WO2022089637A1 - 一种吸附剂、液相加氢催化剂组合物、催化剂床及其用途 - Google Patents

一种吸附剂、液相加氢催化剂组合物、催化剂床及其用途 Download PDF

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Publication number
WO2022089637A1
WO2022089637A1 PCT/CN2021/127928 CN2021127928W WO2022089637A1 WO 2022089637 A1 WO2022089637 A1 WO 2022089637A1 CN 2021127928 W CN2021127928 W CN 2021127928W WO 2022089637 A1 WO2022089637 A1 WO 2022089637A1
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Prior art keywords
hydrogenation
catalyst
component
adsorbent
sulfur
Prior art date
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Ceased
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PCT/CN2021/127928
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English (en)
French (fr)
Inventor
杨成敏
刘丽
段为宇
郭蓉
周勇
李扬
姚运海
郑步梅
孙进
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Original Assignee
China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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Priority claimed from CN202011198740.2A external-priority patent/CN114433058B/zh
Priority claimed from CN202011526437.0A external-priority patent/CN114713145B/zh
Priority claimed from CN202011530014.6A external-priority patent/CN114713240B/zh
Application filed by China Petroleum and Chemical Corp, Sinopec Dalian Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to US18/245,993 priority Critical patent/US20230347322A1/en
Priority to CA3192576A priority patent/CA3192576A1/en
Priority to KR1020237014832A priority patent/KR20230093444A/ko
Priority to CN202180072420.9A priority patent/CN116600894A/zh
Priority to EP21885363.8A priority patent/EP4197631A4/en
Publication of WO2022089637A1 publication Critical patent/WO2022089637A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C10G2300/703—Activation

Definitions

  • the present invention relates to the technical field of liquid-phase hydrogenation of oil products, and more particularly to an adsorbent, a liquid-phase hydrogenation catalyst composition comprising the adsorbent, a catalyst bed comprising the liquid-phase hydrogenation catalyst composition, and an adsorbent thereof in adsorption technology or applications in liquid phase hydrogenation of oil products.
  • Liquid-phase diesel hydrogenation is a new technology emerging in recent years, which hydrogenates diesel raw materials containing impurities such as sulfur in the state of liquid-solid two-phase.
  • the feedstock for liquid-phase diesel hydrogenation is continuously contacted with the catalyst, and the dissolved hydrogen and sulfur-containing compounds to be reacted therein have more advantages in terms of mass transfer.
  • CN103789029A discloses a two-phase hydrogenation combined method.
  • a separator is arranged in the middle of a high-pressure separator of a traditional gas-phase circulating hydrogenation device, and the high-pressure separator is divided into two parts, a gas-liquid separation chamber and a hydrogen-dissolving chamber.
  • the middle distillate oil which is difficult to remove impurities, is processed by the gas-phase circulating hydrogenation process.
  • the generated material enters the gas-liquid separation chamber for gas-liquid separation, and the separated liquid phase enters the fractionation system.
  • the feedstock of the two-phase hydrogenation unit entering the upper part of the hydrogen chamber and the circulating oil are in countercurrent contact.
  • the two-phase hydrogenation unit feedstock and circulating oil after dissolving hydrogen enter the two-phase hydrogenation reactor for hydrogenation reaction.
  • CN102876368A discloses a diesel liquid-phase hydrogenation method, wherein fresh diesel fuel is mixed with hydrogen in a hydrogen mixing tank and then enters a liquid-phase hydrogenation reactor for hydrorefining reaction, and the reaction effluent is decompressed by a pressure reducing valve without heat exchange Then, it enters the high temperature and low pressure flash tank for flash evaporation. A part of the obtained liquid phase is circulated back to the hydrogen mixing tank, mixed with fresh feed, and then mixed with hydrogen in the hydrogen mixing tank. The other part of the liquid phase is mixed with the flash vapor and then separated to obtain diesel products.
  • CN108855115A discloses a coated catalyst, which includes three parts: hydrodesulfurization active component, sulfur adsorbent and carrier.
  • the mass fraction of hydrodesulfurization active component is 2.0-20.0wt%, and the mass fraction of sulfur adsorbent is 30.0- 80.0wt%, and the balance is carrier.
  • Hydrogen sulfide the product of liquid-phase hydrogenation, has an inhibitory effect on the reaction system, so the removal of hydrogen sulfide or the elimination or weakening of its inhibitory effect has always been a technical problem.
  • the prior art has combined an adsorbent component with a hydrodesulfurization catalytic component in an attempt to provide protection for the hydrodesulfurization catalytic component through the chemical adsorption of hydrogen sulfide by the adsorbent component.
  • the inventors of the present invention found that the disadvantage of this type of chemical adsorbent is that due to the existence of a saturation upper limit for chemical adsorption, the adsorption capacity of the chemical adsorbent for hydrogen sulfide is limited, which is manifested in the duration of the adsorption efficiency of the adsorbent for hydrogen sulfide. Short, the hydrodesulfurization catalytic component protection period is short.
  • the inventors of the present invention have found an adsorbent with a specific structure and composition through assiduous research, which can realize temporary adsorption and temporary aggregation of hydrogen sulfide in the liquid phase hydrogenation process, thereby reducing the added
  • concentration of hydrogen sulfide on the catalyst component with hydrogen reaction activity reduces the influence of hydrogen sulfide on the hydrogenation reaction and its inhibitory effect on the hydrodesulfurization catalyst, and the adsorption is reversible (in situ adsorption and desorption).
  • the adsorbent has self-cleaning ability, which can maintain the hydrogen sulfide adsorption efficiency for a long time, and does not require the regeneration process required by chemical adsorbents.
  • the present invention relates to the following aspects.
  • a liquid-phase hydrogenation catalyst composition characterized in that the composition comprises at least one hydrogenation catalytic component with desulfurization activity and at least one sulfur adsorption component;
  • the sulfur adsorption component includes an adsorbent porous material and a hydrogenation active metal supported on the adsorbent porous material. Based on the total weight of the sulfur adsorption component, the mass percentage of the adsorbent porous material is more than 90%, so The mass percentage of the hydrogenation active metal in terms of oxide is less than 10%.
  • liquid-phase hydrogenation catalyst composition according to any one of the preceding or following aspects, characterized in that, by weight, the hydrogenation catalytic component with desulfurization activity accounts for 30%-99%, preferably 40% %-97%, more preferably 60%-95%.
  • liquid-phase hydrogenation catalyst composition according to any one of the preceding or following aspects, wherein the sulfur adsorption component accounts for 1%-70%, preferably 3%-60%, more preferably 5% %-40%.
  • liquid-phase hydrogenation catalyst composition according to any one of the preceding or following aspects, wherein the particle size of the sulfur adsorption component is 0.5-5.0 mm, and the particle size of the hydrogenation catalyst having desulfurization activity is 0.5-5.0 mm. Diameter size is 0.5-4.0 mm.
  • liquid-phase hydrogenation catalyst composition according to any one of the preceding or following aspects, characterized in that the amount of hydrogen sulfide adsorbed by the sulfur adsorbing component at 250-400° C. Hydrogenation catalysts are 20% to 500% higher.
  • liquid-phase hydrogenation catalyst composition according to any one of the preceding or following aspects, wherein the average pore size of the sulfur adsorption component is 10%-80% of the hydrogenation catalyst with desulfurization activity, preferably 20%-60%.
  • liquid-phase hydrogenation catalyst composition according to any one of the preceding or following aspects, wherein the specific surface area of the sulfur adsorption component is 110%-300% of that of the hydrogenation catalyst having desulfurization activity, It is preferably 110%-200%.
  • liquid phase hydrogenation catalyst composition according to any one of the preceding or following aspects, wherein the adsorbent porous material is selected from the group consisting of activated carbon, alumina, silica, magnesia, zirconia, titania and At least one of molecular sieves.
  • liquid-phase hydrogenation catalyst composition according to any one of the preceding or following aspects, wherein the hydrogenation active metal in the sulfur adsorption component is selected from Fe, Co, Ni, Cu, Zn, Cr At least one of , Mo and W.
  • liquid-phase hydrogenation catalyst composition according to any one of the preceding or following aspects, wherein the sulfur adsorption component is prepared by a supported catalyst preparation method: extruding an adsorbent porous material, drying and calcining, impregnating the hydrogenation active metal, and then drying and calcining to obtain the sulfur adsorption component.
  • liquid-phase hydrogenation catalyst composition according to any one of the preceding or following aspects, wherein the hydrogenation catalyst component with desulfurization activity is selected from at least one of a supported catalyst and an unsupported catalyst kind.
  • the liquid-phase hydrogenation catalyst composition according to any one of the preceding or following aspects, characterized in that the supported catalyst comprises a carrier and hydrogenation active components, and a catalyst modified on the basis thereof,
  • the mass content of the hydrogenation active components in terms of metal oxides is 15%-40% based on the total weight of the catalyst.
  • the liquid-phase hydrogenation catalyst composition according to any one of the preceding or following aspects, characterized in that, the unsupported catalyst comprises at least necessary binder and hydrogenation active components, based on the total weight of the catalyst In terms of metal oxides, the mass content of the hydrogenation active components is 30%-80%.
  • liquid-phase hydrogenation catalyst composition according to any one of the preceding or following aspects, wherein the carrier in the supported catalyst and the binder in the unsupported catalyst are inorganic refractory oxidation compound, at least one selected from oxides of elements of Group II, Group III, Group IV and Group IVB of the Periodic Table of the Elements.
  • liquid phase hydrogenation catalyst composition according to any one of the preceding or following aspects, characterized in that the hydrogenation active component is oxides of metals of Group VIB and Group VIII, wherein the metal of Group VIB is Mo and/or W and the Group VIII metal is Co and/or Ni.
  • liquid-phase hydrogenation catalyst composition according to any one of the preceding or following aspects, characterized in that the mass content of the metal oxide of Group VIB in the catalyst is 15%-30%, and the metal oxide of Group VIII is 15%-30% by mass. The content of metal oxide in the catalyst is 2%-10%.
  • liquid-phase hydrogenation catalyst composition according to any one of the preceding or following aspects, wherein the supported catalyst is formed by extruding an inorganic refractory oxide, drying and calcining and then impregnating the hydrogenation The active component is then dried and calcined to obtain the hydrogenation catalytic component with desulfurization activity.
  • liquid-phase hydrogenation catalyst composition according to any one of the preceding or following aspects, wherein the unsupported catalyst is prepared by co-precipitation of the hydrogenation active component and the binder component Homogeneous catalyst.
  • liquid-phase hydrogenation catalyst composition according to any one of the preceding or following aspects in the liquid-phase hydrogenation reaction of oil products.
  • the present invention also relates to the following aspects.
  • An adsorbent especially a hydrogen sulfide adsorbent, characterized in that it comprises a porous material and a hydrogenation active metal supported on the porous material, wherein the adsorbent has an average pore size of 2-15 nm (preferably 2-10 nm), the specific surface area of the adsorbent is 200-500 m 2 /g (preferably 250-400 m 2 /g), and based on the total weight of the adsorbent, the hydrogenation active metal is a metal oxide The total mass content is 2.5 wt % or less (preferably 2 wt % or less, 1.5 wt % or less, or 0.05-1 wt %).
  • the adsorbent according to any of the preceding or following aspects, wherein the hydrogenation-active metal is present in the form of an oxide/sulfide, and/or, the adsorbent is fully sulfided, and/or , based on the total weight of the adsorbent, the sulfur content (calculated as elemental sulfur) of the adsorbent is 3wt% or less (preferably 2wt% or less, 1wt% or less or 0.5wt% or less, but preferably 0.4wt% or more, 0.5 wt% or more, 1.0 wt% or more, or 1.3 wt% or more).
  • the adsorbent according to any one of the aforementioned or the following aspects is a physical adsorbent for hydrogen sulfide, and its hydrogen sulfide retention time is 30-300 min (preferably 40-250 min, more preferably 60-180 min).
  • the mass percentage of the porous material is 90wt% or more (preferably 92wt% or more, 94wt% or more, 95wt% based on the total weight of the adsorbent) above, above 98 wt %, or 98-99.5 wt %), and/or, the porous material is selected from activated carbon, inorganic refractory oxides (especially from alumina, silica, magnesia, zirconia, and titania) at least one of) and at least one of molecular sieves (especially selected from at least one of alumina and silica), and/or, the hydrogenation active metal is selected from Fe, Co, Ni, Cu, At least one of Zn, Cr, Mo and W (preferably at least one selected from Fe, Zn, Ni, Co and Cu, more preferably at least one selected from Fe and Ni).
  • adsorbent according to any one of the preceding or following aspects, wherein the particle size of the adsorbent is 0.5-5.0 mm (preferably 1-4 mm).
  • An adsorption method comprising contacting an adsorbent according to any one of the preceding or following aspects with a material containing a sulfur-containing compound (especially hydrogen sulfide) to adsorb (especially reversibly adsorb) the sulfur-containing compound. step (referred to as an adsorption step), and optionally including a step of subjecting the adsorbent to a sulfurization treatment (referred to as a sulfurization step) prior to performing the adsorption step.
  • a material containing a sulfur-containing compound especially hydrogen sulfide
  • adsorb especially reversibly adsorb
  • a liquid phase hydrogenation catalyst composition comprising at least one hydrogenation catalytic component having desulfurization activity and at least one sulfur adsorption component, wherein the sulfur adsorption component comprises a porous material and is supported on the porous material.
  • a hydrogenation active metal on a material wherein the sulfur adsorption component has an average pore diameter of 2-15 nm (preferably 2-10 nm), and the sulfur adsorption component has a specific surface area of 200-500 m 2 /g (preferably 250-400 m 2 /g), based on the total weight of the sulfur adsorption component, the mass percentage of the hydrogenation active metal in terms of metal oxide is 10 wt % or less (preferably 8 wt % or less, 6 wt % or less, 5 wt % or less, 2.5 wt % or less) wt % or less, 2 wt % or less, 1.5 wt % or less, or 0.05-1 wt %), and the mass content of the hydrogen
  • liquid-phase hydrogenation catalyst composition according to any one of the preceding or following aspects, wherein the weight ratio of the hydrogenation catalytic component with desulfurization activity to the sulfur adsorption component is 30-99: 1- 70 (preferably 40-97:3-60, more preferably 60-95:5-40), and/or, the hydrogenation catalytic component with desulfurization activity is in the form of solid particles, and the sulfur adsorption component is a solid particle form, and the hydrogenation catalytic component with desulfurization activity and the sulfur adsorption component exist in a form independent of each other (such as independent aggregates or physical mixtures).
  • the hydrogenation catalyst component with desulfurization activity is a porous solid particle with a particle size of 0.5-4.0 mm (preferably 1 -4mm), and/or, the average pore size of the hydrogenation catalytic component with desulfurization activity is 2-30 nm (preferably 5-25 nm), and/or, the ratio of the hydrogenation catalytic component with desulfurization activity
  • the surface area is 100-400 m 2 /g (preferably 150-300 m 2 /g), and/or, the hydrogen sulfide retention time of the sulfur adsorption component is 1.3-5.0 times that of the hydrogenation catalyst with desulfurization activity (preferably 1.5-3.0 times or 2.0-3.0 times), and/or, the average pore size of the sulfur adsorption component is 10-80% (preferably 20-60% or 20%) of the average pore size of the hydrogenation catalyst with desulfurization activity -70%, more preferably 40-65%), and/or,
  • liquid-phase hydrogenation catalyst composition according to any one of the preceding or following aspects, wherein the hydrogenation catalytic component having desulfurization activity is selected from at least one of a supported catalyst and an unsupported catalyst.
  • liquid phase hydrogenation catalyst composition according to any one of the preceding or following aspects, wherein the supported catalyst comprises a carrier and a hydrogenation active component, and/or the unsupported catalyst comprises a binder and hydrogenation active components.
  • liquid-phase hydrogenation catalyst composition according to any one of the preceding or following aspects, wherein, based on the total weight of the supported catalyst, the mass content of the hydrogenation active component in terms of metal oxides is 15 -40% (preferably 20-35%), and/or, based on the total weight of the unsupported catalyst, the mass content of the hydrogenation active component in terms of metal oxides is 30-80% (preferably 40%) -65%).
  • the liquid phase hydrogenation catalyst composition according to any one of the preceding or following aspects, wherein the support is an inorganic refractory oxide (preferably selected from Group II, Group III, Group IV and at least one of oxides of group IVB elements, more preferably selected from at least one of alumina and silicon oxide), and/or, the binder is an inorganic refractory oxide (preferably selected from periodic elements Table at least one of oxides of Group II, Group III, Group IV and Group IVB elements, more preferably selected from at least one of alumina and silica), and/or, the hydrogenation
  • the active component is selected from at least one of oxides of metals of group VIB and oxides of metals of group VIII of the periodic table (preferably, the metal of group VIB is Mo and/or W, and the metal of group VIB is Mo and/or W, and the metal of group VIB is Group VIII metals are Co and/or Ni).
  • liquid-phase hydrogenation catalyst composition according to any one of the preceding or following aspects, wherein, based on the total weight of the supported catalyst, the mass content of the Group VIB metal in terms of metal oxide is 15- 30% (preferably 18-27%), the mass content of the Group VIII metal in terms of metal oxide is 2-10% (preferably 3-7%), and/or, based on the total amount of the unsupported catalyst In terms of weight, the mass content of the Group VIB metal in terms of metal oxide is 15-60% (preferably 18-57%), and the mass content of the Group VIII metal in terms of metal oxide is 2-20% ( preferably 3-18%).
  • a catalyst bed (especially a fixed bed) comprising the liquid phase hydrogenation catalyst composition according to any one of the preceding or following aspects.
  • the hydrogenation catalytic component having desulfurization activity forms at least one sub-catalyst bed A (preferably a column-shaped sub-catalyst bed A) along the material flow direction.
  • the sulfur adsorption component forms at least one sub-catalyst bed B (preferably a columnar sub-catalyst bed B) along the material flow direction, and the sub-catalyst bed A and the sub-catalyst bed B alternately phase Adjacent, and/or, the hydrogenation catalytic component having desulfurization activity and the sulfur adsorption component are present in a substantially homogeneous mixture.
  • the sub-catalyst bed B has a cross-section of any shape (such as at least one selected from the group consisting of rectangle, circle, ellipse, triangle, parallelogram, ring and irregular shape), and /or, on any cross section of the catalyst bed, the straight-line distance from the center point of the cross section of any one of the sub catalyst beds A to the center point of the cross section of any one of the sub catalyst beds B adjacent to it not more than 500mm (preferably not more than 200mm), and/or, in any cross-section of the catalyst bed, the area of the cross-section of the sub-catalyst bed A and the cross-section of the sub-catalyst bed B are the same as each other Or different, each independently is not more than 300000mm 2 (preferably not more than 100000mm 2 ), and/or, in any cross section of the catalyst bed, any point on the cross section of any one of the sub-catalyst beds A to its phase
  • the shortest distance of the edge of the cross-section such as at least
  • the proportion of the hydrogenation catalytic component with desulfurization activity is 35-90% (preferably 45%). -80%, more preferably 50-75%), and the proportion of the sulfur adsorption component is 10-65% (preferably 20-55%, more preferably 25-50%).
  • the reaction conditions of the vulcanization treatment include: dry vulcanization or wet vulcanization; the vulcanizing agent is at least one selected from hydrogen sulfide, carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide;
  • the pressure is 1.2-15MPaG (1.2-9.4MPaG)
  • the curing temperature is 280-400°C
  • the curing time is 4-22h.
  • a hydrogenation process (preferably a liquid phase fixed bed hydrogenation process) comprising the liquid phase hydrogenation catalyst composition according to any one of the preceding or following aspects or the liquid phase hydrogenation catalyst composition according to any one of the preceding or following aspects
  • the step in which the catalyst bed is contacted with the oil product under the conditions of liquid-phase hydrogenation reaction and the hydrogenation reaction occurs (called the hydrogenation step).
  • the oil product is selected from at least one of gasoline, kerosene, diesel oil, wax oil, residual oil and coal tar (preferably selected from diesel oil, wax oil and at least one of residual oil), and/or, the sulfur content (converted to hydrogen sulfide) of the oil is 0.01-3.0 wt% (preferably 0.01-2.0 wt%), and/or, the liquid phase added
  • the hydrogen reaction conditions include: reaction temperature 100-500°C (preferably 100-450°C), reaction pressure 1-20MPaG (preferably (2-15MPaG), liquid hourly space velocity 1-10h -1 (preferably 2-10h -1 , more Preferably 2-8h -1 ), the (dissolved) hydrogen content of the oil is 0.01-0.35wt% (preferably 0.05-0.25wt%).
  • the reaction conditions of the vulcanization treatment include: dry vulcanization or wet vulcanization, and the vulcanizing agent is at least one selected from hydrogen sulfide, carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide,
  • the vulcanization pressure is 1.2-15MPaG (1.2-9.4MPaG)
  • the vulcanization temperature is 280-400°C
  • the vulcanization time is 4-22h.
  • FIG. 1 is a schematic cross-sectional view of the reactor after catalyst D1 and catalyst A1 are staged and loaded in Example 35.
  • FIG. 1 is a schematic cross-sectional view of the reactor after catalyst D1 and catalyst A1 are staged and loaded in Example 35.
  • FIG. 2 is a schematic cross-sectional view of the reactor after catalyst D2 and catalyst A2 are staged and loaded in Example 36.
  • FIG. 2 is a schematic cross-sectional view of the reactor after catalyst D2 and catalyst A2 are staged and loaded in Example 36.
  • FIG. 3 is a schematic cross-sectional view of the reactor after the catalyst D3 and catalyst A3 are staged and loaded in Example 37.
  • FIG. 3 is a schematic cross-sectional view of the reactor after the catalyst D3 and catalyst A3 are staged and loaded in Example 37.
  • the adsorbent according to the present invention belongs to the physical adsorbent of hydrogen sulfide, has no upper limit of hydrogen sulfide adsorption capacity, can continuously exert the hydrogen sulfide adsorption effect for a long time, and when used in combination with a hydrodesulfurization catalyst, compared with the existing The technology can effectively extend the protection period of the hydrodesulfurization catalyst.
  • the adsorbent according to the present invention has self-cleaning ability, and when used in combination with a hydrodesulfurization catalyst, can provide effective protection throughout the life cycle of the hydrodesulfurization catalyst without the need for a regeneration process of the chemical adsorbent.
  • the adsorption of hydrogen sulfide can be realized during the liquid phase hydrogenation process, and the flow of the liquid material can be used to promote the adsorption of sulfur
  • the desorption of hydrogen sulfide on the component makes the adsorption and desorption reach a dynamic balance, so as to realize the accumulation of hydrogen sulfide in the material, that is, at the height of each thin layer in the catalyst bed, the hydrogen sulfide in the liquid phase will move to the sulfur adsorption group.
  • the concentration of hydrogen sulfide on the hydrogenation catalytic component with desulfurization activity at the same height is reduced, thereby reducing the influence of hydrogen sulfide on the hydrogenation reaction, improving the reaction efficiency, and achieving better hydrogenation effect. .
  • hydrogen sulfide retention time refers to the time period during which more than 90% of the hydrogen sulfide is desorbed after the hydrogen sulfide is adsorbed by the adsorbent.
  • the method for measuring the retention time of hydrogen sulfide includes: filling the adsorbent in a container with a diameter of 1 m and a height of 7 m (the filling height is 2.3 m), and firstly taking the sulfur content (calculated as hydrogen sulfide) as 0.0003%
  • the diesel oil dissolves hydrogen and hydrogen sulfide, so that the mass content of hydrogen sulfide in it is 0.2%, and the diesel oil is completely infiltrated into the adsorbent bed under the condition of liquid-phase hydrogenation reaction, and the infiltration is kept for 0.2h, and then the sulfur content (with sulfurization) is switched.
  • Hydrogen meter is 0.0003% and has dissolved hydrogen, the adsorbent bed is flushed under the liquid phase hydrogenation reaction conditions, and the mass content of hydrogen sulfide in the effluent is measured until ⁇ 0.01%, from the beginning of flushing to hydrogen sulfide The time taken for the mass content ⁇ 0.01% is the retention time of hydrogen sulfide on the adsorbent.
  • the liquid-phase hydrogenation reaction conditions are: the reaction temperature is 25°C, the reaction pressure is 6.3MPaG, the liquid hourly space velocity is 1.3h -1 , and the amount of dissolved hydrogen is the saturated amount of hydrogen dissolved in diesel at 6.3MPaG.
  • the mean pore size and specific surface area are measured by nitrogen physisorption, and the metal content is measured by inorganic metal analysis methods including colorimetric analysis and inductively coupled plasma atomic emission spectrometry.
  • the particle size refers to the volume average particle size unless otherwise specified, and the measurement method thereof can generally be performed by a laser method.
  • any two or more embodiments of the present invention can be combined arbitrarily, and the technical solutions formed thereby belong to a part of the original disclosure content of this specification, and also fall within the protection scope of the present invention.
  • the present invention relates to an adsorbent, especially a hydrogen sulfide adsorbent.
  • the adsorbent is essentially a physical adsorbent of hydrogen sulfide, the adsorption of hydrogen sulfide by the adsorbent is reversible, and its chemical adsorption effect on hydrogen sulfide can be basically ignored or not required in the present invention. considerate.
  • the adsorbents of the present invention can be used in the sulfurized state. Specifically, the adsorbent of the present invention can be used after vulcanization treatment.
  • the reaction conditions of the vulcanization treatment include: dry vulcanization or wet vulcanization, and the vulcanizing agent is at least one selected from hydrogen sulfide, carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide
  • the vulcanization pressure is 1.2-15MPaG (1.2-9.4MPaG)
  • the vulcanization temperature is 280-400°C
  • the vulcanization time is 4-22h.
  • the adsorbent includes a porous material and a hydrogenation-active metal supported on the porous material.
  • the adsorbent can realize the adsorption of hydrogen sulfide, and this adsorption is a short-term physical adsorption, and the adsorbed hydrogen sulfide will be flushed out with the flow of the liquid material, so that The adsorption vacancy is again left on the adsorbent to adsorb the hydrogen sulfide in the subsequent material.
  • the adsorbent continuously adsorbs and desorbs hydrogen sulfide to achieve dynamic balance, so as to realize the concentration of hydrogen sulfide in the liquid material.
  • the hydrogen sulfide concentration on or near the hydrodesulfurization catalyst is reduced to achieve a better hydrogenation effect.
  • the average pore size of the adsorbent is 2-15 nm, preferably 2-10 nm.
  • the specific surface area of the adsorbent is 200-500 m 2 /g, preferably 250-400 m 2 /g.
  • the adsorbent is a physical adsorbent for hydrogen sulfide.
  • the hydrogen sulfide retention time is generally 30-300min, preferably 40-250min, more preferably 60-180min.
  • the adsorbent of the present invention has no upper limit of adsorption capacity for hydrogen sulfide, and does not require regeneration for hydrogen sulfide adsorption capacity.
  • the adsorbent when used in combination with a hydrodesulfurization catalyst, such as in a liquid-phase hydrogenation reaction environment, the adsorbent should also have a certain amount of carbon due to the existence of carbon deposition reaction. High hydrogenation activity to inhibit carbon deposition, thereby prolonging the stability of the adsorbent to ensure long-term operation in the liquid phase hydrogenation reaction system. This function of inhibiting carbon deposition is referred to in the present invention as the self-cleaning ability of the adsorbent.
  • the mass content of the hydrogenation active metal in terms of metal oxide is 2.5 wt % or less, preferably 2 wt % or less, 1.5 wt % or less, or 0.05- 1 wt%.
  • the hydrogenation active metal exists in the form of oxide/sulfide.
  • the adsorbent of the present invention is in a sulfide state, that is, all the hydrogenation-active metals contained in the adsorbent are in a sulfide state.
  • the sulfur content (calculated as elemental sulfur) of the adsorbent is generally below 3 wt %, preferably below 2 wt %, below 1 wt % or 0.5 wt % below, but preferably 0.4 wt % or more, 0.5 wt % or more, 1.0 wt % or more, or 1.3 wt % or more.
  • the adsorbents of the present invention exhibit substantially no chemisorption of hydrogen sulfide.
  • the mass percentage of the porous material is more than 90wt%, preferably more than 92wt%, more than 94wt%, more than 95wt%, more than 98wt%, or 98- 99.5 wt%.
  • the porous material is selected from at least one of activated carbon, inorganic refractory oxides and molecular sieves, especially selected from at least one of alumina, silica, magnesia, zirconia and titania One, more particularly at least one selected from alumina and silica.
  • the hydrogenation active metal is selected from at least one of Fe, Co, Ni, Cu, Zn, Cr, Mo and W, preferably selected from Fe, Co, Ni, Cu, Zn, Cr, Mo and W. At least one of Zn, Ni, Co and Cu, more preferably at least one selected from Fe and Ni.
  • the particle size of the adsorbent is 0.5-5.0 mm, preferably 1-4 mm.
  • the adsorbent can be prepared by a supported catalyst preparation method well known to those skilled in the art. More specifically, the porous material is extruded, dried and calcined, and then impregnated with the hydrogenation active metal, and then dried and calcined to obtain the adsorbent.
  • the extrusion molding is to mix the porous material with a peptizer, an extrusion aid, etc., mix it uniformly, and extrude it on an extruder. Or strips with a four-leaf clover-shaped cross-section.
  • the impregnation is preferably an equal volume impregnation, in which the extruded porous material is impregnated with an equal volume of the stable salt solution of the hydrogenation active metal.
  • both dryings in the above preparation process are at 70-150° C. for 1-24 hours, and both calcinations are at 300-600° C. for 1-10 hours.
  • an adsorption method comprising a step of contacting the adsorbent of the present invention with a material containing a sulfur-containing compound to adsorb the sulfur-containing compound (referred to as an adsorption step).
  • a material containing a sulfur-containing compound to adsorb the sulfur-containing compound
  • the sulfur-containing compound in particular, hydrogen sulfide.
  • the adsorption method further includes a step of subjecting the adsorbent to a sulfurization treatment (referred to as a sulfurization step) prior to the adsorption step.
  • the reaction conditions of the vulcanization treatment include: dry vulcanization or wet vulcanization, and the vulcanizing agent is at least one selected from hydrogen sulfide, carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide
  • the vulcanization pressure is 1.2-15MPaG (1.2-9.4MPaG)
  • the vulcanization temperature is 280-400°C
  • the vulcanization time is 4-22h.
  • a liquid-phase hydrogenation catalyst composition comprising at least one hydrogenation catalytic component with desulfurization activity and at least one sulfur adsorption component.
  • the at least one sulfur adsorption component the adsorbent (referred to as adsorbent A) described earlier in this specification may be included, or the adsorbent described below (referred to as adsorbent B) in this specification may be included , or a combination of both, but Adsorbent A is preferred.
  • the difference between the adsorbent B and the adsorbent A only lies in the mass content of the hydrogenation active metal in the adsorbent.
  • the mass percentage of the hydrogenation active metal in terms of metal oxide is 10 wt % or less, preferably 8 wt % or less, 6 wt % or less, 5 wt % % or less, 2.5 wt % or less, 2 wt % or less, 1.5 wt % or less, or 0.05-1 wt %.
  • both the adsorbent B and the adsorbent A are collectively referred to as the adsorbent or sulfur adsorption component of the present invention without distinction.
  • the mass content of the hydrogenation active metal of the sulfur adsorption component (based on the total weight of the sulfur adsorption component) , in terms of metal oxides) is the mass content of the hydrogenation active component of the hydrogenation catalytic component with desulfurization activity (based on the total weight of the hydrogenation catalytic component with desulfurization activity, in terms of metal oxides 0.06-66%, preferably 1.88-25%, more preferably 2.30-25%.
  • the weight ratio of the hydrogenation catalytic component with desulfurization activity to the sulfur adsorption component is 30-99:1-70, preferably 40-97:3-60, more preferably 60 -95:5-40.
  • the hydrogenation catalytic component having desulfurization activity is in the form of solid particles
  • the sulfur adsorption component is in the form of solid particles.
  • the hydrogenation catalytic component having desulfurization activity and the sulfur adsorption component exist in independent forms from each other, such as independent aggregates or physical mixtures.
  • the hydrogenation catalytic component with desulfurization activity is not combined with the sulfur adsorption component as a whole, for example, they are combined on the same particle by means of impregnation or the like.
  • the hydrogenation catalytic component with desulfurization activity is porous solid particles, and the particle size thereof is 0.5-4.0 mm, preferably 1-4 mm.
  • the average pore diameter of the hydrogenation catalytic component with desulfurization activity is 2-30 nm, preferably 5-25 nm.
  • the specific surface area of the hydrogenation catalytic component with desulfurization activity is 100-400 m 2 /g, preferably 150-300 m 2 /g.
  • the hydrogen sulfide retention time of the sulfur adsorption component is 1.3-5.0 times, preferably 1.5-3.0 times or 2.0-3.0 times that of the hydrogenation catalyst with desulfurization activity.
  • the average pore size of the sulfur adsorption component is 10-80% of the average pore size of the hydrogenation catalyst with desulfurization activity, preferably 20-60% or 20-70%, more preferably 40% -65%.
  • the specific surface area of the sulfur adsorption component is 110-300%, preferably 110-200%, more preferably 115-160% of the specific surface area of the hydrogenation catalyst with desulfurization activity.
  • the hydrogenation catalytic component with desulfurization activity is a catalyst that can realize desulfurization and is applied to liquid phase hydrogenation well known to those skilled in the art, and is selected from supported catalysts and unsupported catalysts at least one of them.
  • the supported catalyst includes a support and a hydrogenation active component.
  • the mass content of the hydrogenation active component in terms of metal oxide is 15-40%, preferably 20-35%.
  • the unsupported catalyst includes a binder and a hydrogenation active component.
  • the mass content of the hydrogenation active component in terms of metal oxide is 30-80%, preferably 40-65%.
  • the carrier is an inorganic refractory oxide, preferably at least one selected from oxides of elements of Group II, Group III, Group IV and Group IVB of the periodic table, more At least one selected from alumina and silica is preferred.
  • the binder is an inorganic refractory oxide, preferably at least one selected from oxides of elements from Group II, Group III, Group IV and Group IVB of the Periodic Table of the Elements , more preferably at least one selected from alumina and silica.
  • the carrier or binder further includes materials formed by modifying these carriers or binders, and the purpose of the modification includes but is not limited to enhancing the strength of the catalyst and improving the activity of the catalyst Wait.
  • the modification is carried out with modified elements such as B, P, and F, and the weight percentage of the modified elements is 0.8-8 wt% based on the weight of the modified carrier or binder.
  • the hydrogenation active component is selected from at least one of oxides of metals in Group VIB and oxides of metals in Group VIII of the Periodic Table of the Elements, preferably, the Group VIB
  • the metals are Mo and/or W, and the Group VIII metals are Co and/or Ni.
  • the mass content of the metal of Group VIB in terms of metal oxide is 15-30%, preferably 18-27%, and the content of the Group VIII metal is 15-30%, preferably 18-27%.
  • the mass content of the metal in terms of metal oxide is 2-10%, preferably 3-7%.
  • the mass content of the metals of Group VIB in terms of metal oxides is 15-60%, preferably 18-57%, and the content of the Group VIII metals is 15-60%, preferably 18-57%.
  • the mass content of the group metals, calculated as metal oxides, is 2-20%, preferably 3-18%.
  • the supported catalyst is, for example, extruding the carrier, impregnating the hydrogenation active component after drying and calcination, and then drying and calcining to obtain the hydrogenation active component with desulfurization activity.
  • catalytic components are to mix the carrier with a peptizer, an extrusion aid, etc., mix it uniformly, and extrude it on an extruder. Strips with a four-leaf clover-shaped cross-section, or spherical particles obtained by rolling balls, oil column molding, etc.
  • the impregnation is preferably an equal volume impregnation, and the extruded support is impregnated with an equal volume of a stable salt solution of the hydrogenation active component.
  • both dryings in the above preparation process are at 70-150° C. for 1-24 hours, and both calcinations are at 300-600° C. for 1-10 hours.
  • the unsupported catalyst is a homogeneous catalyst prepared by co-precipitation of the hydrogenation active component and the binder component, including but not limited to.
  • the present invention also relates to a catalyst bed, in particular a fixed bed.
  • the catalyst bed comprises the liquid phase hydrogenation catalyst composition of the present invention, eg, is packed with the liquid phase hydrogenation catalyst composition of the present invention.
  • the present invention has no particular limitation on the filling method, and any method known in the art can be used.
  • the hydrogenation catalytic component with desulfurization activity and the sulfur adsorption component may also exist in a substantially uniformly mixed form.
  • the hydrogenation catalytic component with desulfurization activity forms at least one sub-catalyst bed A along the material flow direction
  • the sulfur The adsorbed components form at least one sub-catalyst bed B along the material flow direction
  • the sub-catalyst bed A and the sub-catalyst bed B are alternately adjacent.
  • the at least one sub-catalyst bed A preferably forms a columnar shape
  • the at least one sub-catalyst bed B also preferably forms a columnar shape.
  • the above-mentioned two components are filled in the reactor in an alternately adjacent manner, and the same component is filled into a column-shaped reaction unit in the direction of flow, and two adjacent column-shaped reaction units are viewed from the radial direction. Filled with the above two different components.
  • the cross-section of each columnar reaction unit is in any shape, specifically a rectangle, a circle, a triangle, a parallelogram, a ring or an approximate shape thereof, or any other irregular shape.
  • the cross-sections of the columnar reaction units within the same reactor may be the same or different.
  • the sulfur adsorption component has a smaller average pore size and a larger specific surface area than a hydrogenation catalyst with desulfurization activity, and thus has a relatively stronger resistance to hydrogen sulfide. Moreover, this adsorption is a short-term physical adsorption, and the adsorbed hydrogen sulfide will be flushed out with the flow of the liquid material, so that adsorption vacancies are left on the sulfur adsorption component to adsorb the hydrogen sulfide in the subsequent material.
  • the sulfur adsorption component continuously adsorbs and desorbs hydrogen sulfide to achieve dynamic equilibrium, so as to realize the centralized adsorption of hydrogen sulfide in the liquid material. Therefore, in the flow direction, the hydrogen sulfide in the material is more concentrated and distributed in the columnar reaction unit filled with the sulfur adsorption component, and the hydrogen sulfide concentration in the columnar reaction unit filled with the hydrogenation catalyst with desulfurization activity is reduced.
  • the above gradation packing method can achieve better hydrogenation effect.
  • the columnar reaction unit filled with the sulfur adsorption component should have a hydrogen sulfide adsorption capacity that matches the adjacent columnar reaction unit filled with a hydrogenation catalyst with desulfurization activity. Except depending on the hydrogen sulfide adsorption capacity of the sulfur adsorption component, the larger the contact area of the above-mentioned adjacent columnar reaction units, the better, and the smaller the volume of each columnar reaction unit, the better.
  • the section of the columnar reaction unit with the hydrogenation catalyst with desulfurization activity is not more than 500mm, preferably not more than 300mm, more preferably not more than 200mm, further preferably not more than 100mm, most preferably not more than 50mm.
  • the cross section of any one of the sub-catalyst beds A The straight line distance from the center point of the sub-catalyst bed B to the center point of the cross-section of any one of the sub-catalyst beds B adjacent to it is not more than 500mm, preferably not more than 200mm.
  • the area of the cross section of the sub-catalyst bed A and the area of the cross-section of the sub-catalyst bed B are the same or different from each other, independently of each other. is not more than 300,000 mm 2 , preferably not more than 100,000 mm 2 .
  • the shortest distance is no more than 500mm, preferably no more than 300mm, more preferably no more than 200mm, further preferably no more than 100mm, most preferably no more than 50mm.
  • the hydrogenation catalytic component with desulfurization activity accounts for 35-90%, preferably 45-80%, more preferably 50-75% %.
  • the proportion of the sulfur adsorption component is 10-65%, preferably 20-55%, more preferably 25-50%.
  • the hydrogenation catalytic component having desulfurization activity is subjected to sulfurization treatment, and the sulfur adsorption component is or is not subjected to sulfurization treatment.
  • the reaction conditions of the vulcanization treatment include: dry vulcanization or wet vulcanization, and the vulcanizing agent is at least one selected from hydrogen sulfide, carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide
  • the vulcanization pressure is 1.2-15MPaG (1.2-9.4MPaG)
  • the vulcanization temperature is 280-400°C
  • the vulcanization time is 4-22h.
  • the present invention also relates to a hydrogenation method, especially a liquid-phase fixed bed hydrogenation method.
  • the hydrogenation method includes the step of contacting the liquid-phase hydrogenation catalyst composition of the present invention or the catalyst bed of the present invention with an oil product under liquid-phase hydrogenation reaction conditions to undergo a hydrogenation reaction (referred to as hydrogenation). step).
  • the oil product is selected from at least one of gasoline, kerosene, diesel oil, wax oil, residual oil and coal tar, preferably at least one selected from diesel oil, wax oil and residual oil.
  • the sulfur content (converted to hydrogen sulfide) of the oil is 0.01-3.0 wt %, preferably 0.01-2.0 wt %.
  • the liquid-phase hydrogenation reaction conditions include: a reaction temperature of 100-500° C. (preferably 100-450° C.), a reaction pressure of 1-20 MPaG (preferably (2-15 MPaG), and a liquid hourly space velocity of 1 -10h -1 (preferably 2-10h -1 , more preferably 2-8h -1 ), the (dissolved) hydrogen content of the oil is 0.01-0.35wt% (preferably 0.05-0.25wt%).
  • the hydrogenation method further comprises the step of subjecting the liquid-phase hydrogenation catalyst composition or the catalyst bed to a sulfidation treatment prior to the hydrogenation step.
  • the reaction conditions of the vulcanization treatment include: dry vulcanization or wet vulcanization, and the vulcanizing agent is at least one selected from hydrogen sulfide, carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide
  • the vulcanization pressure is 1.2-15MPaG (1.2-9.4MPaG)
  • the vulcanization temperature is 280-400°C
  • the vulcanization time is 4-22h.
  • the sulfur adsorption component does not have to undergo sulfidation treatment, because the active metal content in the sulfur adsorption component is low, the hydrogen sulfide generated by the liquid-phase hydrogenation reaction system can be used to carry out self-sulfurization in the initial stage, consuming hydrogen sulfide. At the same time, it has hydrogenation activity to avoid carbon deposition in subsequent reactions. Therefore, the hydrogenation catalytic component with desulfurization activity can be sulfurized first and then mixed with the sulfur adsorption component, or the two components can be mixed and sulfurized together, and then the liquid phase hydrogenation reaction can be carried out.
  • the present invention will be further described in detail below through examples and comparative examples, but the present invention is not limited to the following examples.
  • the average pore diameter and specific surface area were measured using an ASAP2400 adsorption instrument.
  • the average pore size of catalyst D1 was 9.5 nanometers, the specific surface area was 268.9 square meters per gram, the particle size was 2 mm, the hydrogen sulfide retention time was 55.3 min, the hydrogenation active metals were Mo and Ni, and the total mass of the hydrogenation active metals was The content is 28 wt%.
  • the average pore diameter of catalyst D2 is 9.8 nanometers
  • the specific surface area is 253.3 square meters/g
  • the particle size is 1.5 mm
  • the hydrogen sulfide retention time is 53.2 min
  • the hydrogenation active metals are Mo and Ni
  • the mass of the hydrogenation active metals is The content is 32 wt%.
  • the average pore diameter of catalyst D3 is 10.7 nanometers
  • the specific surface area is 211.1 square meters/g
  • the particle size is 1.5 mm
  • the hydrogen sulfide retention time is 47.1 min
  • the hydrogenation active metals are Mo and Co
  • the mass of the hydrogenation active metals is The content was 19 wt%.
  • the average pore size of catalyst D4 was 9.3 nanometers, the specific surface area was 259.4 square meters/g, the particle size was 2.3 mm, the hydrogen sulfide retention time was 63.4 min, the hydrogenation active metals were W and Ni, and the mass of the hydrogenation active metals was The content was 29 wt%.
  • the average pore diameter of catalyst D5 is 10.3 nanometers, the specific surface area is 239.1 square meters/g, the particle size is 1.5 mm, the hydrogen sulfide retention time is 49 min, the hydrogenation active metal is Mo, and the mass content of the hydrogenation active metal is 15wt. %.
  • the average pore diameter of catalyst D6 is 6.8 nanometers
  • the specific surface area is 120.7 square meters/g
  • the particle size is 1.7 mm
  • the hydrogen sulfide retention time is 79.3 min
  • the hydrogenation active metals are Mo and Ni
  • the mass of the hydrogenation active metals The content is 28 wt%.
  • the average pore diameter of catalyst D7 is 19.3 nanometers, the specific surface area is 168.3 square meters/g, the particle size is 1.5 mm, the hydrogen sulfide retention time is 23.7 min, the hydrogenation active metals are Mo and Co, and the mass of the hydrogenation active metals is The content was 19 wt%.
  • the average pore size of the sulfur adsorption component A1 is 4.7 nanometers
  • the specific surface area is 427.9 square meters per gram
  • the particle size is 2 mm
  • the hydrogen sulfide retention time is 200.9 min
  • the hydrogenation active metal is Ni
  • the mass of the hydrogenation active metal The content was 2.3 wt%
  • the sulfur content was 0 wt%.
  • the average pore size of the sulfur adsorption component A2 is 5.6 nanometers, the specific surface area is 310.9 square meters/g, the particle size is 3.6 mm, the hydrogen sulfide retention time is 182.1 min, the hydrogenation active metal is Fe, and the hydrogenation active metal is Fe.
  • the mass content is 4 wt%, and the sulfur content is 0 wt%.
  • the average pore size of the sulfur adsorption component A3 is 3.7 nanometers, the specific surface area is 309.3 square meters/g, the particle size is 4.3 mm, the hydrogen sulfide retention time is 197.5 min, the hydrogenation active metal is Co, and the hydrogenation active metal is Co.
  • the mass content is 1.9 wt%, and the sulfur content is 0 wt%.
  • the average pore size of the sulfur adsorption component A4 is 7.3 nanometers, the specific surface area is 330.5 square meters/g, the particle size is 2.6 mm, the hydrogen sulfide retention time is 156.3 min, the hydrogenation active metal is Zn, and the hydrogenation active metal is Zn.
  • the mass content is 0.8 wt%, and the sulfur content is 0 wt%.
  • the average pore size of the sulfur adsorption component A5 is 4.3 nanometers, the specific surface area is 355.1 square meters/g, the particle size is 2.4 mm, the hydrogen sulfide retention time is 205.3 min, the hydrogenation active metal is Fe, and the hydrogenation active metal is Fe.
  • the mass content is 1.9 wt%, and the sulfur content is 0 wt%.
  • the average pore size of the sulfur adsorption component A6 was 5.1 nanometers, the specific surface area was 364.7 square meters per gram, the particle size was 1.5 mm, the hydrogen sulfide retention time was 190.7 min, the hydrogenation active metal was Ni, and the hydrogenation active metal was Ni.
  • the mass content is 10 wt%, and the sulfur content is 0 wt%.
  • the average pore size of the sulfur adsorption component A7 is 7.6 nanometers
  • the specific surface area is 306.5 square meters per gram
  • the particle size is 2 mm
  • the hydrogen sulfide retention time is 132.8 min
  • the hydrogenation active metal is Fe
  • the mass of the hydrogenation active metal The content was 5.6 wt% and the sulfur content was 0 wt%.
  • the average pore size of the sulfur adsorption component A8 is 5.5 nanometers, the specific surface area is 298.7 square meters/g, the particle size is 2 mm, the hydrogen sulfide retention time is 153.1 min, the hydrogenation active metal is Zn, and the mass of the hydrogenation active metal The content was 1.1 wt%, and the sulfur content was 0 wt%.
  • the average pore size of the sulfur adsorption component A9 is 5.4 nanometers, the specific surface area is 342.1 square meters per gram, the particle size is 2.0 mm, the hydrogen sulfide retention time is 187.7 min, the hydrogenation active metal is Ni, and the hydrogenation active metal is Ni.
  • the mass content is 2 wt %, and the sulfur content is 0 wt %.
  • the sulfur adsorption component A9 in Example 16 was vulcanized by dry method, the reactor filled with A9 was filled with hydrogen, and 2% hydrogen sulfide by volume was introduced, the pressure was increased to 3.0 MPa, and the temperature was increased to 310 ° C. Constant temperature vulcanization After 30 min, the reactor was carefully unloaded under nitrogen protection.
  • the average pore size of sulfurized sulfur adsorption component A9 is 5.3 nanometers, the specific surface area is 322.7 square meters/g, the particle size is 2 mm, the hydrogen sulfide retention time is 193.3 min, the hydrogenation active metal is Ni, and the hydrogenation active metal is Ni.
  • the mass content is 2wt%, and the sulfur content is 0.97wt%.
  • the average pore size of the sulfur adsorption component A10 is 4.5 nanometers, the specific surface area is 314.7 square meters/g, the particle size is 2 mm, the hydrogen sulfide retention time is 175.9 min, the hydrogenation active metal is Ni, and the mass of the hydrogenation active metal The content was 0.005 wt%, and the sulfur content was 0 wt%.
  • the average pore size of the sulfur adsorption component A11 is 15.3 nanometers, the specific surface area is 217.6 square meters per gram, the particle size is 2.1 mm, the hydrogen sulfide retention time is 98.3 min, the hydrogenation active metal is Ni, and the hydrogenation active metal is Ni.
  • the mass content is 3 wt%, and the sulfur content is 0 wt%.
  • the average pore size of the sulfur adsorption component A12 is 1.8 nanometers, the specific surface area is 310.3 square meters per gram, the particle size is 2.4 mm, the hydrogen sulfide retention time is 179.8 min, the hydrogenation active metal is Fe, and the hydrogenation active metal is Fe.
  • the mass content is 1.9 wt%, and the sulfur content is 0 wt%.
  • the average pore size of the sulfur adsorption component A13 is 3.8 nanometers, the specific surface area is 510.6 square meters/g, the particle size is 2.2 mm, the hydrogen sulfide retention time is 207.1 min, the hydrogenation active metal is Ni, and the hydrogenation active metal is Ni.
  • the mass content is 3 wt%, and the sulfur content is 0 wt%.
  • the average pore size of the sulfur adsorption component A14 is 5.2 nanometers, the specific surface area is 183.2 square meters per gram, the particle size is 2.6 mm, the hydrogen sulfide retention time is 41.7 min, the hydrogenation active metal is Ni, and the hydrogenation active metal is Ni.
  • the mass content is 2.3 wt%.
  • the average pore size of the sulfur adsorption component A15 is 4.1 nanometers, the specific surface area is 286.1 square meters per gram, the particle size is 3.2 mm, the hydrogen sulfide retention time is 171.3 min, the hydrogenation active metal content is 0wt%, and the sulfur content is 0wt%.
  • the average pore size of the sulfur adsorption component A16 is 2.7 nanometers, the specific surface area is 301.5 square meters per gram, the particle size is 2.7 mm, the hydrogen sulfide retention time is 102.1 min, and the hydrogenation active metals are Ni, W, Zn, and the hydrogenation active metals are Ni, W, and Zn.
  • the mass content of hydrogen-active metal was 29.8 wt%, and the sulfur content was 0 wt%.
  • Vulcanize D1 as follows:
  • the filled reactor of D1 was filled with hydrogen, and 2% hydrogen sulfide by volume was introduced, the pressure was increased to 3.3 MPa, the temperature was increased to 300 ° C, and the vulcanization was performed at a constant temperature for 8 hours, and the reactor was carefully discharged under nitrogen protection.
  • the vulcanized D1 and A1 were mixed in a mass ratio of 85:15 to obtain a catalyst composition Z1.
  • the hydrogen sulfide retention time of the sulfur adsorption component is 3.6 times that of the hydrogenation catalyst
  • the average pore size of the sulfur adsorption component is 49.5% of the average pore size of the hydrogenation catalyst
  • the specific surface area of the sulfur adsorption component is The specific surface area of the hydrogen catalyst is 159.1%
  • the mass content of the hydrogenation active metal of the sulfur adsorption component is 8.2% of the mass content of the hydrogenation active component of the hydrogenation catalytic component.
  • the D2 is vulcanized as follows:
  • the reactor filled with D2 was filled with hydrogen, and 2% hydrogen sulfide by volume was introduced, the pressure was increased to 6.3 MPa, the temperature was raised to 390 ° C, and the temperature was vulcanized for 6 hours.
  • the vulcanized D2 and A2 were mixed in a mass ratio of 88:12 to obtain a catalyst composition Z2.
  • the hydrogen sulfide retention time of the sulfur adsorption component is 2.4 times that of the hydrogenation catalyst
  • the average pore size of the sulfur adsorption component is 57.1% of the average pore size of the hydrogenation catalyst
  • the specific surface area of the sulfur adsorption component is The specific surface area of the hydrogen catalyst is 122.8%
  • the mass content of the hydrogenation active metal of the sulfur adsorption component is 12.5% of the mass content of the hydrogenation active component of the hydrogenation catalyst component.
  • the D4 is vulcanized as follows:
  • the reactor filled with D4 was filled with hydrogen, and 2% hydrogen sulfide by volume was introduced, the pressure was increased to 5.0 MPa, the temperature was raised to 330 ° C, and the temperature was vulcanized for 12 hours.
  • the sulfided D4 and A4 were mixed in a mass ratio of 76:24 to obtain a catalyst composition Z3.
  • the hydrogen sulfide retention time of the sulfur adsorption component is 2.5 times that of the hydrogenation catalyst
  • the average pore size of the sulfur adsorption component is 78.5% of the average pore size of the hydrogenation catalyst
  • the specific surface area of the sulfur adsorption component is The specific surface area of the hydrogen catalyst is 127.4%
  • the mass content of the hydrogenation active metal of the sulfur adsorption component is 2.8% of the mass content of the hydrogenation active component of the hydrogenation catalyst component.
  • the D3 is vulcanized as follows:
  • the reactor filled with D3 was filled with hydrogen, and 2% hydrogen sulfide by volume was introduced, the pressure was increased to 5.3 MPa, the temperature was raised to 340 ° C, and the vulcanization was performed at a constant temperature for 7 hours, and the reactor was carefully unloaded under nitrogen protection.
  • the sulfided D3 and A3 were mixed in a mass ratio of 78:22 to obtain a catalyst composition Z4.
  • the hydrogen sulfide retention time of the sulfur adsorption component is 4.2 times that of the hydrogenation catalyst
  • the average pore size of the sulfur adsorption component is 34.6% of the average pore size of the hydrogenation catalyst
  • the specific surface area of the sulfur adsorption component is The specific surface area of the hydrogen catalyst is 146.5%
  • the mass content of the hydrogenation active metal of the sulfur adsorption component is 10.0% of the mass content of the hydrogenation active component of the hydrogenation catalyst component.
  • the D2 is vulcanized as follows:
  • the reactor filled with D2 was filled with hydrogen, and 2% hydrogen sulfide by volume was introduced, the pressure was increased to 6.3 MPa, the temperature was raised to 390 ° C, and the temperature was vulcanized for 6 hours.
  • the sulfided D2 and A5 were mixed in a mass ratio of 78:22 to obtain a catalyst composition Z5.
  • the hydrogen sulfide retention time of the sulfur adsorption component is 3.9 times that of the hydrogenation catalyst
  • the average pore size of the sulfur adsorption component is 43.9% of the average pore size of the hydrogenation catalyst
  • the specific surface area of the sulfur adsorption component is The specific surface area of the hydrogen catalyst is 140.2%
  • the mass content of the hydrogenation active metal of the sulfur adsorption component is 5.9% of the mass content of the hydrogenation active component of the hydrogenation catalytic component.
  • the D3 is vulcanized as follows:
  • the reactor filled with D3 was filled with hydrogen, and 2% hydrogen sulfide by volume was introduced, the pressure was increased to 5.3 MPa, the temperature was raised to 340 ° C, and the vulcanization was performed at a constant temperature for 7 hours, and the reactor was carefully unloaded under nitrogen protection.
  • the sulfided D3 and A5 were mixed in a mass ratio of 78:22 to obtain a catalyst composition Z6.
  • the hydrogen sulfide retention time of the sulfur adsorption component is 4.4 times that of the hydrogenation catalyst
  • the average pore size of the sulfur adsorption component is 40.2% of the average pore size of the hydrogenation catalyst
  • the specific surface area of the sulfur adsorption component is The specific surface area of the hydrogen catalyst is 168.2%
  • the mass content of the hydrogenation active metal of the sulfur adsorption component is 10.0% of the mass content of the hydrogenation active component of the hydrogenation catalyst component.
  • the D3 is vulcanized as follows:
  • the reactor filled with D3 was filled with hydrogen, and 2% hydrogen sulfide by volume was introduced, the pressure was increased to 5.3 MPa, the temperature was raised to 340 ° C, and the vulcanization was performed at a constant temperature for 7 hours, and the reactor was carefully unloaded under nitrogen protection.
  • the sulfided D3 and A6 were mixed in a mass ratio of 78:22 to obtain a catalyst composition Z7.
  • the hydrogen sulfide retention time of the sulfur adsorption component is 4.0 times that of the hydrogenation catalyst
  • the average pore size of the sulfur adsorption component is 47.7% of the average pore size of the hydrogenation catalyst
  • the specific surface area of the sulfur adsorption component is The specific surface area of the hydrogen catalyst is 172.8%
  • the mass content of the hydrogenation active metal of the sulfur adsorption component is 52.6% of the mass content of the hydrogenation active component of the hydrogenation catalytic component.
  • the D3 is vulcanized as follows:
  • the reactor filled with D3 was filled with hydrogen, and 2% hydrogen sulfide by volume was introduced, the pressure was increased to 5.3 MPa, the temperature was raised to 340 ° C, and the vulcanization was performed at a constant temperature for 7 hours, and the reactor was carefully unloaded under nitrogen protection.
  • the vulcanized D3 and A7 were mixed in a mass ratio of 85:15 to obtain a catalyst composition Z8.
  • the hydrogen sulfide retention time of the sulfur adsorption component is 2.8 times that of the hydrogenation catalyst
  • the average pore size of the sulfur adsorption component is 71.0% of that of the hydrogenation catalyst
  • the specific surface area of the sulfur adsorption component is The specific surface area of the hydrogen catalyst is 145.2%
  • the mass content of the hydrogenation active metal of the sulfur adsorption component is 29.5% of the mass content of the hydrogenation active component of the hydrogenation catalytic component.
  • the D4 is vulcanized as follows:
  • the reactor filled with D4 was filled with hydrogen, and 2% hydrogen sulfide by volume was introduced, the pressure was increased to 5.0 MPa, the temperature was raised to 330 ° C, and the temperature was vulcanized for 12 hours.
  • the sulfided D4 and A8 were mixed in a mass ratio of 76:24 to obtain a catalyst composition Z9.
  • the hydrogen sulfide retention time of the sulfur adsorption component is 2.4 times that of the hydrogenation catalyst
  • the average pore size of the sulfur adsorption component is 59.1% of the average pore size of the hydrogenation catalyst
  • the specific surface area of the sulfur adsorption component is The specific surface area of the hydrogen catalyst is 115.2%
  • the mass content of the hydrogenation active metal of the sulfur adsorption component is 3.8% of the mass content of the hydrogenation active component of the hydrogenation catalytic component.
  • the D3 is vulcanized as follows:
  • the reactor filled with D3 was filled with hydrogen, and 2% hydrogen sulfide by volume was introduced, the pressure was increased to 5.3 MPa, the temperature was raised to 340 ° C, and the vulcanization was performed at a constant temperature for 7 hours, and the reactor was carefully unloaded under nitrogen protection.
  • the sulfided D3 and A1 were mixed in a mass ratio of 78:22 to obtain a catalyst composition Z10.
  • the hydrogen sulfide retention time of the sulfur adsorption component is 4.3 times that of the hydrogenation catalyst
  • the average pore size of the sulfur adsorption component is 43.9% of the average pore size of the hydrogenation catalyst
  • the specific surface area of the sulfur adsorption component is The specific surface area of the hydrogen catalyst is 202.7%
  • the mass content of the hydrogenation active metal of the sulfur adsorption component is 12.1% of the mass content of the hydrogenation active component of the hydrogenation catalytic component.
  • the oxidation state D3 and A2 were mixed in a mass ratio of 68:32 to obtain a catalyst composition Z11.
  • the catalyst composition Z11 needs to be subjected to sulfidation in the reactor before the hydrogenation reaction.
  • wet vulcanization the raw material diesel and hydrogen are introduced into the reactor, and the pressure is increased to 4.0MPa. After the temperature is raised to 160 DEG C, a vulcanizing agent carbon disulfide is introduced, and the dosage is 10% of the total weight of the catalyst. Continue to heat up to 300°C for constant temperature vulcanization for 19 hours, then cool down to room temperature and wait for the next experiment.
  • the hydrogen sulfide retention time of the sulfur adsorption component is 3.9 times that of the hydrogenation catalyst
  • the average pore size of the sulfur adsorption component is 52.3% of the average pore size of the hydrogenation catalyst
  • the specific surface area of the sulfur adsorption component is The specific surface area of the hydrogen catalyst is 147.3%
  • the mass content of the hydrogenation active metal of the sulfur adsorption component is 21.1% of the mass content of the hydrogenation active component of the hydrogenation catalyst component.
  • the D3 is vulcanized as follows:
  • Adopt dry vulcanization fill the reactor filled with D3 with hydrogen, and introduce 2% hydrogen sulfide by volume, increase the pressure to 5.3 MPa, heat up to 340 ° C, vulcanize at constant temperature for 7 hours, and carefully unload the reactor under nitrogen protection.
  • the vulcanized D3 and A9 were mixed in a mass ratio of 88:12 to obtain a catalyst composition Z12.
  • the hydrogen sulfide retention time of the sulfur adsorption component is 4.0 times that of the hydrogenation catalyst
  • the average pore size of the sulfur adsorption component is 50.5% of the average pore size of the hydrogenation catalyst
  • the specific surface area of the sulfur adsorption component is The specific surface area of the hydrogen catalyst is 162.1%
  • the mass content of the hydrogenation active metal of the sulfur adsorption component is 10.5% of the mass content of the hydrogenation active component of the hydrogenation catalyst component.
  • the D3 is vulcanized as follows:
  • the reactor filled with D3 was filled with hydrogen, and 2% hydrogen sulfide by volume was introduced, the pressure was increased to 5.3 MPa, the temperature was raised to 340 ° C, and the vulcanization was performed at a constant temperature for 7 hours, and the reactor was carefully unloaded under nitrogen protection.
  • the sulfided D3 and the sulfided A9 were mixed in a mass ratio of 88:12 to obtain a catalyst composition Z13.
  • the hydrogen sulfide retention time of the sulfur adsorption component is 4.1 times that of the hydrogenation catalyst
  • the average pore size of the sulfur adsorption component is 49.5% of the average pore size of the hydrogenation catalyst
  • the specific surface area of the sulfur adsorption component is The specific surface area of the hydrogen catalyst is 152.9%
  • the mass content of the hydrogenation active metal of the sulfur adsorption component is 10.5% of the mass content of the hydrogenation active component of the hydrogenation catalyst component.
  • the D7 is vulcanized as follows:
  • the reactor filled with D7 was filled with hydrogen, and 2% hydrogen sulfide by volume was introduced, the pressure was increased to 5.0 MPa, the temperature was raised to 330 ° C, and the temperature was vulcanized for 12 hours.
  • the sulfided D7 and A11 were mixed in a mass ratio of 78:22 to obtain a catalyst composition Z14.
  • the hydrogen sulfide retention time of the sulfur adsorption component is 4.1 times that of the hydrogenation catalyst
  • the average pore size of the sulfur adsorption component is 79.3% of the average pore size of the hydrogenation catalyst
  • the specific surface area of the sulfur adsorption component is The specific surface area of the hydrogen catalyst is 129.3%
  • the mass content of the hydrogenation active metal of the sulfur adsorption component is 15.8% of the mass content of the hydrogenation active component of the hydrogenation catalyst component.
  • the D3 is vulcanized as follows:
  • the reactor filled with D3 was filled with hydrogen, and 2% hydrogen sulfide by volume was introduced, the pressure was increased to 5.0 MPa, the temperature was increased to 330 ° C, and the temperature was vulcanized for 12 hours, and the reactor was carefully unloaded under nitrogen protection.
  • the sulfided D3 and A12 were mixed in a mass ratio of 78:22 to obtain a catalyst composition Z15.
  • the hydrogen sulfide retention time of the sulfur adsorption component is 3.8 times that of the hydrogenation catalyst
  • the average pore size of the sulfur adsorption component is 16.8% of the average pore size of the hydrogenation catalyst
  • the specific surface area of the sulfur adsorption component is The specific surface area of the hydrogen catalyst is 147.0%
  • the mass content of the hydrogenation active metal of the sulfur adsorption component is 10.0% of the mass content of the hydrogenation active component of the hydrogenation catalytic component.
  • the D5 is vulcanized as follows:
  • the reactor filled with D5 was filled with hydrogen, and 2% hydrogen sulfide by volume was introduced, the pressure was increased to 4.5 MPa, the temperature was increased to 310 ° C, and the constant temperature was vulcanized for 12 hours, and the reactor was carefully unloaded under nitrogen protection.
  • the sulfided D5 and A13 were mixed in a mass ratio of 78:22 to obtain a catalyst composition Z16.
  • the hydrogen sulfide retention time of the sulfur adsorption component is 4.2 times that of the hydrogenation catalyst
  • the average pore size of the sulfur adsorption component is 36.9 times that of the hydrogenation catalyst
  • the specific surface area of the sulfur adsorption component is 36.9 times that of the hydrogenation catalyst.
  • the specific surface area of the catalyst is 213.6%
  • the mass content of the hydrogenation active metal of the sulfur adsorption component is 20% of the mass content of the hydrogenation active component of the hydrogenation catalytic component.
  • the D6 is vulcanized as follows:
  • the reactor filled with D6 was filled with hydrogen, and 2% hydrogen sulfide by volume was introduced, the pressure was increased to 4.5 MPa, the temperature was increased to 310 ° C, and the constant temperature was vulcanized for 12 hours.
  • the sulfided D6 and A14 were mixed in a mass ratio of 78:22 to obtain a catalyst composition Z17.
  • the hydrogen sulfide retention time of the sulfur adsorption component is 1.5 times that of the hydrogenation catalyst
  • the average pore size of the sulfur adsorption component is 76.5% of the average pore size of the hydrogenation catalyst
  • the specific surface area of the sulfur adsorption component is The specific surface area of the hydrogen catalyst is 151.8%
  • the mass content of the hydrogenation active metal of the sulfur adsorption component is 8.2% of the mass content of the hydrogenation active component of the hydrogenation catalytic component.
  • the D2 is vulcanized as follows:
  • the reactor filled with D2 was filled with hydrogen, and 2% hydrogen sulfide by volume was introduced, the pressure was increased to 6.3 MPa, the temperature was raised to 390 ° C, and the temperature was vulcanized for 6 hours.
  • the sulfided D2 and A15 were mixed in a mass ratio of 89:11 to obtain a catalyst composition Z18.
  • the hydrogen sulfide retention time of the sulfur adsorption component is 3.2 times that of the hydrogenation catalyst
  • the average pore size of the sulfur adsorption component is 41.8% of the average pore size of the hydrogenation catalyst
  • the specific surface area of the sulfur adsorption component is The specific surface area of the hydrogen catalyst is 113%
  • the mass content of the hydrogenation active metal of the sulfur adsorption component is 0% of the mass content of the hydrogenation active component of the hydrogenation catalytic component.
  • the A16 is vulcanized according to the following steps:
  • the reactor filled with A16 was filled with hydrogen, and 2% hydrogen sulfide by volume was introduced, the pressure was increased to 6.8 MPa, the temperature was raised to 330 ° C, and the temperature was vulcanized for 6 hours, and the reactor was carefully unloaded under nitrogen protection.
  • the catalyst system uses only sulfided A16.
  • the D5 is vulcanized as follows:
  • the reactor filled with D5 was filled with hydrogen, and 2% hydrogen sulfide by volume was introduced, the pressure was increased to 4.5 MPa, the temperature was increased to 310 ° C, and the constant temperature was vulcanized for 12 hours, and the reactor was carefully unloaded under nitrogen protection.
  • the sulfided D5 and A6 were mixed in a mass ratio of 78:22 to obtain a catalyst composition Z19.
  • the hydrogen sulfide retention time of the sulfur adsorption component is 3.9 times that of the hydrogenation catalyst
  • the average pore size of the sulfur adsorption component is 49.5% of the average pore size of the hydrogenation catalyst
  • the specific surface area of the sulfur adsorption component is The specific surface area of the hydrogen catalyst is 152.5%
  • the mass content of the hydrogenation active metal of the sulfur adsorption component is 66.7% of the mass content of the hydrogenation active component of the hydrogenation catalytic component.
  • the D3 is vulcanized as follows:
  • the reactor filled with D3 was filled with hydrogen, and 2% hydrogen sulfide by volume was introduced, the pressure was increased to 5.0 MPa, the temperature was increased to 330 ° C, and the temperature was vulcanized for 12 hours, and the reactor was carefully unloaded under nitrogen protection.
  • the vulcanized D3 and A10 were mixed in a mass ratio of 78:22 to obtain a catalyst composition Z20.
  • the hydrogen sulfide retention time of the sulfur adsorption component is 3.7 times that of the hydrogenation catalyst
  • the average pore size of the sulfur adsorption component is 42.1% of the average pore size of the hydrogenation catalyst
  • the specific surface area of the sulfur adsorption component is The specific surface area of the hydrogen catalyst is 149.1%
  • the mass content of the hydrogenation active metal of the sulfur adsorption component is 0.026% of the mass content of the hydrogenation active component of the hydrogenation catalytic component.
  • the above catalyst compositions were evaluated for activity. Evaluation conditions: a liquid-phase hydrogenation device was used, the reaction temperature was 340°C, the reaction pressure was 6.3MPa, the liquid hourly space velocity was 1.3h -1 , and the hydrogen was brought into the reactor from the raw material oil dissolved hydrogen at 6.3MPa.
  • the raw material oil is the third-line straight-run diesel oil of a refinery of Sinopec, with a sulfur content of 1.53% and a nitrogen content of 150ppm.
  • the resultant oil was subjected to sulfur content analysis to determine the desulfurization promoting effect of the catalyst composition.
  • the results are shown in Table 1.
  • composition number Composition Composition ratio Generated oil sulfur content, %
  • Example 19 Z1 Vulcanized D1, A1 85:15 0.0013
  • Example 20 Z2 Vulcanized D2, A2 88:12 0.0003
  • Example 21 Z3 Vulcanized D4, A4 76:24 0.0025
  • Example 22 Z4 Vulcanized D3, A3 78:22 0.0018
  • Example 23 Z5 Vulcanized D2, A5 78:22 0.0002
  • Example 24 Z6 Vulcanized D3, A5 78:22 0.0011
  • Example 25 Z7 Vulcanized D3, A6 78:22 0.0015
  • Example 26 Z8 Vulcanized D3, A7 85:15 0.0008
  • Example 27 Z9 Vulcanized D4, A8 76:24 0.0023
  • Example 28 Z10 Vulcanized D3, A1 78:22 0.0010
  • Example 29 Z11 Oxidation state D3, A2 68:32 0.0015
  • Example 30 Z12 Vulcan
  • the reactor was filled with only the sulfur adsorption component A1. Dissolve hydrogen sulfide to a hydrogen sulfide mass content of 0.2% by using the hydrogen sulfide-free diesel oil with a sulfur content of 0.0003% obtained by catalyzing liquid-phase hydrogenation with the catalyst composition of Example 20 in Example 32, use it to wet A1, and ensure that the diesel oil does not penetrate the catalyst bed. Wetting conditions: temperature 25°C, pressure 6.3MPa, liquid hourly space velocity 1.3h -1 , wetting for 0.2 hours.
  • Desulfurization catalyst component adsorption and desorption equilibrium test of the present invention Desulfurization catalyst component adsorption and desorption equilibrium test of the present invention:
  • Example 32 use the catalyst composition of Example 20 to catalyze the hydrogen sulfide-free diesel oil with a sulfur content of 0.0003% in liquid-phase hydrogenation to dissolve hydrogen sulfide to a hydrogen sulfide mass content of 0.2%, use it to wet the sulfurized D2, and ensure that the diesel oil Does not penetrate the catalyst bed.
  • Wetting conditions temperature 25°C, pressure 6.3MPa, liquid hourly space velocity 1.3h -1 , wetting for 0.2 hours.
  • the catalyst D1 and the catalyst A1 are loaded into the cylindrical liquid-phase hydrogenation reactor:
  • the reactor is divided into several squares, approximately squares and approximately triangular spaces by intersecting horizontal and vertical lines, in which catalyst D1 and catalyst A1 are cross-packed, as shown in FIG. 1 . Except for the edge parts, the side length of the central square is 40mm.
  • the catalyst D2 and the catalyst A2 are loaded into the cylindrical liquid phase hydrogenation reactor:
  • the reactor is divided into several concentric rings, and the catalyst D2 and the catalyst A2 are cross-packed in every two adjacent ring spaces, as shown in FIG. 2 .
  • the radius of the center circle is 20mm, and the thickness of the remaining concentric rings is 20mm.
  • the catalyst D3 and the catalyst A3 are loaded into the cylindrical liquid phase hydrogenation reactor:
  • the reactor is divided into horizontal strips, and catalyst D3 and catalyst A3 are cross-packed in the spaces of every two adjacent horizontal strips, as shown in FIG. 3 .
  • the thickness of each bar is 60mm.
  • the following part is a long-term operation experiment, in which the raw material oil adopts the straight-run diesel oil of a certain Sinopec refinery, the sulfur content is 1.76%, and the nitrogen content is 161ppm:
  • This example involves long-term experiments.
  • Example 23 Using the reactor and reaction conditions in Example 32, the catalyst composition in Example 23 was loaded in the reactor, and a long-term experimental operation was carried out for 1000 hours. The generated oil and sulfur content was stable, and no deactivation was seen.
  • This example involves long-term experiments.
  • Example 35 Using the reactor, catalyst gradation loading scheme and reaction conditions in Example 35, a 1000-hour long-period experimental operation was carried out, and the generated oil and sulfur content was stable, and no deactivation was seen.
  • This comparative example involves a long period experiment.
  • Example 32 Using the reactor and reaction conditions in Example 32, the reactor was filled with the catalyst composition in Comparative Example 11 to carry out a 1000-hour long-period experimental operation.
  • This comparative example involves a long period experiment.
  • Example 32 Using the reactor and reaction conditions in Example 32, the reactor was filled with the sulfur adsorption component containing the hydrogenation active metal Zn in Example 11, and a 1000-hour long-term experimental operation was performed.
  • This comparative example involves a long period experiment.
  • Example 32 Using the reactor and reaction conditions in Example 32, the catalyst composition in Comparative Example 13 was filled in the reactor, and a 1000-hour long-period experimental operation was carried out.
  • This comparative example involves a long period experiment.
  • Example 32 Using the reactor and reaction conditions in Example 32, the reactor was filled with the catalyst composition in Comparative Example 14, and a 1000-hour long-period experimental operation was performed.

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Abstract

本发明涉及一种吸附剂、包含该吸附剂的液相加氢催化剂组合物、包含该液相加氢催化剂组合物的催化剂床、及其在吸附技术或油品液相加氢技术中的应用。所述吸附剂包括多孔材料和负载在所述多孔材料上的加氢活性金属，其中所述吸附剂的平均孔径为2-15nm，所述吸附剂的比表面积是200-500m2/g，并且以所述吸附剂的总重量计，所述加氢活性金属以金属氧化物计的质量含量为2.5wt％以下。所述吸附剂的硫化氢吸附效能高且持续时间长，有效延长加氢脱硫催化剂的保护周期。

Description

一种吸附剂、液相加氢催化剂组合物、催化剂床及其用途 技术领域
本发明涉及油品液相加氢技术领域，更具体涉及一种吸附剂、包含该吸附剂的液相加氢催化剂组合物、包含该液相加氢催化剂组合物的催化剂床、及其在吸附技术或油品液相加氢技术中的应用。
背景技术
传统的柴油加氢脱硫采用滴流床技术，在气液固三相共存的状态下对柴油原料中的含硫化合物等进行加氢以生产符合国家要求的清洁燃料。液相柴油加氢是近年来兴起的新型技术，在液固两相的状态下对含有硫等杂质的柴油原料进行加氢。与滴流床技术相比，液相柴油加氢的原料与催化剂连续接触，其中溶解的氢和待反应的含硫化合物等在传质方面更具有优势。
虽然液相加氢在传质方面具有优势，但是对于高硫原料柴油生产国VI的工况，从原料中加氢脱除下来的硫以硫化氢的形式溶解在反应的液相中，导致反应体系中硫化氢含量高，抑制加氢脱硫反应平衡向脱硫方向移动。当原料柴油中硫含量较高时，则产生明显可观察到的抑制效应，产物柴油硫含量难以达标。
传统的滴流床技术在应对高硫柴油原料方面可以找到解决办法。可以通过增加进入反应器的氢气流量，即增大氢油比，让生成的硫化氢从液相中扩散到气相中，被大量的氢气带出反应体系。但是，液相加氢技术为了维持反应体系呈液、固两相，不能增大氢气流量，缺乏应对高硫柴油原料的有效办法，这削弱了因传质性能提高带来的优势。
CN103789029A公开了一种两相加氢组合方法，在传统气相循环加氢装置的高压分离器中间设置隔板，将高压分离器分割成气液分离室和溶氢室两部分。较难脱除杂质的中间馏分油采用气相循环加氢工艺加工，生成物料进入气液分离室进行气液分离，分离出的液相进入分馏系统，气相通过管道引入溶氢室的底部，与溶氢室中上部进入的两相加氢装置原料和循环油进行逆流接触。溶氢后的两相加氢装置原料和循环油进入两相加氢反应器进行加氢反应。
CN102876368A公开了一种柴油液相加氢方法，其中新鲜柴油进料经混氢罐混氢后进入液相加氢反应器进行加氢精制反应，反应流出物不经换热经减压阀减压后进入高温低压闪蒸罐进行闪蒸，所得液相的一部分循环回混氢罐前，与新鲜进料混合后进入混氢罐混氢，另一部分液相与闪蒸气相混合后进行分离，得到柴油产品。
CN108855115A公开了一种涂层催化剂，其包括加氢脱硫活性组分、硫吸附剂和载体三部分，其加氢脱硫活性组分质量分数为2.0-20.0wt％，硫吸附剂质量分数为30.0-80.0wt％，余量为载体。
发明内容
液相加氢的产物硫化氢对反应体系具有抑制作用，由此硫化氢的脱除或其抑制作用的消除或减弱一直是技术难题。为了解决该技术难题，现有技术已经将吸附剂组分与加氢脱硫催化组分组合在一起，试图通过吸附剂组分对硫化氢的化学吸附来为加氢脱硫催化组分提供保护。但是，本发明的发明人发现，这类化学吸附剂的缺点是由于化学吸附存在饱和上限，由此导致化学吸附剂对硫化氢的吸附容量有限，表现为吸附剂对硫化氢的吸附效能持续时间短，加氢脱硫催化组分保护周期短。为此，本发明的发明人通过刻苦的研究发现了一种吸附剂，其具有特定的结构和组成，能够在液相加氢过程中实现对硫化氢的临时吸附和临时聚集，从而降低具有加氢反应活性的催化剂组分上的硫化氢浓度，降低硫化氢对加氢反应的影响，降低其对加氢脱硫催化剂的抑制作用，同时该吸附可逆(原位吸附和脱附)。而且，该吸附剂具有自清洁能力，可以长时间维持硫化氢吸附效能，不需要化学吸附剂所需的再生过程。
具体而言，本发明涉及以下方面的内容。
1.一种液相加氢催化剂组合物，其特征在于，所述组合物包括至少一种具有脱硫活性的加氢催化组分和至少一种硫吸附组分；
所述硫吸附组分包括吸附性多孔材料和负载在吸附性多孔材料上的加氢活性金属，以硫吸附组分的总重量计，所述吸附性多孔材料的质量百分比为90％以上，所述加氢活性金属以氧化物计的质量百分比为10％以下。
2.根据前述或后述任一方面所述的液相加氢催化剂组合物，其特征在 于，以重量计，所述具有脱硫活性的加氢催化组分占30％-99％，优选为40％-97％，更优选为60％-95％。
3.根据前述或后述任一方面所述的液相加氢催化剂组合物，其特征在于，所述硫吸附组分占1％-70％，优选为3％-60％，更优选为5％-40％。
4.根据前述或后述任一方面所述的液相加氢催化剂组合物，其特征在于，所述硫吸附组分的粒径尺寸为0.5-5.0毫米，具有脱硫活性的加氢催化剂的粒径尺寸为0.5-4.0毫米。
5.根据前述或后述任一方面所述的液相加氢催化剂组合物，其特征在于，所述硫吸附组分在250-400℃条件下对硫化氢的吸附量相比具有脱硫活性的加氢催化剂高20％到500％。
6.根据前述或后述任一方面所述的液相加氢催化剂组合物，其特征在于，所述硫吸附组分的平均孔径是具有脱硫活性的加氢催化剂的10％-80％，优选为20％-60％。
7.根据前述或后述任一方面所述的液相加氢催化剂组合物，其特征在于，所述硫吸附组分的比表面积是具有脱硫活性的加氢催化剂的的110％-300％，优选为110％-200％。
8.根据前述或后述任一方面所述的液相加氢催化剂组合物，其特征在于，所述吸附性多孔材料选自活性炭、氧化铝、氧化硅、氧化镁、氧化锆、氧化钛和分子筛中的至少一种。
9.根据前述或后述任一方面所述的液相加氢催化剂组合物，其特征在于，所述硫吸附组分中的加氢活性金属选自Fe、Co、Ni、Cu、Zn、Cr、Mo和W中的至少一种。
10.根据前述或后述任一方面所述的液相加氢催化剂组合物，其特征在于，所述硫吸附组分采用负载型催化剂制备方法制得：将吸附性多孔材料挤压成型，干燥和焙烧后浸渍所述加氢活性金属，再进行干燥和焙烧得到所述硫吸附组分。
11.根据前述或后述任一方面所述的液相加氢催化剂组合物，其特征在于，所述具有脱硫活性的加氢催化组分选自负载型催化剂和非负载型催化剂中的至少一种。
12.根据前述或后述任一方面所述的液相加氢催化剂组合物，其特征在 于，所述负载型催化剂包括载体和加氢活性组分，及在此基础上进行改性的催化剂，以催化剂的总重量计，所述加氢活性组分以金属氧化物计的质量含量为15％-40％。
13.根据前述或后述任一方面所述的液相加氢催化剂组合物，其特征在于，所述非负载型催化剂至少包括必要的粘结剂和加氢活性组分，以催化剂的总重量计，所述加氢活性组分以金属氧化物计的质量含量为30％-80％。
14.根据前述或后述任一方面所述的液相加氢催化剂组合物，其特征在于，所述负载型催化剂中的载体和所述非负载型催化剂中的粘结剂为无机耐熔氧化物，选自元素周期表第II族、第III族、第IV族和第IVB族元素的氧化物中的至少一种。
15.根据前述或后述任一方面所述的液相加氢催化剂组合物，其特征在于，所述加氢活性组分为第VIB族和第VIII族金属的氧化物，其中第VIB族金属为Mo和/或W，第VIII族金属为Co和/或Ni。
16.根据前述或后述任一方面所述的液相加氢催化剂组合物，其特征在于，所述第VIB族金属氧化物在催化剂中质量含量为15％-30％，所述第VIII族金属氧化物在催化剂中含量为2％-10％。
17.根据前述或后述任一方面所述的液相加氢催化剂组合物，其特征在于，所述负载型催化剂是将无机耐熔氧化物挤压成型，干燥和焙烧后浸渍所述加氢活性组分，再进行干燥和焙烧得到所述具有脱硫活性的加氢催化组分。
18.根据前述或后述任一方面所述的液相加氢催化剂组合物，其特征在于，所述非负载型催化剂是将加氢活性组分与粘结剂组分以共沉淀法制备的均一催化剂。
19.前述或后述任一方面所述的液相加氢催化剂组合物在油品液相加氢反应中的应用。
20.根据前述或后述任一方面所述的应用，其特征在于，是将所述催化剂组合物中的两种组分混合均匀装填至反应器中，通入油品进行加氢。
21.根据前述或后述任一方面所述的应用，其特征在于，所述催化剂组合物中具有脱硫活性的加氢催化组分在使用前需进行硫化处理，所述硫吸附组分不必须进行硫化处理。
具体而言，本发明还涉及以下方面的内容。
1.一种吸附剂(特别是硫化氢吸附剂)，其特征在于，包括多孔材料和负载在所述多孔材料上的加氢活性金属，其中所述吸附剂的平均孔径为2-15nm(优选2-10nm)，所述吸附剂的比表面积是200-500m 2/g(优选250-400m 2/g)，并且以所述吸附剂的总重量计，所述加氢活性金属以金属氧化物计的质量含量为2.5wt％以下(优选2wt％以下、1.5wt％以下、或者0.05-1wt％)。
2.根据前述或后述任一方面所述的吸附剂，其中所述加氢活性金属以氧化物/硫化物的形式存在，和/或，所述吸附剂是完全硫化态的，和/或，以所述吸附剂的总重量计，所述吸附剂的硫含量(以硫元素计)为3wt％以下(优选2wt％以下、1wt％以下或0.5wt％以下，但优选0.4wt％以上、0.5wt％以上、1.0wt％以上或1.3wt％以上)。
3.根据前述或后述任一方面所述的吸附剂，是硫化氢的物理吸附剂，其硫化氢保留时间为30-300min(优选40-250min，更优选60-180min)。
4.根据前述或后述任一方面所述的吸附剂，其中以所述吸附剂的总重量计，所述多孔材料的质量百分比为90wt％以上(优选92wt％以上、94wt％以上、95wt％以上、98wt％以上、或者98-99.5wt％)，和/或，所述多孔材料选自活性炭、无机耐熔氧化物(特别是选自氧化铝、氧化硅、氧化镁、氧化锆和氧化钛中的至少一种)和分子筛中的至少一种(特别是选自氧化铝和氧化硅中的至少一种)，和/或，所述加氢活性金属选自Fe、Co、Ni、Cu、Zn、Cr、Mo和W中的至少一种(优选选自Fe、Zn、Ni、Co和Cu中的至少一种，更优选选自Fe和Ni中的至少一种)。
5.根据前述或后述任一方面所述的吸附剂，其中所述吸附剂的粒径为0.5-5.0mm(优选1-4mm)。
6.一种吸附方法，包括使根据前述或后述任一方面所述的吸附剂与含有含硫化合物(特别是硫化氢)的物料接触以吸附(特别是可逆吸附)所述含硫化合物的步骤(称为吸附步骤)，并且任选包括在进行所述吸附步骤之前，对所述吸附剂进行硫化处理的步骤(称为硫化步骤)。
7.一种液相加氢催化剂组合物，包含至少一种具有脱硫活性的加氢催化组分和至少一种硫吸附组分，其中所述硫吸附组分包括多孔材料和负载在所述多孔材料上的加氢活性金属，其中所述硫吸附组分的平均孔径为2-15nm(优 选2-10nm)，所述硫吸附组分的比表面积是200-500m 2/g(优选250-400m 2/g)，以所述硫吸附组分的总重量计，所述加氢活性金属以金属氧化物计的质量百分比为10wt％以下(优选8wt％以下、6wt％以下、5wt％以下、2.5wt％以下、2wt％以下、1.5wt％以下、或者0.05-1wt％)，并且所述硫吸附组分的加氢活性金属的质量含量(以所述硫吸附组分的总重量计，以金属氧化物计)是所述具有脱硫活性的加氢催化组分的加氢活性组分的质量含量(以所述具有脱硫活性的加氢催化组分的总重量计，以金属氧化物计)的0.06-66％(优选1.88-25％，更优选2.30-25％)。
8.根据前述或后述任一方面所述的液相加氢催化剂组合物，其中所述具有脱硫活性的加氢催化组分与所述硫吸附组分的重量比为30-99：1-70(优选40-97：3-60，更优选60-95：5-40)，和/或，所述具有脱硫活性的加氢催化组分是固体颗粒形态，所述硫吸附组分是固体颗粒形态，并且所述具有脱硫活性的加氢催化组分与所述硫吸附组分以彼此独立的形式存在(比如独立聚集体或物理混合物)。
9.根据前述或后述任一方面所述的液相加氢催化剂组合物，其中所述具有脱硫活性的加氢催化组分为多孔状固体颗粒，其粒径为0.5-4.0mm(优选1-4mm)，和/或，所述具有脱硫活性的加氢催化组分的平均孔径为2-30nm(优选5-25nm)，和/或，所述具有脱硫活性的加氢催化组分的比表面积是100-400m 2/g(优选150-300m 2/g)，和/或，所述硫吸附组分的硫化氢保留时间是所述具有脱硫活性的加氢催化剂的1.3-5.0倍(优选1.5-3.0倍或2.0-3.0倍)，和/或，所述硫吸附组分的平均孔径是所述具有脱硫活性的加氢催化剂的平均孔径的10-80％(优选20-60％或20-70％，更优选40-65％)，和/或，所述硫吸附组分的比表面积是所述具有脱硫活性的加氢催化剂的比表面积的110-300％(优选110-200％，更优选115-160％)。
10.根据前述或后述任一方面所述的液相加氢催化剂组合物，其中所述具有脱硫活性的加氢催化组分选自负载型催化剂和非负载型催化剂中的至少一种。
11.根据前述或后述任一方面所述的液相加氢催化剂组合物，其中所述负载型催化剂包括载体和加氢活性组分，和/或，所述非负载型催化剂包括粘结剂和加氢活性组分。
12.根据前述或后述任一方面所述的液相加氢催化剂组合物，其中以所述负载型催化剂的总重量计，所述加氢活性组分以金属氧化物计的质量含量为15-40％(优选20-35％)，和/或，以所述非负载型催化剂的总重量计，所述加氢活性组分以金属氧化物计的质量含量为30-80％(优选40-65％)。
13.根据前述或后述任一方面所述的液相加氢催化剂组合物，其中所述载体为无机耐熔氧化物(优选选自元素周期表第II族、第III族、第IV族和第IVB族元素的氧化物中的至少一种，更优选选自氧化铝和氧化硅中的至少一种)，和/或，所述粘结剂为无机耐熔氧化物(优选选自元素周期表第II族、第III族、第IV族和第IVB族元素的氧化物中的至少一种，更优选选自氧化铝和氧化硅中的至少一种)，和/或，所述加氢活性组分选自元素周期表第VIB族金属的氧化物和第VIII族金属的氧化物中的至少一种(优选的是，所述第VIB族金属为Mo和/或W，并且所述第VIII族金属为Co和/或Ni)。
14.根据前述或后述任一方面所述的液相加氢催化剂组合物，其中以所述负载型催化剂的总重量计，所述第VIB族金属以金属氧化物计的质量含量为15-30％(优选18-27％)，所述第VIII族金属以金属氧化物计的质量含量为2-10％(优选3-7％)，和/或，以所述非负载型催化剂的总重量计，所述第VIB族金属以金属氧化物计的质量含量为15-60％(优选18-57％)，所述第VIII族金属以金属氧化物计的质量含量为2-20％(优选3-18％)。
15.一种催化剂床(特别是固定床)，包括根据前述或后述任一方面所述的液相加氢催化剂组合物。
16.根据前述或后述任一方面所述的催化剂床，其中所述具有脱硫活性的加氢催化组分沿着物料流动方向形成至少一个子催化剂床A(优选形成柱状的所述子催化剂床A)，所述硫吸附组分沿着物料流动方向形成至少一个子催化剂床B(优选形成柱状的所述子催化剂床B)，并且所述子催化剂床A与所述子催化剂床B交替相邻，和/或，所述具有脱硫活性的加氢催化组分和所述硫吸附组分以基本上均匀混合的形式存在。
17.根据前述或后述任一方面所述的催化剂床，其中所述子催化剂床A的横截面为任意图形(比如选自矩形、圆形、椭圆形、三角形、平行四边形、环形和非规则形状中的至少一种)，所述子催化剂床B的横截面为任意图形(比如选自矩形、圆形、椭圆形、三角形、平行四边形、环形和非规则形状 中的至少一种)，和/或，在所述催化剂床的任意横截面上，任意一个所述子催化剂床A的横截面的中心点到与其相邻的任意一个所述子催化剂床B的横截面的中心点的直线距离不超过500mm(优选不超过200mm)，和/或，在所述催化剂床的任意横截面上，所述子催化剂床A的横截面的面积与所述子催化剂床B的横截面的面积彼此相同或不同，各自独立地为不超过300000mm 2(优选不超过100000mm 2)，和/或，在所述催化剂床的任意横截面上，任意一个所述子催化剂床A的横截面上任一点到与其相邻的任意一个所述子催化剂床B的横截面的边缘的最短距离不超过500mm(优选不超过300mm，更优选不超过200mm，进一步优选不超过100mm，最优选不超过50mm)。
18.根据前述或后述任一方面所述的催化剂床，其中以所述催化剂床的总体积计，所述具有脱硫活性的加氢催化组分所占的比例为35-90％(优选45-80％，更优选50-75％)，并且所述硫吸附组分所占的比例为10-65％(优选20-55％，更优选25-50％)。
19.根据前述或后述任一方面所述的催化剂床，其中所述具有脱硫活性的加氢催化组分经过硫化处理，而所述硫吸附组分经过或没有经过硫化处理，和/或，所述硫化处理的反应条件包括：干法硫化或湿法硫化，硫化剂为选自硫化氢、二硫化碳、二甲基二硫醚、甲基硫醚和正丁基硫醚中的至少一种，硫化压力为1.2-15MPaG(1.2-9.4MPaG)，硫化温度为280-400℃，硫化时间为4-22h。
20.一种加氢方法(优选液相固定床加氢方法)，包括使根据前述或后述任一方面所述的液相加氢催化剂组合物或根据前述或后述任一方面所述的催化剂床与油品在液相加氢反应条件下接触而发生加氢反应的步骤(称为加氢步骤)。
21.根据前述或后述任一方面所述的方法，其中所述油品选自汽油、煤油、柴油、蜡油、渣油和煤焦油中的至少一种(优选选自柴油、蜡油和渣油中的至少一种)，和/或，所述油品的硫含量(换算为硫化氢)为0.01-3.0wt％(优选0.01-2.0wt％)，和/或，所述液相加氢反应条件包括：反应温度100-500℃(优选100-450℃)，反应压力1-20MPaG(优选(2-15MPaG)，液时空速为1-10h -1(优选2-10h -1，更优选2-8h -1)，所述油品的(溶解)氢气含量为0.01-0.35wt％(优选0.05-0.25wt％)。
22.根据前述或后述任一方面所述的方法，还包括在进行所述加氢步骤之前，对所述液相加氢催化剂组合物或所述催化剂床进行硫化处理的步骤，和/或，所述硫化处理的反应条件包括：干法硫化或湿法硫化，硫化剂为选自硫化氢、二硫化碳、二甲基二硫醚、甲基硫醚和正丁基硫醚中的至少一种，硫化压力为1.2-15MPaG(1.2-9.4MPaG)，硫化温度为280-400℃，硫化时间为4-22h。
附图说明
图1是实施例35中催化剂D1和催化剂A1级配装填后的反应器截面示意图。
图2是实施例36中催化剂D2和催化剂A2级配装填后的反应器截面示意图。
图3是实施例37中催化剂D3和催化剂A3级配装填后的反应器截面示意图。
技术效果
根据本发明的吸附剂，属于硫化氢的物理吸附剂，不存在硫化氢吸附容量上限，可以长时间持续发挥硫化氢吸附效果，在与加氢脱硫催化剂组合使用的情况下，相比于现有技术可以有效延长加氢脱硫催化剂的保护周期。
根据本发明的吸附剂，具有自清洁能力，在与加氢脱硫催化剂组合使用的情况下，可以在加氢脱硫催化剂的整个使用周期内提供有效保护，而无需化学吸附剂的再生过程。
根据本发明的液相加氢催化剂组合物，通过组合使用加氢催化组分和硫吸附组分，能在液相加氢过程中实现对硫化氢的吸附，并利用液体物料的流动促使硫吸附组分上硫化氢的脱附，使吸附和脱附达到动态平衡，从而实现物料中硫化氢的聚集，即在催化剂床层中每一薄层高度上，液相中的硫化氢向硫吸附组分上富集，降低了同一高度上具有脱硫活性的加氢催化组分上的硫化氢浓度，从而降低了硫化氢对加氢反应的影响，提高了反应效率，能达到更好的加氢效果。
具体实施方式
下面对本发明的具体实施方式进行详细说明，但是需要指出的是，本发明的保护范围并不受这些具体实施方式的限制，而是由附录的权利要求书来确定。
本说明书提到的所有出版物、专利申请、专利和其它参考文献全都引于此供参考。除非另有定义，本说明书所用的所有技术和科学术语都具有本领域技术人员常规理解的含义。在有冲突的情况下，以本说明书的定义为准。
当本说明书以词头“本领域技术人员公知”、“现有技术”或其类似用语来导出材料、物质、方法、步骤、装置或部件等时，该词头导出的对象涵盖本申请提出时本领域常规使用的那些，但也包括目前还不常用，却将变成本领域公认为适用于类似目的的那些。
在没有明确指明的情况下，本说明书内所提到的所有百分数、份数、比率等都是以重量为基准的，而且压力是表压。
在本说明书的上下文中，硫化氢保留时间指的是硫化氢被吸附剂吸附后，90％以上的硫化氢被脱附的时长。具体而言，硫化氢保留时间的测量方法包括：在直径为1m、高度为7m的容器内装填所述吸附剂(装填高度为2.3m)，先以硫含量(以硫化氢计)为0.0003％的柴油溶解氢气和硫化氢，使其中的硫化氢质量含量为0.2％，在液相加氢反应条件下将所述柴油完全浸润吸附剂床层，保持浸润0.2h，之后切换硫含量(以硫化氢计)为0.0003％且已溶氢的柴油,在液相加氢反应条件下对吸附剂床层进行冲洗，并测定流出物中的硫化氢质量含量直至≯0.01％，从开始冲洗至硫化氢质量含量≯0.01％所用的时间为硫化氢在所述吸附剂上的保留时间。根据本发明，硫化氢保留时间过短则对硫化氢的吸附强度弱，不能发挥选择性吸附功能，保留时间过长则对硫化氢的吸附强度太强，不能形成硫化氢的吸附-脱附动态平衡，不能有效降低加氢催化剂周围的硫化氢浓度。在此，所述液相加氢反应条件是：反应温度25℃，反应压力6.3MPaG，液时空速1.3h -1，溶氢量为氢气在6.3MPaG下在柴油中的饱和溶解量。
在本说明书的上下文中，平均孔径和比表面积采用氮气物理吸附的方法进行测量，金属含量采用无机金属分析法包括比色分析法和电感耦合等离子体原子发射光谱法进行测量。
在本说明书的上下文中，在没有特别明确的情况下，粒径指的是体积平均粒径，其测量方法一般可以通过激光法进行。
在本说明书的上下文中，本发明的任何两个或多个实施方式都可以任意组合，由此而形成的技术方案属于本说明书原始公开内容的一部分，同时也落入本发明的保护范围。
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。
根据本发明的一个实施方式，涉及一种吸附剂，特别是硫化氢吸附剂。需要特别指出的是，该吸附剂在本质上是硫化氢的物理吸附剂，该吸附剂对硫化氢的吸附是可逆的，其对硫化氢的化学吸附作用基本上可以忽略或者是本发明不需要考虑的。为此，不同于现有技术的硫化氢化学吸附剂，本发明的吸附剂可以以硫化态使用。具体而言，本发明的吸附剂可以在硫化处理之后使用。在此，所述硫化处理的反应条件包括：干法硫化或湿法硫化，硫化剂为选自硫化氢、二硫化碳、二甲基二硫醚、甲基硫醚和正丁基硫醚中的至少一种，硫化压力为1.2-15MPaG(1.2-9.4MPaG)，硫化温度为280-400℃，硫化时间为4-22h。通过该硫化处理，本发明的吸附剂基本上不表现出对硫化氢的化学吸附作用。
根据本发明的一个实施方式，所述吸附剂包括多孔材料和负载在所述多孔材料上的加氢活性金属。
根据本发明，本领域技术人员应当理解的是，所述吸附剂能实现对硫化氢的吸附，这种吸附是短暂的物理吸附，被吸附的硫化氢会随液体物料流动而被冲脱，以使吸附剂上再次留出吸附空位吸附后续物料中的硫化氢，随着液体物料的流动，吸附剂上不断地吸附和脱附硫化氢，实现动态平衡，以此实现液体物料中硫化氢的集中吸附，并且在与加氢脱硫催化剂组合使用的情况下，使加氢脱硫催化剂上或附近的硫化氢浓度降低，达到更好的加氢效果。为此，根据本发明，所述吸附剂的平均孔径为2-15nm，优选2-10nm。另外，所述吸附剂的比表面积是200-500m 2/g，优选250-400m 2/g。
根据本发明的一个实施方式，所述吸附剂是硫化氢的物理吸附剂。为此，其硫化氢保留时间一般为30-300min，优选40-250min，更优选60-180min。不同于硫化氢的化学吸附剂，本发明的吸附剂对硫化氢没有吸附容量上限，也不需要为了硫化氢吸附容量而再生。
根据本发明，本领域技术人员应当理解的是，在与加氢脱硫催化剂组合使用的情况下，在比如液相加氢反应环境下，由于积炭反应的存在，所述吸附剂还应具有一定的加氢活性以抑制积炭，从而延长吸附剂的稳定性，以保障在液相加氢反应体系中的长期运行。这种抑制积炭的功能在本发明中被称为吸附剂的自清洁能力。为此，根据本发明，以所述吸附剂的总重量计，所述加氢活性金属以金属氧化物计的质量含量为2.5wt％以下，优选2wt％以下、1.5wt％以下、或者0.05-1wt％。
根据本发明的一个实施方式，在所述吸附剂中，所述加氢活性金属以氧化物/硫化物的形式存在。优选的是，如前文所述，本发明的吸附剂是硫化态的，也即所述吸附剂中包含的所述加氢活性金属全部呈现为硫化物状态。为此，在优选的情况下，以所述吸附剂的总重量计，所述吸附剂的硫含量(以硫元素计)一般为3wt％以下，优选2wt％以下、1wt％以下或0.5wt％以下，但优选0.4wt％以上、0.5wt％以上、1.0wt％以上或1.3wt％以上。通过具有该硫含量(比如通过前文所述的硫化处理)，本发明的吸附剂基本上不表现出对硫化氢的化学吸附作用。
根据本发明的一个实施方式，以所述吸附剂的总重量计，所述多孔材料的质量百分比为90wt％以上，优选92wt％以上、94wt％以上、95wt％以上、98wt％以上、或者98-99.5wt％。
根据本发明的一个实施方式，所述多孔材料选自活性炭、无机耐熔氧化物和分子筛中的至少一种，特别是选自氧化铝、氧化硅、氧化镁、氧化锆和氧化钛中的至少一种，更特别是选自氧化铝和氧化硅中的至少一种。
根据本发明的一个实施方式，从抑制积炭效果来看，所述加氢活性金属选自Fe、Co、Ni、Cu、Zn、Cr、Mo和W中的至少一种，优选选自Fe、Zn、Ni、Co和Cu中的至少一种，更优选选自Fe和Ni中的至少一种。
根据本发明的一个实施方式，所述吸附剂的粒径为0.5-5.0mm，优选1-4mm。
根据本发明，所述吸附剂可以采用本领域技术人员所熟知的负载型催化剂制备方法制得。更为具体的，是将所述多孔材料挤压成型，干燥和焙烧后浸渍所述加氢活性金属，再进行干燥和焙烧得到所述吸附剂。作为更具体的实施方式，所述挤压成型是用胶溶剂、助挤剂等调和所述多孔材料，混合均匀，在挤条机上挤压成型，优选地，是圆形、椭圆形、三叶草形或四叶草形横截面的条状物。所述浸渍优选为等体积浸渍，以所述加氢活性金属的稳定盐溶液等体积浸渍挤压成型的多孔材料。举例而言，以上制备过程中的两次干燥均为在70-150℃干燥1-24小时，两次焙烧均为在300-600℃焙烧1-10小时。
根据本发明的一个实施方式，还涉及一种吸附方法，包括使本发明的吸附剂与含有含硫化合物的物料接触以吸附所述含硫化合物的步骤(称为吸附步骤)。在此，作为所述含硫化合物，特别是硫化氢。
根据本发明的一个实施方式，所述吸附方法还包括在进行所述吸附步骤之前，对所述吸附剂进行硫化处理的步骤(称为硫化步骤)。在此，所述硫化处理的反应条件包括：干法硫化或湿法硫化，硫化剂为选自硫化氢、二硫化碳、二甲基二硫醚、甲基硫醚和正丁基硫醚中的至少一种，硫化压力为1.2-15MPaG(1.2-9.4MPaG)，硫化温度为280-400℃，硫化时间为4-22h。通过该硫化处理，本发明的吸附剂基本上不表现出对硫化氢的化学吸附作用。
根据本发明的一个实施方式，还涉及一种液相加氢催化剂组合物，包含至少一种具有脱硫活性的加氢催化组分和至少一种硫吸附组分。在此，作为所述至少一种硫吸附组分，可以包括本说明书前文所述的吸附剂(称为吸附剂A)，也可以包括本说明书如下所述的吸附剂(称为吸附剂B)，或者包括二者的组合，但优选吸附剂A。
根据本发明，所述吸附剂B与所述吸附剂A的区别仅在于加氢活性金属在吸附剂中的质量含量。具体而言，作为所述吸附剂B，以所述吸附剂的总重量计，所述加氢活性金属以金属氧化物计的质量百分比为10wt％以下，优选8wt％以下、6wt％以下、5wt％以下、2.5wt％以下、2wt％以下、1.5wt％以下、或者0.05-1wt％。在本说明书的上下文中，如无特别明确，将所述吸附剂B与所述吸附剂A二者统称为本发明的吸附剂或硫吸附组分而不加以区分。
根据本发明的一个实施方式，从积炭抑制效果和硫化氢吸附效果的双重 角度出发，以及从所述硫吸附组分和所述具有脱硫活性的加氢催化组分充分发挥各自预期功能的角度出发，同时为了更好的实现硫化氢的动态吸附和脱附平衡以实现加氢性能提高，所述硫吸附组分的加氢活性金属的质量含量(以所述硫吸附组分的总重量计，以金属氧化物计)是所述具有脱硫活性的加氢催化组分的加氢活性组分的质量含量(以所述具有脱硫活性的加氢催化组分的总重量计，以金属氧化物计)的0.06-66％，优选1.88-25％，更优选2.30-25％。
根据本发明的一个实施方式，所述具有脱硫活性的加氢催化组分与所述硫吸附组分的重量比为30-99：1-70，优选40-97：3-60，更优选60-95：5-40。
根据本发明的一个实施方式，所述具有脱硫活性的加氢催化组分是固体颗粒形态，所述硫吸附组分是固体颗粒形态。而且，所述具有脱硫活性的加氢催化组分与所述硫吸附组分以彼此独立的形式存在，比如独立聚集体或物理混合物。换句话说，所述具有脱硫活性的加氢催化组分与所述硫吸附组分并不结合为一个整体，比如通过浸渍等方式结合在同一个颗粒上。
根据本发明的一个实施方式，所述具有脱硫活性的加氢催化组分为多孔状固体颗粒，其粒径为0.5-4.0mm，优选1-4mm。
根据本发明的一个实施方式，所述具有脱硫活性的加氢催化组分的平均孔径为2-30nm，优选5-25nm。
根据本发明的一个实施方式，所述具有脱硫活性的加氢催化组分的比表面积是100-400m 2/g，优选150-300m 2/g。
根据本发明的一个实施方式，从所述硫吸附组分和所述具有脱硫活性的加氢催化组分充分发挥各自预期功能的角度出发，同时为了更好的实现硫化氢的动态吸附和脱附平衡以实现加氢性能提高，所述硫吸附组分的硫化氢保留时间是所述具有脱硫活性的加氢催化剂的1.3-5.0倍，优选1.5-3.0倍或2.0-3.0倍。
根据本发明的一个实施方式，从所述硫吸附组分和所述具有脱硫活性的加氢催化组分充分发挥各自预期功能的角度出发，同时为了更好的实现硫化氢的动态吸附和脱附平衡以实现加氢性能提高，所述硫吸附组分的平均孔径是所述具有脱硫活性的加氢催化剂的平均孔径的10-80％，优选20-60％或20-70％，更优选40-65％。
根据本发明的一个实施方式，从所述硫吸附组分和所述具有脱硫活性的 加氢催化组分充分发挥各自预期功能的角度出发，同时为了更好的实现硫化氢的动态吸附和脱附平衡以实现加氢性能提高，所述硫吸附组分的比表面积是所述具有脱硫活性的加氢催化剂的比表面积的110-300％，优选110-200％，更优选115-160％。
根据本发明的一个实施方式，所述具有脱硫活性的加氢催化组分为本领域技术人员所熟知的应用于液相加氢的能实现脱硫的催化剂，选自负载型催化剂和非负载型催化剂中的至少一种。
根据本发明的一个实施方式，所述负载型催化剂包括载体和加氢活性组分。一般而言，以所述负载型催化剂的总重量计，所述加氢活性组分以金属氧化物计的质量含量为15-40％，优选20-35％。
根据本发明的一个实施方式，所述非负载型催化剂包括粘结剂和加氢活性组分。一般而言，以所述非负载型催化剂的总重量计，所述加氢活性组分以金属氧化物计的质量含量为30-80％，优选40-65％。
根据本发明的一个实施方式，所述载体为无机耐熔氧化物，优选选自元素周期表第II族、第III族、第IV族和第IVB族元素的氧化物中的至少一种，更优选选自氧化铝和氧化硅中的至少一种。
根据本发明的一个实施方式，所述粘结剂为无机耐熔氧化物，优选选自元素周期表第II族、第III族、第IV族和第IVB族元素的氧化物中的至少一种，更优选选自氧化铝和氧化硅中的至少一种。
根据本发明的一个实施方式，所述载体或粘结剂还包括对这些载体或粘结剂进行改性处理后形成的材料，所述改性的目的包括并不限于增强催化剂强度、提高催化剂活性等。举例而言，以B、P、F等改性元素进行改性，以改性后的载体或粘结剂重量为基准，改性元素重量百分含量为0.8-8wt％。
根据本发明的一个实施方式，所述加氢活性组分选自元素周期表第VIB族金属的氧化物和第VIII族金属的氧化物中的至少一种，优选的是，所述第VIB族金属为Mo和/或W，并且所述第VIII族金属为Co和/或Ni。
根据本发明的一个实施方式，以所述负载型催化剂的总重量计，所述第VIB族金属以金属氧化物计的质量含量为15-30％，优选18-27％，所述第VIII族金属以金属氧化物计的质量含量为2-10％，优选3-7％。
根据本发明的一个实施方式，以所述非负载型催化剂的总重量计，所述 第VIB族金属以金属氧化物计的质量含量为15-60％，优选18-57％，所述第VIII族金属以金属氧化物计的质量含量为2-20％，优选3-18％。
根据本发明的一个实施方式，所述具有脱硫活性的加氢催化组分的获得对于本领域技术人员是容易的。作为具体的实施方式之一，所述负载型催化剂是比如将所述载体挤压成型，干燥和焙烧后浸渍所述加氢活性组分，再进行干燥和焙烧得到所述具有脱硫活性的加氢催化组分。作为更具体的实施方式，所述挤压成型是用胶溶剂、助挤剂等调和所述载体，混合均匀，在挤条机上挤压成型，优选地，是圆形、椭圆形、三叶草形或四叶草形横截面的条状物，或以滚球、油柱成型等方式获得的球状颗粒。所述浸渍优选为等体积浸渍，以所述加氢活性组分的稳定盐溶液等体积浸渍挤压成型的载体上。举例而言，以上制备过程中的两次干燥均为在70-150℃干燥1-24小时，两次焙烧均为在300-600℃焙烧1-10小时。另外，所述非负载型催化剂是将所述加氢活性组分与所述粘结剂组分以包括但不限于共沉淀法制备的均一催化剂。
根据本发明的一个实施方式，还涉及一种催化剂床，特别是固定床。根据本发明，所述催化剂床包括本发明的液相加氢催化剂组合物，比如由本发明的液相加氢催化剂组合物装填而成。本发明对于装填方法没有特别的限定，可以本领域已知的任何方法。
根据本发明的一个实施方式，作为所述催化剂床的装填结构，所述具有脱硫活性的加氢催化组分和所述硫吸附组分还可以以基本上均匀混合的形式存在。
根据本发明的一个实施方式，更为优选的是，作为所述催化剂床的装填结构，所述具有脱硫活性的加氢催化组分沿着物料流动方向形成至少一个子催化剂床A，所述硫吸附组分沿着物料流动方向形成至少一个子催化剂床B，并且所述子催化剂床A与所述子催化剂床B交替相邻。另外，所述至少一个子催化剂床A优选形成柱状，所述至少一个子催化剂床B也优选形成柱状。
根据本发明，上述两种组分在反应器中以交替相邻的方式装填，是在物流方向上将同一种组分装填成一个柱状反应单元，从径向上看相邻的两个柱状反应单元内装填的是上述两种不同的组分。每个柱状反应单元的横截面为任意图形，具体的为矩形、圆形、三角形、平行四边形、环形或其近似形状， 或为其他不规则形状均可。而且，在同一反应器内的柱状反应单元横截面可相同也可不同。
根据本发明，本领域技术人员应当理解的是，所述硫吸附组分相比具有脱硫活性的加氢催化剂具有更小的平均孔径和更大的比表面积，因此对硫化氢具有相对更强的吸附能力，而且这种吸附是短暂的物理吸附，被吸附的硫化氢会随液体物料流动而被冲脱，以使硫吸附组分上再次留出吸附空位吸附后续物料中的硫化氢。随着液体物料的流动，硫吸附组分上不断地吸附和脱附硫化氢，实现动态平衡，以此实现液体物料中硫化氢的集中吸附。因此，在物流方向上，物料中的硫化氢更加集中分布于装填硫吸附组分的柱状反应单元，而使装填有具有脱硫活性的加氢催化剂的柱状反应单元中的硫化氢浓度降低，因此降低了硫化氢对加氢催化剂的影响，以上级配装填方法能达到更好的加氢效果。基于以上原理，要取得更好的加氢效果，装填硫吸附组分的柱状反应单元要具有对与其相邻的装填具有脱硫活性的加氢催化剂的柱状反应单元相匹配的硫化氢吸附能力。除了取决于硫吸附组分的硫化氢吸附能力，则上述相邻的柱状反应单元的接触面积越大越好，每个柱状反应单元的体积越小越好。为了减小装填工作难度并同时保证比现有技术更好的加氢效果，根据本发明的一个实施方式，在反应器的同一径向截面上，具有脱硫活性的加氢催化剂的柱状反应单元截面上任一点到与其相邻的硫吸附组分的柱状反应单元截面边缘的最短距离不超过500mm，优选为不超过300mm，更优选不超过200mm，进一步优选不超过100mm，最优选不超过50mm。
根据本发明的一个实施方式，为了减小装填工作难度并同时保证比现有技术更好的加氢效果，在所述催化剂床的任意横截面上，任意一个所述子催化剂床A的横截面的中心点到与其相邻的任意一个所述子催化剂床B的横截面的中心点的直线距离不超过500mm，优选不超过200mm。
根据本发明的一个实施方式，在所述催化剂床的任意横截面上，所述子催化剂床A的横截面的面积与所述子催化剂床B的横截面的面积彼此相同或不同，各自独立地为不超过300000mm 2，优选不超过100000mm 2。
根据本发明的一个实施方式，在所述催化剂床的任意横截面上，任意一个所述子催化剂床A的横截面上任一点到与其相邻的任意一个所述子催化剂床B的横截面的边缘的最短距离不超过500mm，优选不超过300mm，更优选不 超过200mm，进一步优选不超过100mm，最优选不超过50mm。
根据本发明的一个实施方式，以所述催化剂床的总体积计，所述具有脱硫活性的加氢催化组分所占的比例为35-90％，优选45-80％，更优选50-75％。另外，所述硫吸附组分所占的比例为10-65％，优选20-55％，更优选25-50％。
根据本发明的一个实施方式，所述具有脱硫活性的加氢催化组分经过硫化处理，而所述硫吸附组分经过或没有经过硫化处理。在此，所述硫化处理的反应条件包括：干法硫化或湿法硫化，硫化剂为选自硫化氢、二硫化碳、二甲基二硫醚、甲基硫醚和正丁基硫醚中的至少一种，硫化压力为1.2-15MPaG(1.2-9.4MPaG)，硫化温度为280-400℃，硫化时间为4-22h。
根据本发明的一个实施方式，还涉及一种加氢方法，特别是液相固定床加氢方法。在此，所述加氢方法包括使本发明的液相加氢催化剂组合物或本发明的催化剂床与油品在液相加氢反应条件下接触而发生加氢反应的步骤(称为加氢步骤)。
根据本发明的一个实施方式，所述油品选自汽油、煤油、柴油、蜡油、渣油和煤焦油中的至少一种，优选选自柴油、蜡油和渣油中的至少一种。
根据本发明的一个实施方式，所述油品的硫含量(换算为硫化氢)为0.01-3.0wt％，优选0.01-2.0wt％。
根据本发明的一个实施方式，所述液相加氢反应条件包括：反应温度100-500℃(优选100-450℃)，反应压力1-20MPaG(优选(2-15MPaG)，液时空速为1-10h -1(优选2-10h -1，更优选2-8h -1)，所述油品的(溶解)氢气含量为0.01-0.35wt％(优选0.05-0.25wt％)。
根据本发明的一个实施方式，所述加氢方法还包括在进行所述加氢步骤之前，对所述液相加氢催化剂组合物或所述催化剂床进行硫化处理的步骤。在此，所述硫化处理的反应条件包括：干法硫化或湿法硫化，硫化剂为选自硫化氢、二硫化碳、二甲基二硫醚、甲基硫醚和正丁基硫醚中的至少一种，硫化压力为1.2-15MPaG(1.2-9.4MPaG)，硫化温度为280-400℃，硫化时间为4-22h。
根据本发明，所述硫吸附组分不必须进行硫化处理，因硫吸附组分中活性金属含量低，可利用液相加氢反应体系产生的硫化氢在初始阶段进行自硫化，消耗硫化氢的同时具备了加氢活性，避免后续反应中的积炭。因此，可 以将具有脱硫活性的加氢催化组分先进行硫化后再与硫吸附组分混合装填，或将两种组分混合后一起硫化，再进行液相加氢反应。
实施例
以下将通过实施例和对比例对本发明进行进一步的详细描述，但本发明不限于以下实施例。在以下的实施例和对比例中，平均孔径和比表面积采用ASAP2400吸附仪进行测定。
在实施例1-7中制备了具有脱硫活性的加氢催化组分D1-D7：
实施例1
具有脱硫活性的加氢催化组分D1的制备：
取1000克大孔氢氧化铝，加入硝酸和水，获得HNO 3含量为2.2％，水含量为65％的膏状混合物，在挤条机上挤出上述混合物，获得直径1.5毫米的三叶草形条，100℃干燥2小时，然后在600℃焙烧5小时获得载体，取七钼酸铵、硝酸镍配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化钼含量24％、氧化镍含量4％(按焙烧后干基计)的湿条，100℃干燥2小时，然后550℃焙烧2小时获得催化剂D1。
经测定，催化剂D1的平均孔径为9.5纳米，比表面积为268.9平方米/克，粒径为2mm，硫化氢保留时间为55.3min，加氢活性金属为Mo和Ni，加氢活性金属的总质量含量为28wt％。
实施例2
具有脱硫活性的加氢催化组分D2的制备：
取1000克大孔无定型硅铝，加入硝酸和水，获得HNO 3含量为2.3％，水含量为68％的膏状混合物，在挤条机上挤出上述混合物，获得直径1.5毫米的圆柱形条，80℃干燥18小时，然后在500℃焙烧9小时获得载体，取七钼酸铵、硝酸镍配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化钼含量27％、氧化镍含量5％(按焙烧后干基计)的湿条，100℃干燥2小时，然后500℃焙烧9小时获得催化剂D2。
经测定，催化剂D2的平均孔径为9.8纳米，比表面积为253.3平方米/ 克，粒径为1.5mm，硫化氢保留时间为53.2min，加氢活性金属为Mo和Ni，加氢活性金属的质量含量为32wt％。
实施例3
具有脱硫活性的加氢催化组分D3的制备：
取1000克含氟0.9％的氢氧化铝，加入硝酸和水，获得HNO 3含量为1.3％，水含量为60％的膏状混合物，在挤条机上挤出上述混合物，获得直径1.5毫米的圆柱形条，140℃干燥6小时，然后在550℃焙烧2小时获得载体，取七钼酸铵、硝酸钴配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化钼含量16％、氧化钴含量3％(按焙烧后干基计)的湿条，100℃干燥2小时，然后500℃焙烧3小时获得催化剂D3。
经测定，催化剂D3的平均孔径为10.7纳米，比表面积为211.1平方米/克，粒径为1.5mm，硫化氢保留时间为47.1min，加氢活性金属为Mo和Co，加氢活性金属的质量含量为19wt％。
实施例4
具有脱硫活性的加氢催化组分D4的制备：
取1000克大孔氢氧化铝，加入硝酸和水，获得HNO 3含量为1.6％，水含量为55％的膏状混合物，在挤条机上挤出上述混合物，获得直径1.5毫米的圆柱形条，130℃干燥6小时，然后在500℃焙烧3小时获得载体，取偏钨酸铵、硝酸镍配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化钨含量22％、氧化镍含量7％(按焙烧后干基计)的湿条，100℃干燥2小时，然后500℃焙烧7小时获得催化剂D4。
经测定，催化剂D4的平均孔径为9.3纳米，比表面积为259.4平方米/克，粒径为2.3mm，硫化氢保留时间为63.4min，加氢活性金属为W和Ni，加氢活性金属的质量含量为29wt％。
实施例5
具有脱硫活性的加氢催化组分D5的制备：
取1000克大孔无定型硅铝，加入硝酸和水，获得HNO 3含量为1.8％，水 含量为65％的膏状混合物，在挤条机上挤出上述混合物，获得直径1.5毫米的圆柱形条，100℃干燥8小时，然后在600℃焙烧9小时获得载体，取七钼酸铵配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化钼含量15％(按焙烧后干基计)的湿条，100℃干燥2小时，然后600℃焙烧2小时获得催化剂D5。
经测定，催化剂D5的平均孔径为10.3纳米，比表面积为239.1平方米/克，粒径为1.5mm，硫化氢保留时间为49min，加氢活性金属为Mo，加氢活性金属的质量含量为15wt％。
实施例6
具有脱硫活性的加氢催化组分D6的制备：
取1000克含氧化锆2.3％的氢氧化铝，加入硝酸和水，获得HNO 3含量为1.1％，水含量为55％的膏状混合物，在挤条机上挤出上述混合物，获得直径1.7毫米的圆柱形条，100℃干燥3小时，然后在540℃焙烧8小时获得载体，取七钼酸铵、硝酸镍配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化钼含量24％、氧化镍含量4％(按焙烧后干基计)的湿条，80℃干燥2小时，然后500℃焙烧2小时获得催化剂D6。
经测定，催化剂D6的平均孔径为6.8纳米，比表面积为120.7平方米/克，粒径为1.7mm，硫化氢保留时间为79.3min，加氢活性金属为Mo和Ni，加氢活性金属的质量含量为28wt％。
实施例7
具有脱硫活性的加氢催化组分D7的制备：
取1000克含氟0.7％的大孔径氢氧化铝，加入硝酸和水，获得HNO 3含量为1.7％，水含量为58％的膏状混合物，在挤条机上挤出上述混合物，获得直径1.5毫米的圆柱形条，110℃干燥6小时，然后在480℃焙烧2小时获得载体，取七钼酸铵、硝酸钴配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化钼含量16％、氧化钴含量3％(按焙烧后干基计)的湿条，130℃干燥2小时，然后520℃焙烧3小时获得催化剂D7。
经测定，催化剂D7的平均孔径为19.3纳米，比表面积为168.3平方米/ 克，粒径为1.5mm，硫化氢保留时间为23.7min，加氢活性金属为Mo和Co，加氢活性金属的质量含量为19wt％。
在实施例8-18中制备了硫吸附组分A1-A10：
实施例8
硫吸附组分A1的制备：
取1000克小孔氢氧化铝，加入硝酸和水，获得HNO 3含量为2％，水含量为70％的膏状混合物，在挤条机上挤出上述混合物，获得直径2毫米的圆柱形条，100℃干燥2小时，然后在550℃焙烧5小时获得载体。取硝酸镍配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化镍含量2.3％(按焙烧后干基计)的湿条，100℃干燥2小时，然后550℃焙烧2小时获得硫吸附组分A1。
经测定，硫吸附组分A1的平均孔径为4.7纳米，比表面积为427.9平方米/克，粒径为2mm，硫化氢保留时间为200.9min，加氢活性金属为Ni，加氢活性金属的质量含量为2.3wt％，硫含量为0wt％。
实施例9
硫吸附组分A2的制备：
取1000克小孔无定型硅铝，加入硝酸和水，获得HNO 3含量为1.1％，水含量为63％的膏状混合物，在挤条机上挤出上述混合物，获得直径2毫米的圆柱形条，70℃干燥20小时，然后在580℃焙烧9小时获得载体。取硝酸铁配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化铁含量4％(按焙烧后干基计)的湿条，100℃干燥2小时，然后580℃焙烧8小时获得硫吸附组分A2。
经测定，硫吸附组分A2的平均孔径为5.6纳米，比表面积为310.9平方米/克，粒径为3.6mm，硫化氢保留时间为182.1min，加氢活性金属为Fe，加氢活性金属的质量含量为4wt％，硫含量为0wt％。
实施例10
硫吸附组分A3的制备：
取1000克含氧化镁5％的氢氧化铝，加入硝酸和水，获得HNO 3含量为1.8％，水含量为60％的膏状混合物，在挤条机上挤出上述混合物，获得直径2毫米的圆柱形条，140℃干燥3小时，然后在400℃焙烧2小时获得载体。取硝酸钴配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化钴含量1.9％(按焙烧后干基计)的湿条，100℃干燥2小时，然后400℃焙烧5小时获得硫吸附组分A3。
经测定，硫吸附组分A3的平均孔径为3.7纳米，比表面积为309.3平方米/克，粒径为4.3mm，硫化氢保留时间为197.5min，加氢活性金属为Co，加氢活性金属的质量含量为1.9wt％，硫含量为0wt％。
实施例11
硫吸附组分A4的制备：
取1000克含氧化硅3％的小孔氢氧化铝，加入硝酸和水，获得HNO 3含量为2.8％，水含量为50％的膏状混合物，在挤条机上挤出上述混合物，获得直径2毫米的圆柱形条，130℃干燥6小时，然后在490℃焙烧7小时获得载体。取硝酸锌配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化锌含量0.8％(按焙烧后干基计)的湿条，100℃干燥2小时，然后490℃焙烧6小时获得硫吸附组分A4。
经测定，硫吸附组分A4的平均孔径为7.3纳米，比表面积为330.5平方米/克，粒径为2.6mm，硫化氢保留时间为156.3min，加氢活性金属为Zn，加氢活性金属的质量含量为0.8wt％，硫含量为0wt％。
实施例12
硫吸附组分A5的制备：
取1000克小孔氢氧化铝，加入硝酸和水，获得HNO 3含量为2.5％，水含量为68％的膏状混合物，在挤条机上挤出上述混合物，获得直径2毫米的圆柱形条，80℃干燥24小时，然后在650℃焙烧6小时获得载体。取硝酸铁配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化铁含量1.9％(按焙烧后干基计)的湿条，110℃干燥5小时，然后650℃焙烧4小时获得硫吸附组分A5。
经测定，硫吸附组分A5的平均孔径为4.3纳米，比表面积为355.1平方米/克，粒径为2.4mm，硫化氢保留时间为205.3min，加氢活性金属为Fe，加氢活性金属的质量含量为1.9wt％，硫含量为0wt％。
实施例13
硫吸附组分A6的制备：
取1000克小孔氢氧化铝，加入硝酸和水，获得HNO 3含量为1.7％，水含量为63％的膏状混合物，在挤条机上挤出上述混合物，获得直径2毫米的圆柱形条，110℃干燥4小时，然后在500℃焙烧5小时获得载体。取硝酸镍配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化镍含量10％(按焙烧后干基计)的湿条，80℃干燥8小时，然后500℃焙烧3小时获得硫吸附组分A6。
经测定，硫吸附组分A6的平均孔径为5.1纳米，比表面积为364.7平方米/克，粒径为1.5mm，硫化氢保留时间为190.7min，加氢活性金属为Ni，加氢活性金属的质量含量为10wt％，硫含量为0wt％。
实施例14
硫吸附组分A7的制备：
取1000克大孔氢氧化铝，加入硝酸和水，获得HNO 3含量为1.9％，水含量为57％的膏状混合物，在挤条机上挤出上述混合物，获得直径2毫米的圆柱形条，70℃干燥20小时，然后在700℃焙烧7小时获得载体。取硝酸铁配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化铁含量5.6％(按焙烧后干基计)的湿条，100℃干燥5小时，然后700℃焙烧4小时获得硫吸附组分A7。
经测定，硫吸附组分A7的平均孔径为7.6纳米，比表面积为306.5平方米/克，粒径为2mm，硫化氢保留时间为132.8min，加氢活性金属为Fe，加氢活性金属的质量含量为5.6wt％，硫含量为0wt％。
实施例15
硫吸附组分A8的制备：
取1000克小孔无定型硅铝，加入硝酸和水，获得HNO 3含量为2.1％，水含量为66％的膏状混合物，在挤条机上挤出上述混合物，获得直径2毫米的圆柱形条，100℃干燥24小时，然后在500℃焙烧6小时获得载体。取硝酸锌配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化锌含量1.1％(按焙烧后干基计)的湿条，110℃干燥5小时，然后500℃焙烧1小时获得硫吸附组分A8。
经测定，硫吸附组分A8的平均孔径为5.5纳米，比表面积为298.7平方米/克，粒径为2mm，硫化氢保留时间为153.1min，加氢活性金属为Zn，加氢活性金属的质量含量为1.1wt％，硫含量为0wt％。
实施例16
硫吸附组分A9的制备：
取1000克含二氧化硅2.5％的小孔氢氧化铝，加入硝酸和水，获得HNO 3含量为2.5％，水含量为75％的膏状混合物，在挤条机上挤出上述混合物，获得直径2毫米的圆柱形条，120℃干燥8小时，然后在710℃焙烧4小时获得载体。取硝酸镍配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化镍含量2.0％(按焙烧后干基计)的湿条，100℃干燥3小时，然后600℃焙烧2小时，得到硫吸附组分A9。
经测定，硫吸附组分A9的平均孔径为5.4纳米，比表面积为342.1平方米/克，粒径为2.0mm，硫化氢保留时间为187.7min，加氢活性金属为Ni，加氢活性金属的质量含量为2wt％，硫含量为0wt％。
实施例17
制备硫化态硫吸附组分A9：
将实施例16中的硫吸附组分A9采用干法进行硫化，将装填好A9的反应器充满氢气，并引入体积比2％的硫化氢，升压到3.0MPa，升温到310℃，恒温硫化30min，氮气保护下小心卸出反应器。
经测定，硫化态硫吸附组分A9的平均孔径为5.3纳米，比表面积为322.7平方米/克，粒径为2mm，硫化氢保留时间为193.3min，加氢活性金属为Ni，加氢活性金属的质量含量为2wt％，硫含量为0.97wt％。
实施例18
硫吸附组分A10的制备：
取1000克含3％氧化锆的小孔氢氧化铝，加入硝酸和水，获得HNO 3含量为2.1％，水含量为70％的膏状混合物，在挤条机上挤出上述混合物，获得直径2毫米的圆柱形条，80℃干燥8小时，然后在520℃焙烧8小时获得载体。取硝酸镍配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化镍含量0.005％(按焙烧后干基计)的湿条，120℃干燥2小时，然后520℃焙烧4小时获得硫吸附组分A10。
经测定，硫吸附组分A10的平均孔径为4.5纳米，比表面积为314.7平方米/克，粒径为2mm，硫化氢保留时间为175.9min，加氢活性金属为Ni，加氢活性金属的质量含量为0.005wt％，硫含量为0wt％。
在对比例1-6中制备了硫吸附组分A11-A16：
对比例1
硫吸附组分A11的制备：
取1000克大孔氢氧化铝，加入硝酸和水，获得HNO 3含量为1.5％，水含量为62％的膏状混合物，在挤条机上挤出上述混合物，获得直径2毫米的圆柱形条，100℃干燥2小时，然后在1000℃焙烧6小时获得载体。取硝酸镍配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化镍含量3％(按焙烧后干基计)的湿条，100℃干燥2小时，然后500℃焙烧2小时获得硫吸附组分A11。
经测定，硫吸附组分A11的平均孔径为15.3纳米，比表面积为217.6平方米/克，粒径为2.1mm，硫化氢保留时间为98.3min，加氢活性金属为Ni，加氢活性金属的质量含量为3wt％，硫含量为0wt％。
对比例2
硫吸附组分A12的制备：
取1000克小孔无定型硅铝，加入硝酸和水，获得HNO 3含量为3.1％，水含量为50％的膏状混合物，在挤条机上挤出上述混合物，获得直径2毫米的 圆柱形条，80℃干燥24小时，然后在550℃焙烧5小时获得载体。取硝酸铁配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化铁含量1.9％(按焙烧后干基计)的湿条，100℃干燥5小时，然后550℃焙烧5小时获得催化剂A12。
经测定，硫吸附组分A12的平均孔径为1.8纳米，比表面积为310.3平方米/克，粒径为2.4mm，硫化氢保留时间为179.8min，加氢活性金属为Fe，加氢活性金属的质量含量为1.9wt％，硫含量为0wt％。
对比例3
硫吸附组分A13的制备：
取1000克小孔氢氧化铝，加入硝酸和水，获得HNO 3含量为2.3％，水含量为74％的膏状混合物，在挤条机上挤出上述混合物，获得直径2毫米的圆柱形条，90℃干燥3小时，然后在890℃焙烧5小时获得载体。取硝酸镍配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化镍含量3％(按焙烧后干基计)的湿条，90℃干燥3小时，然后600℃焙烧2小时获得催化剂A13。
经测定，硫吸附组分A13的平均孔径为3.8纳米，比表面积为510.6平方米/克，粒径为2.2mm，硫化氢保留时间为207.1min，加氢活性金属为Ni，加氢活性金属的质量含量为3wt％，硫含量为0wt％。
对比例4
硫吸附组分A14的制备：
取1000克小孔无定型硅铝，加入硝酸和水，获得HNO 3含量为3.2％，水含量为52％的膏状混合物，在挤条机上挤出上述混合物，获得直径2毫米的圆柱形条，75℃干燥14小时，然后在450℃焙烧6小时获得载体，取硝酸镍配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化镍含量2.3％(按焙烧后干基计)的湿条，75℃干燥2小时，然后450℃焙烧5小时获得硫吸附组分A14。
经测定，硫吸附组分A14的平均孔径为5.2纳米，比表面积为183.2平方米/克，粒径为2.6mm，硫化氢保留时间为41.7min，加氢活性金属为Ni，加氢活性金属的质量含量为2.3wt％。
对比例5
硫吸附组分A15的制备：
取1000克含氧化钛3.5％的小孔氢氧化铝，加入硝酸和水，获得HNO 3含量为2.8％，水含量为65％的膏状混合物，在挤条机上挤出上述混合物，获得直径2毫米的圆柱形条，85℃干燥12小时，然后在700℃焙烧6小时获得载体，该载体上不浸渍任何加氢活性金属，经过挤条干燥后，得到硫吸附组分A15。
经测定，硫吸附组分A15的平均孔径为4.1纳米，比表面积为286.1平方米/克，粒径为3.2mm，硫化氢保留时间为171.3min，加氢活性金属含量为0wt％，硫含量为0wt％。
对比例6
硫吸附组分A16的制备：
取1000克含氧化镁5％的氢氧化铝，加入硝酸和水，获得HNO 3含量为2.3％，水含量为63％的膏状混合物，在挤条机上挤出上述混合物，获得直径2毫米的圆柱形条，120℃干燥4小时，然后在450℃焙烧5小时获得载体。取硝酸锌、偏钨酸铵、硝酸镍配制成水溶液，用上述载体等体积浸渍30分钟，获得氧化锌含量0.8％，氧化钨含量为22％，氧化镍含量为7％(按焙烧后干基计)的湿条，100℃干燥2小时，然后450℃焙烧5小时获得硫吸附组分A16。
经测定，硫吸附组分A16的平均孔径为2.7纳米，比表面积为301.5平方米/克，粒径为2.7mm，硫化氢保留时间为102.1min，加氢活性金属为Ni、W、Zn，加氢活性金属的质量含量为29.8wt％，硫含量为0wt％。
取D1-D7中的至少一种和A1-A16中的至少一种混合均匀，得到液相加氢催化剂组合物：
实施例19
将D1按以下步骤进行硫化：
采用干法硫化，将装填好D1的反应器充满氢气，并引入体积比2％的硫化氢，升压到3.3MPa，升温到300℃，恒温硫化8小时，氮气保护下小心卸 出反应器。
将硫化后的D1和A1按质量比为85:15混合，得到催化剂组合物Z1。
在该实施例中，硫吸附组分的硫化氢保留时间是加氢催化剂的3.6倍，硫吸附组分的平均孔径是加氢催化剂的平均孔径的49.5％，硫吸附组分的比表面积是加氢催化剂的比表面积的159.1％，硫吸附组分的加氢活性金属的质量含量是加氢催化组分的加氢活性组分的质量含量的8.2％。
实施例20
将D2按以下步骤进行硫化：
采用干法硫化，将装填好D2的反应器充满氢气，并引入体积比2％的硫化氢，升压到6.3MPa，升温到390℃，恒温硫化6小时，氮气保护下小心卸出反应器。
将硫化后的D2和A2按质量比为88:12混合，得到催化剂组合物Z2。
在该实施例中，硫吸附组分的硫化氢保留时间是加氢催化剂的2.4倍，硫吸附组分的平均孔径是加氢催化剂的平均孔径的57.1％，硫吸附组分的比表面积是加氢催化剂的比表面积的122.8％，硫吸附组分的加氢活性金属的质量含量是加氢催化组分的加氢活性组分的质量含量的12.5％。
实施例21
将D4按以下步骤进行硫化：
采用干法硫化，将装填好D4的反应器充满氢气，并引入体积比2％的硫化氢，升压到5.0MPa，升温到330℃，恒温硫化12小时，氮气保护下小心卸出反应器。
将硫化后的D4和A4按质量比为76:24混合，得到催化剂组合物Z3。
在该实施例中，硫吸附组分的硫化氢保留时间是加氢催化剂的2.5倍，硫吸附组分的平均孔径是加氢催化剂的平均孔径的78.5％，硫吸附组分的比表面积是加氢催化剂的比表面积的127.4％，硫吸附组分的加氢活性金属的质量含量是加氢催化组分的加氢活性组分的质量含量的2.8％。
实施例22
将D3按以下步骤进行硫化：
采用干法硫化，将装填好D3的反应器充满氢气，并引入体积比2％的硫化氢，升压到5.3MPa，升温到340℃，恒温硫化7小时，氮气保护下小心卸出反应器。
将硫化后的D3和A3按质量比为78:22混合，得到催化剂组合物Z4。
在该实施例中，硫吸附组分的硫化氢保留时间是加氢催化剂的4.2倍，硫吸附组分的平均孔径是加氢催化剂的平均孔径的34.6％，硫吸附组分的比表面积是加氢催化剂的比表面积的146.5％，硫吸附组分的加氢活性金属的质量含量是加氢催化组分的加氢活性组分的质量含量的10.0％。
实施例23
将D2按以下步骤进行硫化：
采用干法硫化，将装填好D2的反应器充满氢气，并引入体积比2％的硫化氢，升压到6.3MPa，升温到390℃，恒温硫化6小时，氮气保护下小心卸出反应器。
将硫化后的D2和A5按质量比为78:22混合，得到催化剂组合物Z5。
在该实施例中，硫吸附组分的硫化氢保留时间是加氢催化剂的3.9倍，硫吸附组分的平均孔径是加氢催化剂的平均孔径的43.9％，硫吸附组分的比表面积是加氢催化剂的比表面积的140.2％，硫吸附组分的加氢活性金属的质量含量是加氢催化组分的加氢活性组分的质量含量的5.9％。
实施例24
将D3按以下步骤进行硫化：
采用干法硫化，将装填好D3的反应器充满氢气，并引入体积比2％的硫化氢，升压到5.3MPa，升温到340℃，恒温硫化7小时，氮气保护下小心卸出反应器。
将硫化后的D3和A5按质量比为78:22混合，得到催化剂组合物Z6。
在该实施例中，硫吸附组分的硫化氢保留时间是加氢催化剂的4.4倍，硫吸附组分的平均孔径是加氢催化剂的平均孔径的40.2％，硫吸附组分的比表面积是加氢催化剂的比表面积的168.2％，硫吸附组分的加氢活性金属的质 量含量是加氢催化组分的加氢活性组分的质量含量的10.0％。
实施例25
将D3按以下步骤进行硫化：
采用干法硫化，将装填好D3的反应器充满氢气，并引入体积比2％的硫化氢，升压到5.3MPa，升温到340℃，恒温硫化7小时，氮气保护下小心卸出反应器。
将硫化后的D3和A6按质量比为78:22混合，得到催化剂组合物Z7。
在该实施例中，硫吸附组分的硫化氢保留时间是加氢催化剂的4.0倍，硫吸附组分的平均孔径是加氢催化剂的平均孔径的47.7％，硫吸附组分的比表面积是加氢催化剂的比表面积的172.8％，硫吸附组分的加氢活性金属的质量含量是加氢催化组分的加氢活性组分的质量含量的52.6％。
实施例26
将D3按以下步骤进行硫化：
采用干法硫化，将装填好D3的反应器充满氢气，并引入体积比2％的硫化氢，升压到5.3MPa，升温到340℃，恒温硫化7小时，氮气保护下小心卸出反应器。
将硫化后的D3和A7按质量比为85:15混合，得到催化剂组合物Z8。
在该实施例中，硫吸附组分的硫化氢保留时间是加氢催化剂的2.8倍，硫吸附组分的平均孔径是加氢催化剂的平均孔径的71.0％，硫吸附组分的比表面积是加氢催化剂的比表面积的145.2％，硫吸附组分的加氢活性金属的质量含量是加氢催化组分的加氢活性组分的质量含量的29.5％。
实施例27
将D4按以下步骤进行硫化：
采用干法硫化，将装填好D4的反应器充满氢气，并引入体积比2％的硫化氢，升压到5.0MPa，升温到330℃，恒温硫化12小时，氮气保护下小心卸出反应器。
将硫化后的D4和A8按质量比为76:24混合，得到催化剂组合物Z9。
在该实施例中，硫吸附组分的硫化氢保留时间是加氢催化剂的2.4倍，硫吸附组分的平均孔径是加氢催化剂的平均孔径的59.1％，硫吸附组分的比表面积是加氢催化剂的比表面积的115.2％，硫吸附组分的加氢活性金属的质量含量是加氢催化组分的加氢活性组分的质量含量的3.8％。
实施例28
将D3按以下步骤进行硫化：
采用干法硫化，将装填好D3的反应器充满氢气，并引入体积比2％的硫化氢，升压到5.3MPa，升温到340℃，恒温硫化7小时，氮气保护下小心卸出反应器。
将硫化后的D3和A1按质量比为78:22混合，得到催化剂组合物Z10。
在该实施例中，硫吸附组分的硫化氢保留时间是加氢催化剂的4.3倍，硫吸附组分的平均孔径是加氢催化剂的平均孔径的43.9％，硫吸附组分的比表面积是加氢催化剂的比表面积的202.7％，硫吸附组分的加氢活性金属的质量含量是加氢催化组分的加氢活性组分的质量含量的12.1％。
实施例29
将氧化态D3和A2按质量比为68:32混合，得到催化剂组合物Z11。
催化剂组合物Z11在进行加氢反应之前需要进行反应器内的硫化处理。采用湿法硫化，反应器中引入原料柴油和氢气，升压到4.0MPa。升温到160℃后引入硫化剂二硫化碳，用量为催化剂总重量的10％。继续升温到300℃恒温硫化19小时，降温到室温等待下一步实验。
在该实施例中，硫吸附组分的硫化氢保留时间是加氢催化剂的3.9倍，硫吸附组分的平均孔径是加氢催化剂的平均孔径的52.3％，硫吸附组分的比表面积是加氢催化剂的比表面积的147.3％，硫吸附组分的加氢活性金属的质量含量是加氢催化组分的加氢活性组分的质量含量的21.1％。
实施例30
将D3按以下步骤进行硫化：
采用干法硫化，将装填好D3的反应器充满氢气，并引入体积比2％的硫 化氢，升压到5.3MPa，升温到340℃，恒温硫化7小时，氮气保护下小心卸出反应器。
将硫化后的D3和A9按质量比为88:12混合，得到催化剂组合物Z12。
在该实施例中，硫吸附组分的硫化氢保留时间是加氢催化剂的4.0倍，硫吸附组分的平均孔径是加氢催化剂的平均孔径的50.5％，硫吸附组分的比表面积是加氢催化剂的比表面积的162.1％，硫吸附组分的加氢活性金属的质量含量是加氢催化组分的加氢活性组分的质量含量的10.5％。
实施例31
将D3按以下步骤进行硫化：
采用干法硫化，将装填好D3的反应器充满氢气，并引入体积比2％的硫化氢，升压到5.3MPa，升温到340℃，恒温硫化7小时，氮气保护下小心卸出反应器。
将硫化后的D3和硫化后的A9按质量比为88:12混合，得到催化剂组合物Z13。
在该实施例中，硫吸附组分的硫化氢保留时间是加氢催化剂的4.1倍，硫吸附组分的平均孔径是加氢催化剂的平均孔径的49.5％，硫吸附组分的比表面积是加氢催化剂的比表面积的152.9％，硫吸附组分的加氢活性金属的质量含量是加氢催化组分的加氢活性组分的质量含量的10.5％。
对比例7
将D7按以下步骤进行硫化：
采用干法硫化，将装填好D7的反应器充满氢气，并引入体积比2％的硫化氢，升压到5.0MPa，升温到330℃，恒温硫化12小时，氮气保护下小心卸出反应器。
将硫化后的D7和A11按质量比为78:22混合，得到催化剂组合物Z14。
在该实施例中，硫吸附组分的硫化氢保留时间是加氢催化剂的4.1倍，硫吸附组分的平均孔径是加氢催化剂的平均孔径的79.3％，硫吸附组分的比表面积是加氢催化剂的比表面积的129.3％，硫吸附组分的加氢活性金属的质量含量是加氢催化组分的加氢活性组分的质量含量的15.8％。
对比例8
将D3按以下步骤进行硫化：
采用干法硫化，将装填好D3的反应器充满氢气，并引入体积比2％的硫化氢，升压到5.0MPa，升温到330℃，恒温硫化12小时，氮气保护下小心卸出反应器。
将硫化后的D3和A12按质量比为78:22混合，得到催化剂组合物Z15。
在该实施例中，硫吸附组分的硫化氢保留时间是加氢催化剂的3.8倍，硫吸附组分的平均孔径是加氢催化剂的平均孔径的16.8％，硫吸附组分的比表面积是加氢催化剂的比表面积的147.0％，硫吸附组分的加氢活性金属的质量含量是加氢催化组分的加氢活性组分的质量含量的10.0％。
对比例9
将D5按以下步骤进行硫化：
采用干法硫化，将装填好D5的反应器充满氢气，并引入体积比2％的硫化氢，升压到4.5MPa，升温到310℃，恒温硫化12小时，氮气保护下小心卸出反应器。
将硫化后的D5和A13按质量比为78:22混合，得到催化剂组合物Z16。
在该实施例中，硫吸附组分的硫化氢保留时间是加氢催化剂的4.2倍，硫吸附组分的平均孔径是加氢催化剂的平均孔径的36.9，硫吸附组分的比表面积是加氢催化剂的比表面积的213.6％，硫吸附组分的加氢活性金属的质量含量是加氢催化组分的加氢活性组分的质量含量的20％。
对比例10
将D6按以下步骤进行硫化：
采用干法硫化，将装填好D6的反应器充满氢气，并引入体积比2％的硫化氢，升压到4.5MPa，升温到310℃，恒温硫化12小时，氮气保护下小心卸出反应器。
将硫化后的D6和A14按质量比为78:22混合，得到催化剂组合物Z17。
在该实施例中，硫吸附组分的硫化氢保留时间是加氢催化剂的1.5倍， 硫吸附组分的平均孔径是加氢催化剂的平均孔径的76.5％，硫吸附组分的比表面积是加氢催化剂的比表面积的151.8％，硫吸附组分的加氢活性金属的质量含量是加氢催化组分的加氢活性组分的质量含量的8.2％。
对比例11
将D2按以下步骤进行硫化：
采用干法硫化，将装填好D2的反应器充满氢气，并引入体积比2％的硫化氢，升压到6.3MPa，升温到390℃，恒温硫化6小时，氮气保护下小心卸出反应器。
将硫化后的D2和A15按质量比为89:11混合，得到催化剂组合物Z18。
在该实施例中，硫吸附组分的硫化氢保留时间是加氢催化剂的3.2倍，硫吸附组分的平均孔径是加氢催化剂的平均孔径的41.8％，硫吸附组分的比表面积是加氢催化剂的比表面积的113％，硫吸附组分的加氢活性金属的质量含量是加氢催化组分的加氢活性组分的质量含量的0％。
对比例12
将A16按以下步骤进行硫化：
采用干法硫化，将装填好A16的反应器充满氢气，并引入体积比2％的硫化氢，升压到6.8MPa，升温到330℃，恒温硫化6小时，氮气保护下小心卸出反应器。
催化剂体系只采用硫化后的A16。
对比例13
将D5按以下步骤进行硫化：
采用干法硫化，将装填好D5的反应器充满氢气，并引入体积比2％的硫化氢，升压到4.5MPa，升温到310℃，恒温硫化12小时，氮气保护下小心卸出反应器。
将硫化后的D5和A6按质量比为78:22混合，得到催化剂组合物Z19。
在该实施例中，硫吸附组分的硫化氢保留时间是加氢催化剂的3.9倍，硫吸附组分的平均孔径是加氢催化剂的平均孔径的49.5％，硫吸附组分的比 表面积是加氢催化剂的比表面积的152.5％，硫吸附组分的加氢活性金属的质量含量是加氢催化组分的加氢活性组分的质量含量的66.7％。
对比例14
将D3按以下步骤进行硫化：
采用干法硫化，将装填好D3的反应器充满氢气，并引入体积比2％的硫化氢，升压到5.0MPa，升温到330℃，恒温硫化12小时，氮气保护下小心卸出反应器。
将硫化后的D3和A10按质量比为78:22混合，得到催化剂组合物Z20。
在该实施例中，硫吸附组分的硫化氢保留时间是加氢催化剂的3.7倍，硫吸附组分的平均孔径是加氢催化剂的平均孔径的42.1％，硫吸附组分的比表面积是加氢催化剂的比表面积的149.1％，硫吸附组分的加氢活性金属的质量含量是加氢催化组分的加氢活性组分的质量含量的0.026％。
对比例15
催化剂体系不加入硫吸附组分，只采用脱硫催化剂组分D2。催化剂D2按实施例20所述条件进行硫化获得硫化D2。
实施例32
对上述催化剂组合物进行活性评价。评价条件：采用液相加氢装置，反应温度340℃、反应压力6.3MPa、液时空速1.3h -1，氢气在6.3MPa条件下由原料油溶氢带入反应器。
原料油为中国石化某炼厂常三线直馏柴油，硫含量1.53％，氮含量150ppm。
生成油进行硫含量分析以判明催化剂组合物的脱硫促进效果。结果见表1。
表1.活性评价
  组合物编号 组合物组成 组合物比例 生成油硫含量，％
实施例19 Z1 硫化D1、A1 85:15 0.0013
实施例20 Z2 硫化D2、A2 88:12 0.0003
实施例21 Z3 硫化D4、A4 76:24 0.0025
实施例22 Z4 硫化D3、A3 78:22 0.0018
实施例23 Z5 硫化D2、A5 78:22 0.0002
实施例24 Z6 硫化D3、A5 78:22 0.0011
实施例25 Z7 硫化D3、A6 78:22 0.0015
实施例26 Z8 硫化D3、A7 85:15 0.0008
实施例27 Z9 硫化D4、A8 76:24 0.0023
实施例28 Z10 硫化D3、A1 78:22 0.0010
实施例29 Z11 氧化态D3、A2 68:32 0.0015
实施例30 Z12 硫化D3、A9 88:12 0.0013
实施例31 Z13 硫化D3、硫化A9 88:12 0.0006
对比例7 Z14 硫化D7、A11 78:22 0.0031
对比例8 Z15 硫化D3、A12 78:22 0.0035
对比例9 Z16 硫化D5、A13 78:22 0.0029
对比例10 Z17 硫化D6、A14 78:22 0.0032
对比例11 Z18 硫化D2、A15 89:11 0.0029
对比例12 —— 硫化A16 100 0.0033
对比例13 Z19 硫化D5、A6 78:22 0.0037
对比例14 Z20 硫化D3、A10 78:22 0.0024
对比例15 —— 硫化D2 100 0.0035
实施例33
本发明的硫吸附组分吸附与脱附平衡试验：
反应器内只装填硫吸附组分A1。先用实施例32中以实施例20的催化剂组合物催化液相加氢所得硫含量0.0003％的无硫化氢柴油溶解硫化氢至硫化氢质量含量0.2％，用其润湿A1，并保证柴油不穿透催化剂床层。润湿条件：温度25℃、压力6.3MPa、液时空速1.3h -1，润湿0.2小时。
之后切换柴油，用实施例32中以实施例20的催化剂组合物催化液相加氢所得硫含量0.0003％的无硫化氢柴油持续冲洗润湿后的A1，冲洗条件同润湿条件。每30分钟采集一个液体样品，分析其中硫化氢含量，实验结果如表2。
实施例34
本发明的脱硫催化剂组分吸附与脱附平衡试验：
反应器内只装填实施例10制备的硫化D2催化剂。先用实施例32中以实施例20的催化剂组合物催化液相加氢所得硫含量0.0003％的无硫化氢柴油溶解硫化氢至硫化氢质量含量0.2％，用其润湿硫化D2，并保证柴油不穿透催化剂床层。润湿条件：温度25℃、压力6.3MPa、液时空速1.3h -1，润湿0.2小时。
之后切换柴油，再用硫含量0.0003％的无硫化氢柴油继续冲洗润湿后的硫化D2，冲洗条件同润湿条件。每30分钟采集一个液体样品，分析其中硫化氢含量，实验结果如表2。
表2.吸附与脱附平衡试验结果
Figure PCTCN2021127928-appb-000001
实施例35
将催化剂D1和催化剂A1装填于圆筒状的液相加氢反应器：
从截面上看，反应器被交叉的横线和纵线分割成若干正方形、近似正方形和近似三角形的空间，在其中交叉装填催化剂D1和催化剂A1，如图1所示。除了边缘部分，中央正方形格的边长为40mm。
对比例16
在与实施例35相同的加氢反应器中只装填催化剂D1，其中催化剂D1的装填体积等于实施例35中两种催化剂的总体积。
实施例36
将催化剂D2和催化剂A2装填于圆筒状的液相加氢反应器：
从截面上看，反应器被分成若干同心圆环，每两个相邻圆环空间内交叉装填催化剂D2和催化剂A2，如图2所示。中心圆半径为20mm，其余同心圆环的厚度为20mm。
对比例17
在与实施例36相同的加氢反应器中只装填催化剂D2，其中催化剂D2的装填体积等于实施例36中两种催化剂的总体积。
实施例37
将催化剂D3和催化剂A3装填于圆筒状的液相加氢反应器：
从截面上看，反应器被分成横条，每两个相邻横条空间内交叉装填催化剂D3和催化剂A3，如图3所示。每个横条的厚度为60mm。
对比例18
在与实施例37相同的加氢反应器中只装填催化剂D3，其中催化剂D3的装填体积等于实施例37中两种催化剂的总体积。
反应性能测定：
利用实施例35-37和对比例16-18中装填好催化剂的反应器按以下步骤进行反应：
(1)硫化：采用湿法硫化，反应器中引入原料柴油和氢气，升压到4.0MPa。升温到160℃后引入硫化剂二硫化碳，用量为催化剂总重量的10％。继续升温到300℃恒温硫化19小时，降温到室温等待下一步实验。
(2)加氢脱硫反应：反应温度360℃、反应压力6.5MPa、液时空速1.2h -1，氢气在6.5MPa条件下由原料油溶氢带入反应器，原料油为中国石化某炼厂常三线直馏柴油，硫含量1.76％，氮含量161ppm。
生成油进行硫含量分析。结果见表3。
表3活性评价
编号 级配催化剂 生成油硫含量，％
实施例35 D1+A1 0.0009
对比例16 D1 0.0011
实施例36 D2+A2 0.0003
对比例17 D2 0.0007
实施例37 D3+A3 0.0016
对比例18 D3 0.0021
以下部分为长周期运转实验，其中原料油均采用中国石化某炼厂常三线直馏柴油，硫含量1.76％，氮含量161ppm：
实施例38
此实施例涉及到长周期实验。
采用实施例32中的反应器以及反应条件，反应器内装填实施例23中的催化剂组合物，进行1000小时长周期实验运转，生成油硫含量稳定，未见失活。
实施例39
此实施例涉及到长周期实验。
采用实施例35中的反应器、催化剂级配装填方案以及反应条件，进行1000小时长周期实验运转，生成油硫含量稳定，未见失活。
对比例19
此对比例涉及到长周期实验。
采用实施例32中反应器以及反应条件，反应器内装填对比例11中催化剂组合物进行1000小时长周期实验运转。
对比例20
此对比例涉及到长周期实验。
采用实施例32中反应器以及反应条件，反应器内装填实施例11中含有 加氢活性金属Zn的硫吸附组分，进行1000小时长周期实验运转。
对比例21
此对比例涉及到长周期实验。
采用实施例32中反应器以及反应条件，反应器内装填对比例13中催化剂组合物，进行1000小时长周期实验运转。
对比例22
此对比例涉及到长周期实验。
采用实施例32中反应器以及反应条件，反应器内装填对比例14中催化剂组合物，进行1000小时长周期实验运转。
对实施例38-39和对比例19-22的反应中期(500h)生成油硫含量和反应末期生成油硫含量及运转时间进行测定，结果见表4。
表4长周期运转结果
Figure PCTCN2021127928-appb-000002

Claims (22)

  1. 一种吸附剂(特别是硫化氢吸附剂)，其特征在于，包括多孔材料和负载在所述多孔材料上的加氢活性金属，其中所述吸附剂的平均孔径为2-15nm(优选2-10nm)，所述吸附剂的比表面积是200-500m 2/g(优选250-400m 2/g)，并且以所述吸附剂的总重量计，所述加氢活性金属以金属氧化物计的质量含量为2.5wt％以下(优选2wt％以下、1.5wt％以下、或者0.05-1wt％)。
  2. 根据权利要求1所述的吸附剂，其中所述加氢活性金属以氧化物/硫化物的形式存在，和/或，所述吸附剂是完全硫化态的，和/或，以所述吸附剂的总重量计，所述吸附剂的硫含量(以硫元素计)为3wt％以下(优选2wt％以下、1wt％以下或0.5wt％以下，但优选0.4wt％以上、0.5wt％以上、1.0wt％以上或1.3wt％以上)。
  3. 根据权利要求1所述的吸附剂，是硫化氢的物理吸附剂，其硫化氢保留时间为30-300min(优选40-250min，更优选60-180min)。
  4. 根据权利要求1所述的吸附剂，其中以所述吸附剂的总重量计，所述多孔材料的质量百分比为90wt％以上(优选92wt％以上、94wt％以上、95wt％以上、98wt％以上、或者98-99.5wt％)，和/或，所述多孔材料选自活性炭、无机耐熔氧化物(特别是选自氧化铝、氧化硅、氧化镁、氧化锆和氧化钛中的至少一种)和分子筛中的至少一种(特别是选自氧化铝和氧化硅中的至少一种)，和/或，所述加氢活性金属选自Fe、Co、Ni、Cu、Zn、Cr、Mo和W中的至少一种(优选选自Fe、Zn、Ni、Co和Cu中的至少一种，更优选选自Fe和Ni中的至少一种)。
  5. 根据权利要求1所述的吸附剂，其中所述吸附剂的粒径为0.5-5.0mm(优选1-4mm)。
  6. 一种吸附方法，包括使根据权利要求1所述的吸附剂与含有含硫化合物(特别是硫化氢)的物料接触以吸附(特别是可逆吸附)所述含硫化合物的步骤(称为吸附步骤)，并且任选包括在进行所述吸附步骤之前，对所述吸附剂进行硫化处理的步骤(称为硫化步骤)。
  7. 一种液相加氢催化剂组合物，包含至少一种具有脱硫活性的加氢催化组分和至少一种硫吸附组分，其中所述硫吸附组分包括多孔材料和负载在所述多孔材料上的加氢活性金属，其中所述硫吸附组分的平均孔径为2-15nm(优选2-10nm)，所述硫吸附组分的比表面积是200-500m 2/g(优选250-400m 2/g)，以所述硫吸附组分的总重量计，所述加氢活性金属以金属氧化物计的质量百分比为10wt％以下(优选8wt％以下、6wt％以下、5wt％以下、2.5wt％以下、2wt％以下、1.5wt％以下、或者0.05-1wt％)，并且所述硫吸附组分的加氢活性金属的质量含量(以所述硫吸附组分的总重量计，以金属氧化物计)是所述具有脱硫活性的加氢催化组分的加氢活性组分的质量含量(以所述具有脱硫活性的加氢催化组分的总重量计，以金属氧化物计)的0.06-66％(优选1.88％-25％，更优选2.30％-25％)。
  8. 根据权利要求7所述的液相加氢催化剂组合物，其中所述具有脱硫活性的加氢催化组分与所述硫吸附组分的重量比为30-99：1-70(优选40-97：3-60，更优选60-95：5-40)，和/或，所述具有脱硫活性的加氢催化组分是固体颗粒形态，所述硫吸附组分是固体颗粒形态，并且所述具有脱硫活性的加氢催化组分与所述硫吸附组分以彼此独立的形式存在(比如独立聚集体或物理混合物)。
  9. 根据权利要求7所述的液相加氢催化剂组合物，其中所述具有脱硫活性的加氢催化组分为多孔状固体颗粒，其粒径为0.5-4.0mm(优选1-4mm)，和/或，所述具有脱硫活性的加氢催化组分的平均孔径为2-30nm(优选5-25nm)，和/或，所述具有脱硫活性的加氢催化组分的比表面积是100-400m 2/g(优选150-300m 2/g)，和/或，所述硫吸附组分的硫化氢保留时间是所述具有脱硫活性的加氢催化剂的1.3-5.0倍(优选1.5-3.0倍或2.0-3.0倍)，和/或，所述硫吸附组分的平均孔径是所述具有脱硫活性的加氢催化剂的平均孔径的10-80％(优选20-60％或20-70％，更优选40-65％)，和/或，所述硫吸附组分的比表面积是所述具有脱硫活性的加氢催化剂的比表面积的110-300％(优选110-200％，更优选115-160％)。
  10. 根据权利要求7所述的液相加氢催化剂组合物，其中所述具有脱硫活性的加氢催化组分选自负载型催化剂和非负载型催化剂中的至少一种。
  11. 根据权利要求10所述的液相加氢催化剂组合物，其中所述负载型催 化剂包括载体和加氢活性组分，和/或，所述非负载型催化剂包括粘结剂和加氢活性组分。
  12. 根据权利要求11所述的液相加氢催化剂组合物，其中以所述负载型催化剂的总重量计，所述加氢活性组分以金属氧化物计的质量含量为15-40％(优选20-35％)，和/或，以所述非负载型催化剂的总重量计，所述加氢活性组分以金属氧化物计的质量含量为30-80％(优选40-65％)。
  13. 根据权利要求11所述的液相加氢催化剂组合物，其中所述载体为无机耐熔氧化物(优选选自元素周期表第II族、第III族、第IV族和第IVB族元素的氧化物中的至少一种，更优选选自氧化铝和氧化硅中的至少一种)，和/或，所述粘结剂为无机耐熔氧化物(优选选自元素周期表第II族、第III族、第IV族和第IVB族元素的氧化物中的至少一种，更优选选自氧化铝和氧化硅中的至少一种)，和/或，所述加氢活性组分选自元素周期表第VIB族金属的氧化物和第VIII族金属的氧化物中的至少一种(优选的是，所述第VIB族金属为Mo和/或W，并且所述第VIII族金属为Co和/或Ni)。
  14. 根据权利要求13所述的液相加氢催化剂组合物，其中以所述负载型催化剂的总重量计，所述第VIB族金属以金属氧化物计的质量含量为15-30％(优选18-27％)，所述第VIII族金属以金属氧化物计的质量含量为2-10％(优选3-7％)，和/或，以所述非负载型催化剂的总重量计，所述第VIB族金属以金属氧化物计的质量含量为15-60％(优选18-57％)，所述第VIII族金属以金属氧化物计的质量含量为2-20％(优选3-18％)。
  15. 一种催化剂床(特别是固定床)，包括根据权利要求7所述的液相加氢催化剂组合物。
  16. 根据权利要求15所述的催化剂床，其中所述具有脱硫活性的加氢催化组分沿着物料流动方向形成至少一个子催化剂床A(优选形成柱状的所述子催化剂床A)，所述硫吸附组分沿着物料流动方向形成至少一个子催化剂床B(优选形成柱状的所述子催化剂床B)，并且所述子催化剂床A与所述子催化剂床B交替相邻，和/或，所述具有脱硫活性的加氢催化组分和所述硫吸附组分以基本上均匀混合的形式存在。
  17. 根据权利要求16所述的催化剂床，其中所述子催化剂床A的横截面为任意图形(比如选自矩形、圆形、椭圆形、三角形、平行四边形、环形和 非规则形状中的至少一种)，所述子催化剂床B的横截面为任意图形(比如选自矩形、圆形、椭圆形、三角形、平行四边形、环形和非规则形状中的至少一种)，和/或，在所述催化剂床的任意横截面上，任意一个所述子催化剂床A的横截面的中心点到与其相邻的任意一个所述子催化剂床B的横截面的中心点的直线距离不超过500mm(优选不超过200mm)，和/或，在所述催化剂床的任意横截面上，所述子催化剂床A的横截面的面积与所述子催化剂床B的横截面的面积彼此相同或不同，各自独立地为不超过300000mm 2(优选不超过100000mm 2)，和/或，在所述催化剂床的任意横截面上，任意一个所述子催化剂床A的横截面上任一点到与其相邻的任意一个所述子催化剂床B的横截面的边缘的最短距离不超过500mm(优选不超过300mm，更优选不超过200mm，进一步优选不超过100mm，最优选不超过50mm)。
  18. 根据权利要求15所述的催化剂床，其中以所述催化剂床的总体积计，所述具有脱硫活性的加氢催化组分所占的比例为35-90％(优选45-80％，更优选50-75％)，并且所述硫吸附组分所占的比例为10-65％(优选20-55％，更优选25-50％)。
  19. 根据权利要求15所述的催化剂床，其中所述具有脱硫活性的加氢催化组分经过硫化处理，而所述硫吸附组分经过或没有经过硫化处理，和/或，所述硫化处理的反应条件包括：干法硫化或湿法硫化，硫化剂为选自硫化氢、二硫化碳、二甲基二硫醚、甲基硫醚和正丁基硫醚中的至少一种，硫化压力为1.2-15MPaG(1.2-9.4MPaG)，硫化温度为280-400℃，硫化时间为4-22h。
  20. 一种加氢方法(优选液相固定床加氢方法)，包括使根据权利要求7所述的液相加氢催化剂组合物或根据权利要求15所述的催化剂床与油品在液相加氢反应条件下接触而发生加氢反应的步骤(称为加氢步骤)。
  21. 根据权利要求20所述的方法，其中所述油品选自汽油、煤油、柴油、蜡油、渣油和煤焦油中的至少一种(优选选自柴油、蜡油和渣油中的至少一种)，和/或，所述油品的硫含量(换算为硫化氢)为0.01-3.0wt％(优选0.01-2.0wt％)，和/或，所述液相加氢反应条件包括：反应温度100-500℃(优选100-450℃)，反应压力1-20MPaG(优选(2-15MPaG)，液时空速为1-10h -1(优选2-10h -1，更优选2-8h -1)，所述油品的(溶解)氢气含量为0.01-0.35wt％(优选0.05-0.25wt％)。
  22. 根据权利要求20所述的方法，还包括在进行所述加氢步骤之前，对所述液相加氢催化剂组合物或所述催化剂床进行硫化处理的步骤，和/或，所述硫化处理的反应条件包括：干法硫化或湿法硫化，硫化剂为选自硫化氢、二硫化碳、二甲基二硫醚、甲基硫醚和正丁基硫醚中的至少一种，硫化压力为1.2-15MPaG(1.2-9.4MPaG)，硫化温度为280-400℃，硫化时间为4-22h。
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4447314A (en) * 1982-05-05 1984-05-08 Mobil Oil Corporation Demetalation, desulfurization, and decarbonization of petroleum oils by hydrotreatment in a dual bed system prior to cracking
CN102876368A (zh) 2011-07-11 2013-01-16 中国石油化工股份有限公司 一种柴油液相加氢方法
CN103789029A (zh) 2012-11-03 2014-05-14 中国石油化工股份有限公司 一种两相加氢组合方法
CN108855115A (zh) 2018-06-05 2018-11-23 中国科学院山西煤炭化学研究所 一种涂层催化剂及制备方法和应用
CN111068750A (zh) * 2018-10-22 2020-04-28 中国石油化工股份有限公司 一种改性氧化铝载体及其制备方法和加氢精制催化剂
CN111073689A (zh) * 2018-10-22 2020-04-28 中国石油化工股份有限公司 一种重质油加氢处理方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69925580D1 (de) * 1998-12-08 2005-07-07 Japan Energy Corp Katalysator zur hydrodesulforierung und verfahren zu seiner herstellung
CN101928592B (zh) * 2009-06-26 2012-07-18 中国石油天然气股份有限公司 一种加氢催化剂的级配组合
CN103769038B (zh) * 2012-10-23 2016-08-24 中国石油化工股份有限公司 一种气体脱硫吸附剂、其制备方法及应用
FR3022156B1 (fr) * 2014-06-13 2018-02-23 Ifp Energies Now Catalyseur mesoporeux et macroporeux a phase active comalaxee, son procede de preparation et son utilisation en hydrotraitement de residus
US11325107B2 (en) * 2019-02-13 2022-05-10 King Fahd University Of Petroleum And Minerals Method for producing activated carbon supported Ni/Mo catalyst for hydrodesulfurization

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4447314A (en) * 1982-05-05 1984-05-08 Mobil Oil Corporation Demetalation, desulfurization, and decarbonization of petroleum oils by hydrotreatment in a dual bed system prior to cracking
CN102876368A (zh) 2011-07-11 2013-01-16 中国石油化工股份有限公司 一种柴油液相加氢方法
CN103789029A (zh) 2012-11-03 2014-05-14 中国石油化工股份有限公司 一种两相加氢组合方法
CN108855115A (zh) 2018-06-05 2018-11-23 中国科学院山西煤炭化学研究所 一种涂层催化剂及制备方法和应用
CN111068750A (zh) * 2018-10-22 2020-04-28 中国石油化工股份有限公司 一种改性氧化铝载体及其制备方法和加氢精制催化剂
CN111073689A (zh) * 2018-10-22 2020-04-28 中国石油化工股份有限公司 一种重质油加氢处理方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4197631A4

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