催化剂CT-0，硫化液SQ-0，硫化催化剂SCT-0的制备过程同实施例D1。
将反应管温度降低至280℃，反应压力调整至6.0MPa，向反应管中通入氢气和硫化氢的混合气体，氢气与硫化氢的体积比为350:1，混合气体的总流量为350mL/min，处理时间为12小时。得到的催化剂记为TCT-4。
将反应管温度降低至140℃，氢气压力调整至3.0MPa，气体流量为120.0mL/min，向反应管中通入ZQ-1，流量为80.0mL/h，处理时间为3.0小时。得到的催化剂记为ECT-4。
实施例D5
载体S-0，溶液Q-0，氧化态加氢催化剂CT-0，硫化液SQ-0，硫化催化剂SCT-0的制备过程同实施例D1。
将反应管温度降低至300℃，反应压力调整至6.0MPa，向反应管中通入氢气和硫化氢的混合气体，氢气与硫化氢的体积比为450:1，混合气体的总流量为450mL/min，处理时间为12小时。得到的催化剂记为TCT-5。
将反应管温度降低至140℃，氢气压力调整至3.0MPa，气体流量为120.0mL/min，向反应管中通入ZQ-1，流量为80.0mL/h，处理时间为3.0小时。得到的催化剂记为ECT-5。
对比例D1
取20.0g CT-0装入反应管中，使用SQ-0进行硫化，硫化过程中，氢气的压力为6.0MPa，氢气的流量为300.0mL/min，硫化液SQ-0的流量为40.0mL/h，硫化温度为350℃，硫化时间为6.0小时，硫化后的催化剂记为DCT-1。
对比例D2
催化剂DCT-1的制备过程同对比例D1。
将装有DCT-1的反应管降温至260℃，氢气压力调整至5.0MPa，氢气的流量为200.0mL/min，向反应管中通入TQ-1，流量为30.0mL/h，处理时间为9小时。得到的催化剂记为DCT-2。
对比例D3
硫化态加氢催化剂SCT-0的制备过程同实施例D1。
将装有SCT-0的反应管降温至140℃，压力调整至3.0MPa，气体流量为120.0mL/min，向反应管中通入ZQ-1，流量为80.0mL/h，处理时间为3.0小时。得到的催化剂记为DCT-3。
对比例D4
催化剂DCT-1的制备过程同对比例D1。
将装有DCT-1的反应管降温至260℃，氢气压力调整至5.0MPa，氢气的流量为200.0mL/min，处理时间为9小时。得到的催化剂记为DTCT-4。
将反应管温度降低至140℃，压力调整至3.0MPa，气体流量为120.0mL/min，向反应管中通入ZQ-1，流量为80.0mL/h，处理时间为3.0小时。得到的催化剂记为DCT-4。
对比例D5
载体S-0的制备过程同实施例D1。
称取50.0g四水合七钼酸铵，30.0g六水合硝酸镍，80.0g无水硝酸锌，150.0g去离子水，在60℃下，充分搅拌30min后，冷却至室温，再用去离子水定容到200.0mL，得到的溶液记为DQ-5。
取200g载体S-0，使用DQ-5浸渍，自然晾干24小时，后120℃干燥4小时，后在420℃下焙烧4.0小时，得到的氧化态加氢催化剂记为DCT-0。
取20.0g DCT-0装入反应管中，使用SQ-0(同实施例D1)进行硫化，硫化过程中，氢气的压力为6.0MPa，氢气的流量为300.0mL/min，硫化液SQ-0的流量为40.0mL/h，硫化温度为350℃，硫化时间为6小时，得到的硫化态加氢催化剂记为DCT-5。
以上催化剂的组成如表D1所示。
表D1各例所得催化剂的物化组成

对Zn改性加氢脱硫催化剂进行TEM-EDS表征，得出催化剂中分布在Ni-Mo-S活性相区域内的Zn含量占总Zn含量的百分数以及Ni-Mo-S活性相边角位的硫含量占Ni-Mo-S活性相中总硫含量的百分数。具体见表D2。
表D2
测试例D1
分别对实施例D1-D5所得的催化剂进行活性评价，脱沥青油的性质见表D3。采用固定床工艺，在上述催化剂之前装填加氢保护剂(FZC-100B)，所述保护剂与实施例所得加氢脱硫催化剂的装填体积比为1:4。操作条件为：反应温度385℃，反应压力18.0MPa，氢油体积比800:1，液时体积空速为0.15h-1。反应评价2000h后针对加氢生成油不低于200℃馏分中，残炭值，硫含量和氮含量进行分析，结果如表D4所示。
对比测试例D1
分别对对比例D1-D5所得的催化剂进行活性评价，脱沥青油的性质见表D3。采用固定床工艺，在上述催化剂之前装填加氢保护剂(FZC-100B)，所述保护剂与实施例所得加氢脱硫催化剂的装填体积比为1:4。操作条件为：反应温度385℃，反应压力18.0MPa，氢油体积比800:1，液时体积空速为0.15h-1。反应评价2000h后针对加氢生成油不低于200℃馏分中，残炭值，硫含量和氮含量进行分析，结果如表D4所示。
表D3脱沥青油性质

表D4评价结果
从表D4的评价结果中可以看出，本发明加氢脱硫催化剂，不仅有很好的加氢脱硫能力，而且也具有良好的加氢脱氮能力和加氢脱残炭能力。
本发明中以下实施例E1-E5和对比例E1-E5所采用的氧化态加氢催化剂，均采用以下方法制备而得：
称取氧化铝干胶粉1000.0g，加入柠檬酸20.0g，田菁粉20.0g，混合均匀后，加入含硝酸质量分数1.0％的水溶液1000.0g，碾压20.0min后，用直径1.8mm的三叶草孔板挤条。经120℃干燥6.0h后700℃焙烧6.0h。焙烧后的载体记为S-0(经分析，载体的性质如下：比表面积为270m2/g，孔容为0.9cm3/g)。称取74.2g四水合七钼酸铵，47.3g六水合硝酸镍，150.0g去离子水，在60℃下，充分搅拌20min后，冷却至室温，再用去离子水定容到200.0mL，得到的溶液记为 Q-0。
取200g载体S-0，使用Q-0浸渍，自然晾干24小时，后120℃干燥4小时，后在450℃下焙烧5.0小时，得到的氧化态加氢催化剂记为CT-0(以催化剂的重量计，载体的含量为73.3％，钼以氧化物计的含量为22.2％，镍以氧化物计的含量为4.5％)。
实施例E1
取1000g环己烷，50.0g二甲基二硫，配制成的硫化液记为SQ-0。
取1000g环己烷，2.0g二甲基二硫，配制成的硫化液记为TQ-1。
取20.0g CT-0装入反应管中，使用SQ-0进行硫化处理，硫化过程中，氢气的压力为6.0MPa，氢气的流量为300.0mL/min，硫化液SQ-0的流量为40.0mL/h，硫化温度为350℃，硫化时间为6小时，得到的硫化态加氢催化剂记为SCT-0。
将反应管温度降低至260℃，氢气压力调整至5.0MPa，氢气的流量为200.0mL/min，向反应管中通入TQ-1，流量为30.0mL/h，处理时间为9小时。得到的催化剂记为TCT-1。
将反应管温度降低至160℃，压力调整至5.0MPa，向反应管中通入氢气和硒化氢的混合气体，其中，混合气体中，氢气体积分数为95％，硒化氢的体积分数为5％，混合气体的流量为300.0mL/min，处理时间为3.0小时。得到的催化剂记为ECT-1。
实施例E2
硫化态加氢催化剂SCT-0的制备过程同实施例E1。
取1000g环己烷，3.0g二硫化碳，配制成的硫化液记为TQ-2。
将装有硫化态加氢催化剂SCT-0的反应管温度降低至280℃，氢气压力调整至6.0MPa，氢气的流量为300.0mL/min，向反应管中通入TQ-2，流量为40.0mL/h，处理时间为12小时。得到的催化剂记为TCT-2。
将反应管温度降低至180℃，压力调整至8.0MPa，向反应管中通入氢气和硒化氢的混合气体，其中，氢气体积分数为93％，硒化氢的体积分数为7％，混合气体流量为400.0mL/min，处理时间为4.0小时。得到的催化剂记为ECT-2。
实施例E3
硫化态加氢催化剂SCT-0的制备过程同实施例E1。
取1000g环己烷，4.0g二甲基亚砜，配制成的硫化液记为TQ-3。
将装有硫化态加氢催化剂SCT-0的反应管温度降低至300℃，氢气压力调整至10.0MPa，氢 气的流量为400.0mL/min，向反应管中通入TQ-3，流量为40.0mL/h，处理时间为12小时。得到的催化剂记为TCT-3。
将反应管温度降低至200℃，压力调整至7.0MPa，向反应管中通入氢气和硒化氢的混合气体，其中，氢气体积分数为90％，硒化氢的体积分数为10％，混合气体流量为500.0mL/min，处理时间为5.0小时。得到的催化剂记为ECT-3。
实施例E4
硫化态加氢催化剂SCT-0的制备过程同实施例E1。
将装有硫化态加氢催化剂SCT-0的反应管温度降低至270℃，反应压力调整至6.0MPa，同时通入氢气和硫化氢的混合气体，氢气与硫化氢的分压比例为400:1，混合气体流量为400.0mL/min，处理时间为12小时。得到的催化剂记为TCT-4。
将反应管温度降低至180℃，压力调整至8.0MPa，向反应管中通入氢气和硒化氢的混合气体，其中，氢气体积分数为93％，硒化氢的体积分数为7％，混合气体流量为500.0mL/min，处理时间为4.0小时。得到的催化剂记为ECT-4。
实施例E5
硫化态加氢催化剂SCT-0的制备过程同实施例E1。
将装有硫化态加氢催化剂SCT-0的反应管温度降低至250℃，反应压力调整至6.0MPa，同时通入氢气和硫化氢的混合气体，氢气与硫化氢的分压比例为400:1，混合气体流量为400.0mL/min，处理时间为12小时。得到的催化剂记为TCT-5。
将反应管温度降低至210℃，压力调整至7.0MPa，向反应管中通入氢气和硒化氢的混合气体，其中，氢气体积分数为88％，硒化氢的体积分数为12％，混合气体流量为300.0mL/min，处理时间为5.0小时。得到的催化剂记为ECT-5。
对比例E1
取20.0g CT-0装入反应管中，使用SQ-0进行硫化，硫化过程中，氢气的压力为6.0MPa，氢气的流量为300.0mL/min，硫化液SQ-0的流量为40.0mL/h，硫化温度为350℃，硫化时间为6.0小时，硫化后的催化剂记为DCT-1。
对比例E2
催化剂DCT-1的制备过程同对比例E1。
将装有DCT-1的反应管降温至260℃，氢气压力调整至5.0MPa，氢气的流量为200.0mL/min，向反应管中通入TQ-1，流量为30.0mL/h，处理时间为9小时。得到的催化剂记为DCT-2。
对比例E3
硫化态加氢催化剂SCT-0的制备过程同实施例E1。
将装有SCT-0的反应管降温至180℃，氢气压力调整至8.0MPa，向反应管中通入氢气和硒化氢的混合气体，其中，氢气体积分数为93％，硒化氢的体积分数为7％，气体流量为400.0mL/min，处理时间为4.0小时。得到的催化剂记为DCT-3。
对比例E4
催化剂DCT-1的制备过程同对比例E1。
将装有DCT-1的反应管降温至260℃，氢气压力调整至5.0MPa，氢气的流量为200.0mL/min，处理时间为9小时。得到的催化剂记为DTCT-4。
将反应管温度降低至160℃，压力调整至5.0MPa，向反应管中通入氢气和硒化氢的混合气体，其中，氢气体积分数为95％，硒化氢的体积分数为5％，混合气体流量为300.0mL/min，处理时间为3.0小时。得到的催化剂记为DCT-4。
对比例E5
取20.0g CT-0装入反应管中，向反应管中通入氢气和硒化氢的混合气体，其中氢气的体积分数为90％，硒化氢的体积分数为10％，反应温度为200℃，反应压力为7.0MPa，混合气体流量为500.0mL/min，处理时间为5.0小时。得到的催化剂记为DCT-5。
以上催化剂的组成如表E1所示。
表E1各例所得催化剂的物化组成

对加氢脱残炭催化剂进行TEM-EDS表征，得出催化剂中分布在Ni-Mo-S活性相区域内的Se含量占总Se含量的百分数以及Ni-Mo-S活性相边角位的硫含量占Ni-Mo-S活性相中总硫含量的百分数。具体见表E2。
表E2
测试例E1
分别对实施例E1-E5所得的催化剂进行活性评价，渣油原料性质见表E3。采用固定床工艺，在上述催化剂之前装填加氢保护剂(FZC-100B)、加氢脱金属催化剂(FZC-204A)、加氢脱硫催化剂(FZC-33B)，所述保护剂、加氢脱金属催化剂、加氢脱硫催化剂、实施例所得催化剂的装填体积比为1.5：2.0：2.0：4.5。操作条件为：反应温度380℃，反应压力16.0MPa，氢油体积比1200:1，液时体积空速为0.2h-1。反应评价2000h后针对加氢生成油不低于200℃馏分中，残炭值，饱和分和氮含量进行分析，结果如表E4所示。
对比测试例E1
分别对对比例E1-E5所得的催化剂进行活性评价，渣油原料性质见表E3。采用固定床工艺，在上述催化剂之前装填加氢保护剂(FZC-100B)、加氢脱金属催化剂(FZC-204A)、加氢脱硫催化剂(FZC-33B)，所述保护剂、加氢脱金属催化剂、加氢脱硫催化剂、对比例所得催化剂的装填体积比为1.5：2.0：2.0：4.5。操作条件为：反应温度380℃，反应压力16.0MPa，氢油体积比1200:1，液时体积空速为0.2h-1。反应评价2000h后针对加氢生成油不低于200℃馏分中，残炭值，饱和分和氮含量进行分析，结果如表E4所示。
表E3原料油性质
表E4各催化剂2000h加氢评价结果
从表E4的评价结果中可以看出，本发明催化剂有良好的加氢脱残炭、加氢饱和能力和较好的加氢脱氮能力。

Claims (16)

  1. 一种加氢催化剂，所述加氢催化剂为硫化态加氢催化剂，包括载体以及活性组分A、活性组分B和改性助剂组分，所述活性组分A选自第VIII族金属元素中的至少一种，所述活性组分B选自第VIB族金属元素中的至少一种，所述改性助剂组分选自IB、IIA、IIB、IIIA和VIA族元素中的至少一种；
    其中，所述加氢催化剂采用TEM-EDS方法表征，分布在A-B-S活性相区域内的改性助剂组分含量占总改性助剂组分含量的60％-98％，优选为75％-98％。
  2. 根据权利要求1所述的加氢催化剂，其中，所述加氢催化剂采用TEM-EDS方法表征，A-B-S活性相边角位的硫含量占A-B-S活性相中总硫含量的6.0％以下，优选为0.5％-4.5％。
  3. 根据权利要求1所述的加氢催化剂，其中，以加氢催化剂的质量为基准，以元素计，活性组分A的含量为1-10％，优选1.5％-6％；以元素计，活性组分B的含量为6％-24％，优选8％-18％；
    优选地，以加氢催化剂的质量为基准，以元素计，改性助剂组分的含量为0.2％-4％，优选0.8％-4％；
    优选地，以加氢催化剂的质量为基准，硫元素的含量为3％-20％，优选4％-15％。
  4. 根据权利要求1-3中任意一项所述的加氢催化剂，其中，所述活性组分A为Co和/或Ni，所述活性组分B为Mo和/或W；
    优选地，所述活性组分A为Ni，所述活性组分B为Mo；
    优选地，所述改性助剂组分选自Cu、Ag、Au、Mg、Ca、Zn、Cd、Ga和Se中的至少一种，更优选为Ag、Mg、Zn、Ga和Se中的至少一种；
    优选地，所述载体选自氧化铝、氧化硅和无定形硅铝中的至少一种。
  5. 一种加氢催化剂的制备方法，该方法包括以下步骤：
    (1)对氧化态加氢催化剂进行硫化，得到硫化态加氢催化剂；
    (2)将所述硫化态加氢催化剂进行失硫化处理；
    (3)将步骤(2)得到的处理后的催化剂与含有改性助剂组分前驱物的物料进行接触反应；
    其中，所述改性助剂组分选自IB、IIA、IIB、IIIA和VIA族元素中的至少一种。
  6. 根据权利要求5所述的制备方法，其中，所述氧化态加氢催化剂包括载体以及活性组分A和活性组分B，所述活性组分A选自第VIII族金属元素中的至少一种，所述活性组分B选自第VIB族金属元素中的至少一种；
    优选地，所述活性组分A为Co和/或Ni，所述活性组分B为Mo和/或W；
    优选地，所述活性组分A为Ni，所述活性组分B为Mo；
    优选地，所述载体选自氧化铝、氧化硅和无定形硅铝中的至少一种；
    优选地，以氧化态加氢催化剂的重量为基准，载体的含量为50％-90％，以氧化物计的活性组分B的含量为10％-35％，以氧化物计的活性组分A的含量为2％-8％。
  7. 根据权利要求5或6所述的制备方法，其中，所述硫化包括干法硫化和/或湿法硫化；
    优选地，所述硫化的条件包括：硫化温度为240-400℃，硫化时间为2-10h，氢气的压力为2-12MPa，氢气的流量为2-25mL·min-1·g-1氧化态加氢催化剂。
  8. 根据权利要求5-7中任意一项所述的制备方法，其中，步骤(2)所述失硫化处理的温度低于所述硫化的温度，优选所述失硫化处理的温度比所述硫化的温度低50-100℃；
    优选地，所述失硫化处理的条件包括：温度为180-370℃，优选200-300℃；处理时间为4-24小时，优选6-16小时，总压力为2-18MPa，优选4-15MPa。
  9. 根据权利要求5-8中任意一项所述的制备方法，其中，步骤(2)中，所述失硫化处理为轻度失硫化处理，优选采用如下至少一种方式进行：
    (a)用含有硫化氢的氢气对所述硫化态加氢催化剂进行失硫化处理；
    (b)在氢气存在下，用硫化液对所述硫化态加氢催化剂进行失硫化处理。
  10. 根据权利要求9所述的制备方法，其中，方式(a)中，硫化氢与氢气的体积比为200∶1-800∶1，优选300∶1-600∶1，总气体流量为5-30mL·min-1·g-1氧化态加氢催化剂，优选10-20mL·min-1·g-1氧化态加氢催化剂；
    和/或，方式(b)中，硫化液包括含硫化合物和有机溶剂，其中，含硫化合物选自二甲基二硫、二硫化碳、二乙基硫、乙硫醇、正丁硫醇、二叔任基多硫化物和二甲基亚砜中的至少一种；有机溶剂选自环己烷、正庚烷、航空煤油和柴油中的至少一种；
    优选地，所述硫化液中含硫化合物的质量分数为0.1％-0.6％；
    优选地，失硫化处理过程中，硫化液的流量为0.5-4.5mL·h-1·g-1氧化态加氢催化剂，优选1-4mL·h-1·g-1氧化态加氢催化剂；
    优选地，失硫化处理过程中，氢气流量为5-30mL·min-1·g-1氧化态加氢催化剂，优选10-20mL·min-1·g-1氧化态加氢催化剂。
  11. 根据权利要求5-10中任意一项所述的制备方法，其中，所述改性助剂组分选自Cu、Ag、Au、Mg、Ca、Zn、Cd、Ga和Se中的至少一种，更优选为Ag、Mg、Zn、Ga和Se中的至少一种；
    优选地，所述改性助剂组分前驱物选自乙酰丙酮镓、三乙基镓、硬脂酸银、乙酰丙酮银、环己烷丁酸银、硬脂酸镁、二丁基镁、丙酮酸镁、L-天门冬氨酸镁、四苯基卟啉镁中、环烷酸锌、甘油锌、二乙基硒和硒化氢中的至少一种。
  12. 根据权利要求5-11中任意一项所述的制备方法，其中，所述含有改性助剂组分前驱物的物料为含有改性助剂组分前驱物的有机溶液；
    优选地，含有改性助剂组分前驱物的有机溶液中，改性助剂组分前驱物的质量含量为0.5％-5％；
    优选地，含有改性助剂组分前驱物的有机溶液中，溶剂选自甲苯、环己烷、十氢萘、四氢萘和正庚烷中的一种或几种。
  13. 根据权利要求12所述的制备方法，其中，所述含有改性助剂组分前驱物的有机溶液中还含有稳定剂，所述稳定剂选自有机碱性氮化物；
    优选地，所述稳定剂选自三乙醇胺、二乙醇胺、一乙醇胺、吡啶、喹啉和苯胺中的至少一种；
    优选地，所述含有改性助剂组分前驱物的有机溶液中，稳定剂的质量含量为2％-8％。
  14. 根据权利要求5-13中任意一项所述的制备方法，其中，步骤(3)所述接触反应的条件包括：温度为80-220℃，优选100-200℃，压力为0.2-8MPa，优选0.5-6MPa，反应时间为2-24小时，优选4-20小时；氢气的用流为2-20mL·min-1·g-1氧化态加氢催化剂，优选5-15mL·min-1·g-1氧化态加氢催化剂；含有改性助剂组分前驱物的物料的流量为2-10mL·h-1·g-1氧化态加氢催化剂，优选3-8mL·h-1·g-1氧化态加氢催化剂。
  15. 根据权利要求5-11中任意一项所述的制备方法，其中，所述含有改性助剂组分前驱物的物料为含有改性助剂组分前驱物的混合气体，所述混合气体中还含有氢气；
    优选地，含有改性助剂组分前驱物的混合气体中，改性助剂组分前驱物的体积含量为1％-20％，优选3％-15％，氢气的体积含量为80％-99％，优选85％-97％；
    优选地，所述改性助剂组分前驱物为硒化氢；
    优选地，步骤(3)所述接触反应的条件包括：温度为120-250℃，优选150-220℃，反应时间为1-8小时，优选2-6小时；反应压力为2-12MPa，优选4-8MPa，含有改性助剂组分前驱物的混合气体的流量为5-40mL·min-1·g-1氧化态加氢催化剂，优选10-30mL·min-1·g-1氧化态加氢催化剂。
  16. 权利要求1-4中任意一项所述加氢催化剂或按照权利要求5-15中任意一项所述方法制备的加氢催化剂在油品加氢中的应用。
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CN113559884A (zh) * 2020-04-28 2021-10-29 中国石油化工股份有限公司 硫化态重油加氢催化剂及其制备方法和应用
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