CN114621784A - Ultra-deep hydrodesulfurization method for diesel oil - Google Patents
Ultra-deep hydrodesulfurization method for diesel oil Download PDFInfo
- Publication number
- CN114621784A CN114621784A CN202011462030.6A CN202011462030A CN114621784A CN 114621784 A CN114621784 A CN 114621784A CN 202011462030 A CN202011462030 A CN 202011462030A CN 114621784 A CN114621784 A CN 114621784A
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- CN
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- Prior art keywords
- catalyst
- hydrogenation
- hydrodesulfurization
- hydrodesulfurization catalyst
- group metal
- Prior art date
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a diesel oil ultra-deep hydrodesulfurization method, which comprises the following steps: hydrodesulfurization catalyst A and hydrodesulfurization catalyst B are filled in the hydrodesulfurization reactor from top to bottom in sequence, and the filling volume ratio of the hydrodesulfurization catalyst A to the hydrodesulfurization catalyst B is 5: 5-9: 1; the hydrodesulfurization catalyst A comprises VIB group metal sulfide and VIII group metal sulfide; the hydrodesulfurization catalyst B comprises a first hydrogenation active metal, a second hydrogenation active metal and a hydrogenation catalyst carrier; the first hydrogenation active metal is present in a sulfided form; the second hydrogenation active component is present in an oxidized form. The invention can gradually release the hydrogenation activity of the catalyst by the grading filling of two hydrodesulfurization catalysts with different activities, and can further prolong the operation period of the device in the ultra-deep desulfurization reaction of diesel oil.
Description
Technical Field
The invention relates to a diesel oil ultra-deep hydrodesulfurization method.
Background
With the strictness of environmental regulations, low sulfur, low aromatic hydrocarbon, low density and high cetane number become the development trend of new diesel specifications in countries and regions in the world. European vi emission standards performed in the european union in 2013, month 1. China executes the national IV diesel quality standard from 1/2015, requires that the sulfur content of the automotive diesel is no more than 50 mu g/g, the national V diesel quality standard is comprehensively executed from 1/2018, the national V diesel quality standard is started to be executed from 1/2017 in advance, 11 provinces and cities in the east are executed from 1/2016 in advance, and the national VI diesel quality standard is started to be executed from 1/2019. The demand of oil refining enterprises on the device operation cycle is also in the trend of prolonging 4-5 years, and the catalyst is required to have higher activity stability.
The hydrodesulfurization catalyst and the process technology are the basis for realizing ultra-deep desulfurization and meeting the requirement of oil refining enterprises on realizing long-period stable operation from one overhaul in three years to one overhaul in 5 years.
MoS of diesel oil hydrodesulfurization catalyst2The activity of the wafer is generally the highest in 3-5 layers, and the carrier of the diesel hydrodesulfurization catalyst is generally modified alumina, so that the carrier has strong interaction with active metals, the dispersibility of the active metals is poor, and the generation of active centers is reduced. In order to inhibit the generation of overlarge sulfide active phase stack layer, weaken the interaction between the carrier and the active metal, improve the dispersion degree of the active metal and reduce MoS2Wafer length to generate more proportion of 3-5 layers of MoS2The proportion of the wafer and the Co-Mo-S phase in all Co species can effectively improve the activity of the catalyst.
The diesel hydrogenation device generally adopts multiple beds, can be operated at relatively low reaction temperature at the initial stage of operation of the device, particularly has lower reaction temperature at the upper bed, realizes the service life consistency of the catalyst of the whole bed of the hydrogenation device aiming at the temperature difference of the material flow feeding of the reactor from top to bottom and different intervals, ensures the long-period stable operation, and effectively improves the operation period of the device by the reasonable combined filling of the catalyst.
CN201811322068.6 discloses a distillate oil hydrotreating catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: (1) preparing an impregnation solution, wherein the solution contains hydrogenation active metal, an organic auxiliary agent, methylene dinaphthalene sodium sulfonate and aluminum salt; (2) mixing and kneading the macroporous alumina powder and the dipping solution, molding, drying and roasting to obtain an oxidation state hydrogenation catalyst; (3) and carrying out vulcanization treatment on the oxidation state catalyst to obtain the catalyst.
MoS in the above patent2The length of the wafer is 5.8 to 7.3, 3 to 5 layers of MoS2The proportion of the wafer is 36-47%, and the proportion of the Co-Mo-S phase in all Co species is 50-60%.
CN201110321355.7 discloses a combined loading method of hydrofining catalysts, raw material diesel oil and hydrogen gas are mixed and then sequentially pass through four hydrogenation reaction zones, wherein hydrofining catalysts with different metal contents and different acid amounts are respectively loaded in different reaction zones, and a diesel oil product is obtained after reaction effluent is separated and fractionated.
The combined filling purpose of the patents is to enable the graded filling system to have higher reactivity as a whole, and although the stability of the catalyst can be increased, the device needs a vulcanization process, which affects the industrial application efficiency, and is not suitable for oil refining enterprises without an online vulcanization unit.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a diesel ultra-deep hydrodesulfurization method. The invention can gradually release the hydrogenation activity of the catalyst by the grading filling of two hydrodesulfurization catalysts with different activities, and can further prolong the operation period of the device in the ultra-deep desulfurization reaction of diesel oil.
The diesel oil ultra-deep hydrodesulfurization method comprises the following steps: under the condition of hydrogenation reaction, the diesel raw material and hydrogen are subjected to hydrogenation reaction in a hydrogenation reactor, and the reaction product flows out of the reactor; hydrodesulfurization catalyst A (vulcanized hydrodesulfurization catalyst) and hydrodesulfurization catalyst B (vulcanized-oxidation state composite catalyst) are sequentially filled in the hydrodesulfurization reactor along the material flow direction, and the filling volume ratio of the hydrodesulfurization catalyst A to the hydrodesulfurization catalyst B is 5: 5-9: 1, preferably 6: 4-7: 3. the hydrodesulfurization catalyst A comprises a hydrogenation catalyst carrier and a hydrogenation active component, wherein the hydrogenation active component comprises a VIB group metal sulfide and a VIII group metal sulfide; wherein at least one of VIB group is Mo, and can also comprise active components such as W, etc., and VIII group is at least Co and Fe, and can also comprise active components such as Ni, etc.; the molar proportion of species of the group VIII metal and the group VIB metal which interact with each other (such as adjoining, laminating, covering, loading, attaching, mixing, scattering, wrapping or any combination thereof, particularly the group VIII metal compound loaded on the group VIB metal sulfide) accounts for 60-90%, preferably 65-80% of the total amount of the group VIII metal (such as the proportion of Co-Mo-S phase in all Co species is 60-90%, preferably 65-80%);
the hydrodesulfurization catalyst B comprises a first hydrogenation active metal, a second hydrogenation active metal and a hydrogenation catalyst carrier; the first hydrogenation active metal is Mo and/or W, Co and/or Ni and Fe, and exists in a sulfuration state; the second hydrogenation active component is Co and/or Ni and exists in an oxidation state; MoS based on the total weight of the catalyst2And/or WS29 to 47wt%, preferably 15 to 35wt%, Co9S8And/or Ni3S21 to 4%, preferably 1.5 to 3.5wt%, FeS 3.0 to 18.0wt%, preferably 5.0 to 13.0wt%, CoO and/or NiO 0.6 to 2.5wt%, preferably 0.7 to 2.0 wt%. The catalyst is analyzed by X-ray photoelectron spectroscopy (XPS spectroscopy for short) after self-vulcanization, wherein the molar proportion of the +4 valence VIB group metal content in the total VIB group metal content is 60-90%.
In the method, the diesel raw material is one or any mixed raw material of direct-flow diesel, coking diesel and catalytic diesel. The diesel raw material and the hydrogen are preferably fed in an upper feeding mode.
In the method of the present invention, the hydrodesulfurization reactor is generally a fixed bed hydrogenation reactor.
The hydrodesulfurization catalyst A is analyzed by adopting X-ray photoelectron spectroscopy (XPS spectroscopy for short), wherein the molar proportion of the VIB group metal content with +4 valence state in the total VIB group metal content is 60-90%.
The hydrodesulfurization catalyst A and the active phase MoS2The average length of the platelets is 4-7 nm, the average number of the platelets in a single stack is 1-5, and the proportion of stacks with 3-5 layers is 40-90%, preferably 40-70%, based on the total number of stacks.
The hydrodesulfurization catalyst A is composed of 9-47 wt% of VIB group metal sulfide and 4.5-25 wt% of VIII group metal sulfide, based on the total weight of the catalyst, and MoS is preferred215wt%~30wt%，Co9S82-6 wt%, FeS 5.5-11 wt%, and the balance hydrogenation catalyst carrier.
After the hydrodesulfurization catalyst B is vulcanized, the active phase (in MoS)2For example) has an average length of 4-7 nm, the average number of the platelets in a single stacked layer is 1-5, and the ratio of stacked layers with 3-5 layers is 40-90%, preferably 40-70%, based on the total number of stacked layers. The Co-Mo-S phase accounts for 60-90%, preferably 65-80% of the total Co species in Co (Co-Mo-S)/Co (total).
In the method of the present invention, the hydrogenation catalyst carrier is a porous inorganic refractory oxide, preferably one or more oxides of elements selected from group II, group III, group IV and group IVB of the periodic table of elements, preferably one or more oxides selected from silica, alumina, magnesia, zirconia, titania, silica alumina, magnesia silica and alumina-magnesia, preferably alumina. The properties of the vector are generally required as follows: the pore volume is 0.3-1.5 mL/g, the specific surface area is 150-450 m2/g。
In the method, the hydrodesulfurization catalyst A and the hydrodesulfurization catalyst B further comprise one or more modification elements selected from B, P and F, and the weight percentage of the modification elements (calculated as the modification elements) is 0.5-10 wt% based on the total weight of the modification elements and the hydrogenation catalyst carrier.
The preparation method of the hydrodesulfurization catalyst A comprises the following steps: (1) impregnating a hydrogenation catalyst carrier with an impregnating solution containing VIB group metals, VIII group metals and a first auxiliary agent, drying the impregnated carrier, and then vulcanizing; (2) dipping the vulcanized material obtained in the step (1) by using a solution containing a VIB group metal, a VIII group metal and a second auxiliary agent, and drying and roasting to obtain a vulcanized hydrodesulfurization catalyst precursor; (3) and (3) carrying out vulcanization treatment on the vulcanized hydrodesulfurization catalyst precursor obtained in the step (2) to obtain a product.
In the reactor, the VIB group metal and the VIII group metal in the step (1) are VIB group Mo and/or W, VIII group Ni and/or Co; the first auxiliary agent in step (1) is at least one selected from organic acids with at least two carboxyl groups (such as at least one selected from citric acid and ethylene diamine tetraacetic acid, preferably citric acid) and organic alcohols with at least three hydroxyl groups (such as at least one selected from glycerol and glucose, preferably glycerol), and the molar ratio of the first auxiliary agent to the hydrogenation active metals (calculated as hydrogenation active metal elements), namely, the VIB group metal and the VIII group metal, is 0.1-2.0 (preferably 0.2-0.8).
The VIB group metal and the VIII group metal in the step (2) are VIB group Mo and/or W, VIII group Ni and/or Co and Fe; the second auxiliary agent in step (2) is at least one selected from organic acids with at least two carboxyl groups (such as at least one selected from citric acid and ethylene diamine tetraacetic acid, preferably citric acid), organic alcohols with at least one double bond (such as allyl alcohol) and organic alcohols with at least two hydroxyl groups (such as at least one selected from ethylene glycol, glycerol and glucose, preferably ethylene glycol), and the molar ratio of the second auxiliary agent to the hydrogenation-active metals (calculated by hydrogenation-active metal elements), namely, group VIB metals and group VIII metals, is 0.1-2.0 (preferably 0.2-0.8).
The preparation method of the hydrodesulfurization catalyst B comprises the following steps: (a) impregnating a hydrogenation catalyst carrier with an impregnation liquid containing a first hydrogenation active metal and an organic compound, drying the impregnated carrier, and then vulcanizing; (b) impregnating the vulcanized material obtained in the step (a) with an impregnation liquid containing a second hydrogenation active metal and an organic compound, and drying and roasting to obtain a catalyst product; the organic compound is one or more of organic acid, organic alcohol and sugar.
Wherein the organic acid is at least one selected from dibasic acids with 2-10 carbon atoms; the organic acid is one or more of citric acid, citric anhydride, isocitric acid, malic acid, tartaric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, phthalic acid, isophthalic acid, salicylic acid or malonic acid; the organic alcohol is selected from one or more of aliphatic alcohol with 3-10 carbon atoms and dihydric alcohol; the organic alcohol is one or more of fatty alcohol, ethylene glycol, propylene glycol, glycerol, trimethylene ethane, trimethylene propane, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, tetrapropylene glycol, polyethylene glycol, diethylene methyl glycol, diethylene ethyl glycol, diethylene allyl glycol and diethylene butyl glycol; the saccharide is at least one of monosaccharide and disaccharide with carbon number of 3-10, such as arabinose, xylose, fructose, glucose, sedoheptulose, sucrose, maltose, mannotriose, stachyose, and verbascose. The addition amount of the organic compound is 0.1 to 0.5 times of the total mole number of the first and second hydrogenation active metal oxides.
The preparation of the impregnation solution is well known to those skilled in the art, and the concentration and addition amount of the impregnation solution using a compound containing a metal element as a source are generally determined according to the composition of the catalyst. For example, molybdenum trioxide, ammonium metatungstate and VIII group metals Ni and/or Co are generally adopted as the VIB group metal Mo and/or W, basic cobalt carbonate and basic nickel carbonate are generally adopted as the VIII group metal Ni and/or Co, and iron acetate is adopted as Fe.
The drying temperature is 80-200 ℃, and the drying time is 3-24 hours. The roasting temperature is 300-350 ℃, and the roasting time is 3-4 hours.
The vulcanization treatment adopts an in-situ or out-of-situ vulcanization process, the amount of the introduced vulcanizing agent is 90-150% of the theoretical sulfur demand of the catalyst, and the vulcanization process adopts temperature programming, wherein the temperature is raised to 200-350 ℃ and is kept constant for 1-16 hours. The vulcanizing agent is typically one or more of carbon disulfide, dimethyl disulfide, methyl sulfide, or n-butyl sulfide.
In the diesel oil deep hydrodesulfurization method of the invention, the general hydrogenation reaction conditions are as follows: the pressure is 6.0-8.0 MPa, and the airspeed is 1.0-2.5 h-1The temperature is 300-390 ℃, and the volume ratio of hydrogen to oil is 100-800.
Compared with the prior art, the invention has the following advantages:
1. the hydrodesulfurization catalyst A is prepared by dipping a VIB group metal Mo and/or W, a VIII group metal Ni and/or Co and a Fe metal on a sulfidized VIB group metal Mo and/or W and a VIII group metal Ni and/or Co for step-by-step dipping and sulfidation; the hydrodesulfurization catalyst B adopts the method that Ni and/or Co metal is impregnated on the sulfuration state Mo and/or W, Ni and/or Co metal and Fe metal, so that the difficulty of impregnation and activation of active metal in each step is reduced;
2. because Mo and/or W is harder to vulcanize than Ni and/or Co metals and is liable to cause the phenomenon that the vulcanized Mo and/or W is wrapped by Ni and/or Co metals, the hydrodesulfurization catalyst A is prepared by impregnating part of Mo and/or W and part of Ni and/or Co metals, drying, vulcanizing and not roasting; the hydrodesulfurization catalyst B is prepared by firstly impregnating Mo and/or W and partial Ni and/or Co metals and Fe metals, drying and vulcanizing, wherein roasting is not required in the process, so that the phenomenon that the vulcanized VIII group metal is wrapped by the vulcanized VIB group metal can be avoided, stronger adsorption sites on the surface of a carrier can be covered, the interaction force between the subsequent impregnated active metal and the surface of the carrier is weakened, the subsequent dispersion of the Mo and/or W active metal is facilitated, and the auxiliary effect of the Ni and/or Co metals can be fully exerted;
3. the hydrodesulfurization catalyst A first sulfurizes the group VIB metal and the group VIII metal to form Ni and/or Co modified MoS2By additional impregnation of Mo and/or W, Ni and/or Co metals and Fe metals; and the hydrodesulfurization catalyst B is subjected to second step of impregnation of the residual Ni and/or Co metal, so that on one hand, the regulating activity of the additive content is increased, on the other hand, the additive is more dispersed, the effect of the Ni and/or Co metal additive can be fully exerted, and the aggregation of the Ni and/or Co metal is not caused, thereby improving the content of species interacting with the VIB group metal, promoting the generation of II type active centers and further improving the activity of the catalyst.
4. The hydrodesulfurization catalyst A and the hydrodesulfurization catalyst B adopt Fe acetate as Fe metal, and the adoption of organic iron salt compounds can overcome the defects that the competitive combination of inorganic iron salt and VIII group Ni and/or Co metal and VIB group metal in the solution preparation process in the prior art is adopted, and the addition of Fe generates synergistic promotion on the catalysis of Mo and/or W metalThe strong adsorption sites on the surface of the catalyst can be covered, and MoS is caused by the existence of Fe2(WS2) The crystals are separated from each other, the probability of coalescence among the crystals is reduced, the interaction force between the impregnated active metal and the surface of the carrier is weakened, on one hand, the content modulation activity of the auxiliary agent is increased, on the other hand, the auxiliary agent is more dispersed, the action of the VIII group Ni and/or Co metal auxiliary agent can be fully exerted, the aggregation of the VIII group Ni and/or Co metal cannot be caused, so that the dispersion degree of Mo and/or W on the carrier is improved, and the generation of II-type active centers is promoted.
5. The hydrodesulfurization catalyst A and the hydrodesulfurization catalyst B are filled in the reactor from top to bottom in a combined mode, the initial activity of a vulcanized catalyst at the initial stage of reaction is high, the reaction is mild, the requirement of ultra-deep hydrodesulfurization can be met by only depending on the hydrodesulfurization catalyst A (vulcanized) only, the hydrodesulfurization catalyst B (vulcanized state-oxidized state composite type) is subjected to a slow self-vulcanization process through hydrogen sulfide generated by self ultra-deep desulfurization in the operation process of the device, the activity of the catalyst is gradually released, the optimal vulcanization state is achieved after the device is operated for a period of time, the optimal action is played at the middle stage of the operation of the device, the defect that the inactivation rate of a high-temperature area is relatively high is overcome, and the whole operation period of the ultra-deep hydrodesulfurization reaction of the device is prolonged.
Drawings
FIGS. 1 and 2 are transmission electron micrographs of catalysts of examples 1 and 5 of the present invention.
FIG. 3 is a transmission electron micrograph of a comparative example 1 catalyst.
Detailed Description
In the present invention, the specific surface area and the pore volume are measured by a low-temperature liquid nitrogen adsorption method. The length of the lamella and the layer number ratio of the stacking layers are measured by a field emission transmission electron microscope, and the specific method comprises the following steps: selecting more than 350 MoS2Counting and arranging the average layer number, the average length and the proportion of 3-5 layers of wafers by using the platelets, wherein the statistical formula is as follows:
wherein liRepresenting the wafer length, NiRepresents the number of i layers, aiRepresentative wafer liNumber of (a), (b)iNumber of representative layers NiThe number of (2). In the present invention, wt% means mass percentage.
XPS characterization was performed on a MultiLab 2000X-ray photoelectron spectrometer, zemer hewler technologies. Al Ka-photoelectron source, Eb = 1486.6 eV. the position of the peak of the Al 2p spectrum of the reference catalyst support (C1 s, 285.0eV) corrected for the charge induced spectral peak shift. The peak separation fitting is carried out on the Co2pXPS spectrogram of the vulcanized catalyst prepared by the method, the spectrogram of Co2p mainly has 3 peaks, which are respectively attributed to Co-Mo-S phase around 779ev, Co-O vibration peak around 781ev and Co-O vibration peak around 785ev2+. The ratio of Co-Mo-S phase to Co (Co-Mo-S)/Co (total) in all Co species can be calculated by fitting the peak-to-peak area, relative to MoS2As for the active phase, the Co-Mo-S phase has higher desulfurization activity.
Example 1
100g of alumina carrier (water absorption rate of 80mL/100 g) is placed in a rolling pot, under the condition of rotation, 80mL of aqueous solution containing 21.5g of molybdenum trioxide, 6.4g of basic cobalt carbonate, 0.4g of ethylene glycol and 4.3g of citric acid is sprayed into the alumina carrier in the rolling pot in an atomizing mode, after the solution is sprayed, the rolling pot is rotated for 30 minutes, and drying is carried out for 4 hours at 110 ℃ to prepare the primary oxidation state catalyst A. And (3) carrying out vulcanization treatment on the first-stage oxidation state catalyst A by adopting an in-situ vulcanization process, introducing dimethyl disulfide accounting for 120% of the theoretical sulfur demand of the catalyst, and carrying out temperature programming in the vulcanization process, wherein the temperature is raised to 320 ℃ and is kept constant for 10 hours, so as to obtain the first-stage vulcanization catalyst A. Putting a section of sulfidation catalyst A into a rolling pot, spraying 40mL of aqueous solution containing 8.6g of molybdenum trioxide, 20.8g of iron acetate, 3.1g of basic cobalt carbonate, 0.7g of ethylene glycol and 3.3g of citric acid into an alumina carrier in the rolling pot in an atomization mode under the rotating condition, after the solution is sprayed, continuously rotating the rolling pot for 30 minutes, drying the solution at 110 ℃ for 4 hours, and roasting the solution at 300 ℃ for 4 hours to prepare the sulfidation type hydrodesulfurization catalyst precursor A. And (2) carrying out vulcanization treatment on the vulcanization type hydrodesulfurization catalyst precursor A by adopting an in-situ vulcanization process, introducing 120% of dimethyl disulfide of the theoretical sulfur demand of the catalyst, raising the temperature by adopting a program in the vulcanization process, and keeping the temperature at 320 ℃ for 10 hours to obtain the finished product vulcanization type hydrodesulfurization catalyst A.
Example 2
100g of alumina carrier (water absorption rate of 80mL/100 g) is placed in a rolling pot, under the condition of rotation, 80mL of aqueous solution containing 22.9g of molybdenum trioxide, 9.2g of basic cobalt carbonate, 1.6g of ethylene glycol and 4.5g of citric acid is sprayed into the alumina carrier in the rolling pot in an atomizing mode, after the solution is sprayed, the rolling pot is rotated for 30 minutes, and drying is carried out for 4 hours at 110 ℃ to obtain the primary oxidation state catalyst B. And (3) carrying out vulcanization treatment on the first-stage oxidation catalyst B by adopting an in-situ vulcanization process, introducing 120% of the theoretical sulfur demand of the catalyst by using the amount of dimethyl disulfide, raising the temperature to 320 ℃ by adopting a temperature program in the vulcanization process, and keeping the temperature for 10 hours to obtain the first-stage vulcanization catalyst B. Putting a section of sulfidation catalyst A into a rolling pot, spraying 38mL of aqueous solution containing 8.1g of molybdenum trioxide, 21.1g of iron acetate, 4.1g of basic cobalt carbonate, 0.7g of ethylene glycol and 3.3g of citric acid into an alumina carrier in the rolling pot in an atomization mode under the rotating condition, after the solution is sprayed, continuously rotating the rolling pot for 30 minutes, drying the solution at 110 ℃ for 4 hours, and roasting the solution at 350 ℃ for 4 hours to prepare a sulfidation type hydrodesulfurization catalyst precursor B. And (2) carrying out vulcanization treatment on the vulcanization type hydrodesulfurization catalyst precursor B by adopting an in-situ vulcanization process, introducing 120% of the theoretical sulfur demand of the catalyst by using the amount of dimethyl disulfide, and carrying out temperature programming in the vulcanization process, wherein the temperature is raised to 320 ℃ and is kept for 10 hours to obtain the finished product vulcanization type hydrodesulfurization catalyst B.
Example 3
100g of alumina carrier (water absorption rate of 80mL/100 g) is placed in a rolling pot, under the condition of rotation, 80mL of aqueous solution containing 19.4g of molybdenum trioxide, 6.4g of basic cobalt carbonate, 0.4g of glycerol and 2.0g of oxalic acid is sprayed into the alumina carrier in the rolling pot in an atomizing mode, after the solution is sprayed, the rolling pot is rotated for 30 minutes, and the primary oxidation state catalyst C is prepared after drying at 110 ℃ for 4 hours. And (3) carrying out vulcanization treatment on the first-stage oxidation state catalyst C by adopting an in-situ vulcanization process, introducing dimethyl disulfide accounting for 120% of the theoretical sulfur demand of the catalyst, and carrying out temperature programming in the vulcanization process, wherein the temperature is raised to 320 ℃ and is kept constant for 10 hours, so as to obtain the first-stage vulcanization catalyst C. Putting a section of the sulfidation catalyst C into a rolling pot, spraying 42mL of aqueous solution containing 10.5g of molybdenum trioxide, 21.2g of iron acetate, 0.7g of glycerol and 1.4g of oxalic acid into the alumina carrier in the rolling pot in an atomization mode under the rotation condition, continuing rotating the rolling pot for 30 minutes after the solution is sprayed, drying the solution at 110 ℃ for 4 hours, and roasting the solution at 350 ℃ for 4 hours to prepare the sulfidation type hydrodesulfurization catalyst precursor C. And (2) carrying out vulcanization treatment on the vulcanization type hydrodesulfurization catalyst precursor C by adopting an in-situ vulcanization process, introducing dimethyl disulfide accounting for 120% of the theoretical sulfur demand of the catalyst, raising the temperature to 320 ℃ by adopting a temperature program in the vulcanization process, and keeping the temperature for 10 hours to obtain the finished product vulcanization type hydrodesulfurization catalyst C.
Example 4
100g of alumina carrier (water absorption rate of 80mL/100 g) is placed in a rolling pot, under the condition of rotation, 80mL of aqueous solution containing 3.5g of molybdenum trioxide, 15.7g of ammonium metatungstate, 6.6g of basic nickel carbonate, 0.8g of ethylene glycol and 2.5g of citric acid is sprayed into the alumina carrier in the rolling pot in an atomizing mode, after the solution is sprayed, the rolling pot is rotated for 30 minutes continuously, and the drying is carried out for 4 hours at 110 ℃, so that the primary oxidation state catalyst D is prepared. And (3) carrying out vulcanization treatment on the first-stage oxidation catalyst D by adopting an in-situ vulcanization process, introducing dimethyl disulfide accounting for 120% of the theoretical sulfur demand of the catalyst, raising the temperature to 320 ℃ by adopting a temperature program in the vulcanization process, and keeping the temperature constant for 10 hours to obtain the first-stage vulcanization catalyst D. Putting a section of sulfidation catalyst D into a rolling pot, spraying 39mL of an aqueous solution containing 2.7g of molybdenum trioxide, 5.7g of ammonium metatungstate, 2.7g of basic nickel carbonate, 14.4g of iron acetate, 0.3g of ethylene glycol and 2.2g of citric acid into an alumina carrier in the rolling pot in an atomization mode under the rotation condition, continuing to rotate in the rolling pot for 30 minutes after the solution is sprayed, drying at 110 ℃ for 4 hours, and roasting at 300 ℃ for 4 hours to obtain the sulfidation type hydrodesulfurization catalyst precursor D. And (2) carrying out vulcanization treatment on the vulcanization type hydrodesulfurization catalyst precursor D by adopting an in-reactor vulcanization process, introducing 120% of dimethyl disulfide of the theoretical sulfur demand of the catalyst, raising the temperature to 320 ℃ by adopting a program in the vulcanization process, and keeping the temperature for 10 hours to obtain the finished product vulcanization type hydrodesulfurization catalyst precursor D.
Example 5
100g of alumina carrier (water absorption rate of 80mL/100 g) is placed in a rolling pot, under the condition of rotation, 80mL of aqueous solution containing 31.8g of molybdenum trioxide, 25.7g of ferric acetate, 7.6g of basic cobalt carbonate, 1.7g of ethylene glycol and 6.2g of citric acid is sprayed into the alumina carrier in the rolling pot in an atomizing mode, after the solution is sprayed, the rolling pot is rotated for 30 minutes, and the primary oxidation state catalyst E is prepared after drying for 4 hours at 110 ℃. And (3) carrying out vulcanization treatment on the first-stage oxidation state catalyst E by adopting an in-situ vulcanization process, introducing dimethyl disulfide accounting for 120% of the theoretical sulfur demand of the catalyst, and carrying out temperature programming in the vulcanization process, wherein the temperature is raised to 320 ℃ and is kept constant for 10 hours, so as to obtain the first-stage vulcanization catalyst E. And (2) placing the first-stage sulfidation catalyst E in a rolling pot, spraying 40mL of aqueous solution containing 1.7g of basic cobalt carbonate, 0.06g of ethylene glycol and 0.3g of citric acid into the alumina carrier in the rolling pot in an atomization mode under the rotation condition, continuing rotating the rolling pot for 30 minutes after the solution is sprayed, drying the solution at 110 ℃ for 4 hours, and roasting the solution at 300 ℃ for 4 hours to obtain the finished sulfide-oxide composite catalyst E.
Example 6
100g of alumina carrier (water absorption rate of 80mL/100 g) is placed in a rolling pot, under the condition of rotation, 80mL of aqueous solution containing 32.5g of molybdenum trioxide, 26.1g of ferric acetate, 8.9g of basic cobalt carbonate, 1.7g of ethylene glycol and 6.3g of citric acid is sprayed into the alumina carrier in the rolling pot in an atomizing mode, after the solution is sprayed, the rolling pot is rotated for 30 minutes, and the primary oxidation state catalyst F is prepared after drying for 4 hours at 110 ℃. And (3) carrying out vulcanization treatment on the first-stage oxidation state catalyst F by adopting an in-situ vulcanization process, introducing 120% of the theoretical sulfur demand of the catalyst based on the amount of dimethyl disulfide, and carrying out temperature programming in the vulcanization process, wherein the temperature is raised to 320 ℃ and is kept for 10 hours, so as to obtain the first-stage vulcanization catalyst F. Putting a section of sulfidation catalyst F into a rolling pot, spraying 38mL of aqueous solution containing 3.5g of basic cobalt carbonate, 0.1g of ethylene glycol and 0.4g of citric acid into the alumina carrier in the rolling pot in an atomization mode under the rotation condition, continuing to rotate in the rolling pot for 30 minutes after the solution is sprayed, drying at 110 ℃ for 4 hours, and roasting at 350 ℃ for 4 hours to obtain the finished product sulfide-oxide composite catalyst F.
Example 7
100G of alumina carrier (water absorption rate of 80 mL/100G) is placed in a rolling pot, under the condition of rotation, 80mL of aqueous solution containing 31.7G of molybdenum trioxide, 25.5G of ferric acetate, 6.3G of basic cobalt carbonate, 1.3G of glycerol and 2.6G of oxalic acid is sprayed into the alumina carrier in the rolling pot in an atomizing mode, after the solution is sprayed, the rolling pot is rotated for 30 minutes, and the primary oxidation state catalyst G is prepared after drying at 110 ℃ for 4 hours. And (3) carrying out vulcanization treatment on the first-stage oxidation state catalyst G by adopting an in-situ vulcanization process, introducing dimethyl disulfide accounting for 120% of the theoretical sulfur demand of the catalyst, and carrying out temperature programming in the vulcanization process, wherein the temperature is raised to 320 ℃ and is kept constant for 10 hours, so as to obtain the first-stage vulcanization catalyst G. Putting a section of sulfidation catalyst G into a rolling pot, spraying 42mL of aqueous solution containing 2.6G of basic cobalt carbonate, 0.06G of glycerol and 0.2G of oxalic acid into the alumina carrier in the rolling pot in an atomization mode under the rotation condition, continuing to rotate in the rolling pot for 30 minutes after the solution is sprayed, drying at 110 ℃ for 4 hours, and roasting at 350 ℃ for 4 hours to obtain the finished sulfide-oxide composite catalyst G.
Example 8
100g of alumina carrier (water absorption rate of 80mL/100 g) is placed in a rolling pot, under the condition of rotation, 80mL of aqueous solution containing 6.2g of molybdenum trioxide, 21.1g of ammonium metatungstate, 5.0g of basic nickel carbonate, 14.5g of iron acetate, 1.1g of ethylene glycol and 3.6g of citric acid is sprayed into the alumina carrier in the rolling pot in an atomizing mode, after the solution is sprayed, the rolling pot is rotated for 30 minutes continuously, and the drying is carried out for 4 hours at 110 ℃, so that the primary oxidation state catalyst H is prepared. And (3) carrying out vulcanization treatment on the first-stage oxidation state catalyst H by adopting an in-situ vulcanization process, introducing dimethyl disulfide accounting for 120% of the theoretical sulfur demand of the catalyst, and carrying out temperature programming in the vulcanization process, wherein the temperature is raised to 320 ℃ and is kept constant for 10 hours, so as to obtain the first-stage vulcanization catalyst H. Putting a section of sulfidation catalyst H into a rolling pot, spraying 39mL of an aqueous solution containing 3.8g of basic nickel carbonate, 0.2g of ethylene glycol and 0.4g of citric acid into an alumina carrier in the rolling pot in an atomization mode under the rotating condition, continuing rotating the rolling pot for 30 minutes after the solution is sprayed, drying the rolling pot for 4 hours at 110 ℃, and roasting the rolling pot for 4 hours at 300 ℃ to obtain a finished product sulfide-oxide composite catalyst H.
Example 9
A, B, C, D, E, F, G, H, (50% A +50% E), (70% C +30% G) catalysts are respectively adopted on a 200mL small-sized fixed bed hydrogenation device, the hydrogen partial pressure is 6.4MPa, and the liquid hourly volume space velocity is 1.5h-1The volume ratio of hydrogen to oil is 500Nm3/m3And the average reaction temperature is 360 ℃, and the raw materials in the table 1 are hydrotreated.
TABLE 1 Properties of the raw materials
| Raw oil | Normal-temperature straight-run diesel oil |
| Density (20 ℃ C.), g/cm3 | 0.854 |
| Distillation range (ASTM-D86), DEG C | |
| IBP/10% | 210/272 |
| 30%/50% | 294/308 |
| 70%/90% | 322/345 |
| 95%/FBP | 357/364 |
| Sulfur content, μ g/g | 15500 |
| Nitrogen content,. mu.g/g | 284 |
Comparative example 1
Preparing 80mL of aqueous solution containing 28.8g of molybdenum trioxide, 9.1g of basic cobalt carbonate, 1.4g of ethylene glycol and 5.6g of citric acid, putting 100g of alumina carrier in a rolling pot, spraying the solution into the alumina carrier in the rolling pot in an atomization mode under the rotating condition, rotating the rolling pot for 30 minutes after the solution is sprayed, then standing for 18 hours, and drying at 110 ℃ for 5 hours to prepare the oxidation state catalyst I. Carrying out vulcanization treatment on the oxidation-state catalyst I by adopting an in-situ vulcanization process, introducing dimethyl disulfide accounting for 120% of the theoretical sulfur demand of the catalyst, raising the temperature to 320 ℃ by adopting a program in the vulcanization process, and keeping the temperature for 10 hours to obtain a finished product catalyst I.
Comparative example 2
Preparing 80mL of aqueous solution containing 29.6g of molybdenum trioxide, 12.8g of basic cobalt carbonate, 1.9g of ethylene glycol and 5.7g of citric acid, putting 100g of alumina carrier in a rolling pot, spraying the solution into the alumina carrier in the rolling pot in an atomization mode under the rotating condition, continuing rotating the rolling pot for 30 minutes after the solution is sprayed, then standing for 18 hours, and drying at 110 ℃ for 5 hours to prepare the oxidation state catalyst J. Carrying out vulcanization treatment on the oxidation state catalyst J by adopting an in-situ vulcanization process, wherein the amount of introduced dimethyl disulfide is 120% of the theoretical sulfur demand of the catalyst, and the vulcanization process adopts temperature programming, and the temperature is raised to 320 ℃ and kept constant for 10 hours to obtain the finished product catalyst J.
Comparative example 3
Preparing 80mL of aqueous solution containing 28.8g of molybdenum trioxide, 9.1g of basic cobalt carbonate, 0.4g of glycerol and 2.4g of oxalic acid, putting 100g of alumina carrier in a rolling pot, spraying the solution into the alumina carrier in the rolling pot in an atomization mode under the rotating condition, after the solution is sprayed, continuously rotating the rolling pot for 30 minutes, then standing for 18 hours, and drying for 5 hours at 110 ℃ to obtain the oxidation state catalyst K. Carrying out vulcanization treatment on the oxidation state catalyst K by adopting an in-situ vulcanization process, introducing 120% of dimethyl disulfide of the theoretical sulfur demand of the catalyst, and carrying out temperature programming in the vulcanization process, raising the temperature to 320 ℃ and keeping the temperature for 10 hours to obtain the finished product catalyst K.
Comparative example 4
100g of alumina carrier (water absorption of 80mL/100 g) is placed in a rolling pot, under the condition of rotation, 80mL of aqueous solution containing 9.1g of basic nickel carbonate, 6.1g of molybdenum trioxide, 20.6g of ammonium metatungstate, 0.8g of ethylene glycol and 4.7g of citric acid is sprayed into the alumina carrier in the rolling pot in an atomizing manner, after the solution is sprayed, the rolling pot is rotated for 30 minutes continuously, and the drying is carried out for 4 hours at 110 ℃, so that the oxidation state catalyst L is prepared. And (3) carrying out vulcanization treatment on the oxidation state catalyst L by adopting an in-situ vulcanization process, introducing 120% of dimethyl disulfide of the theoretical sulfur demand of the catalyst, and carrying out temperature programming in the vulcanization process, wherein the temperature is raised to 320 ℃ and is kept constant for 10 hours to obtain a finished product catalyst L.
Comparative example 6
The catalyst I, J, K, L was evaluated in the same manner as in example 5.
Example 6
The results of comparing the physical and chemical properties of the catalysts prepared in the above examples with those of the above examples operated on a small-sized hydrogenation apparatus for 8000 hours are shown in tables 2-1, 2-2, 3-1 and 3-2.
TABLE 2-1 catalyst essential Properties
| Catalyst numbering | A | B | C | D | E | F | G | H |
| Catalyst Properties | ||||||||
| MoS2，wt% | 24.0 | 24.2 | 24.0 | 6 | 24.0 | 24.2 | 24.0 | 6.0 |
| Co9S8，wt% | 4.0 | 5.5 | 4.0 | - | 4.0 | 5.5 | 4.0 | - |
| Ni3S2，wt% | - | - | - | 4.3 | - | - | - | 4.3 |
| WS2，wt% | - | - | - | 17.6 | - | - | - | 17.6 |
| FeS，wt% | 8.8 | 8.9 | 8.8 | 4.2 | 8.8 | 8.9 | 8.8 | 6.4 |
| Active phase MoS2Average platelet length of, nm | 5.8 | 6.0 | 5.9 | 5.9 | 5.9 | 6.1 | 6.0 | 6.0 |
| Average number of wafers in a single stack, layers | 3.4 | 3.7 | 3.9 | 3.7 | 3.5 | 3.8 | 4.0 | 3.8 |
| The ratio of the number of stacked layers of 3 to 5% | 50.8 | 50.1 | 51.0 | 51.0 | 47.6 | 46.9 | 47.9 | 47.8 |
| Mo4+/(Mo4++Mo5++ Mo6+)/% | 75 | 76 | 76 | 74 | 74 | 75 | 77 | 73 |
| Co(Co-Mo-S)/Co(total) | 66 | 68 | 67 | - | 67 | 66 | 68 |
TABLE 2-2 catalyst key Properties
| Catalyst numbering | I | J | K | L |
| Properties of the catalyst | ||||
| MoS2，wt% | 24.0 | 24.2 | 24.0 | 6.0 |
| Co9S8，wt% | 4.0 | 5.5 | 4.0 | - |
| Ni3S2，wt% | - | - | - | 4.3 |
| WS2，wt% | - | - | - | 17.6 |
| FeS，wt% | ||||
| Active phase MoS2Average platelet length of, nm | 7.1 | 7.3 | 7.2 | 7.1 |
| Average number of wafer layers in a single stack | 5.2 | 5.4 | 5.3 | 5.2 |
| A ratio of the number of stacked layers of 3 to 5% | 38.4 | 39.0 | 37.1 | 36.4 |
| Mo4+/(Mo4++Mo5++ Mo6+)/% | 55 | 54 | 52 | 53 |
| Co(Co-Mo-S)/Co(total) | 56 | 55 | 53 | - |
TABLE 3-1 test results of the catalysts
| Catalyst numbering | A | B | C | D | E | F | G | H |
| Process conditions | ||||||||
| Partial pressure of hydrogen, MPa | 6.4 | 6.4 | 6.4 | 6.4 | 6.4 | 6.4 | 6.4 | 6.4 |
| Volumetric space velocity h-1 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Reaction temperature of | 360 | 360 | 360 | 360 | 360 | 360 | 360 | 360 |
| Generating oily substance | ||||||||
| Sulfur,. mu.g/g | 9.6 | 9.7 | 9.8 | 9.4 | 9.7 | 9.8 | 9.6 | 9.5 |
| Nitrogen,. mu.g/g | 1.7 | 1.8 | 1.6 | 1.5 | 1.6 | 1.5 | 1.7 | 1.4 |
TABLE 3-2 test results of catalysts
| Catalyst numbering | 50v%A+50v%E | 70v%C+30v%G | I | J | K | L |
| Process conditions | ||||||
| Partial pressure of hydrogen, MPa | 6.4 | 6.4 | 6.4 | 6.4 | 6.4 | 6.4 |
| Volumetric space velocity h-1 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Reaction temperature of | 360 | 360 | 360 | 360 | 360 | 360 |
| Generating oily substance | ||||||
| Sulfur,. mu.g/g | 6.6 | 6.7 | 18.4 | 19.8 | 19.9 | 19.8 |
| Nitrogen,. mu.g/g | 1.1 | 1.1 | 2.4 | 2.3 | 2.5 | 2.4 |
The results in Table 3 show that the ultra-deep hydrogenation combined filling desulfurization method for diesel oil has better long-period stable ultra-deep desulfurization and denitrification performance.
Claims (10)
1. A diesel oil ultra-deep hydrodesulfurization method is characterized by comprising the following steps: under the condition of hydrogenation reaction, adding diesel oil raw material and hydrogenCarrying out hydrogenation reaction in the hydrogen reactor, and enabling reaction products to flow out of the reactor; wherein, loading hydrodesulfurization catalyst A and hydrodesulfurization catalyst B in the hydrogenation reactor along the material flow direction in sequence, wherein the loading volume ratio of the hydrodesulfurization catalyst A to the hydrodesulfurization catalyst B is 5: 5-9: 1; the hydrodesulfurization catalyst A comprises a hydrogenation catalyst carrier and a hydrogenation active component, wherein the hydrogenation active component comprises a VIB group metal sulfide and a VIII group metal sulfide; wherein at least one of group VIB is Mo, and group VIII is at least Co and Fe; the molar ratio of the interaction species of the VIII group metal and the VIB group metal to the total amount of the VIII group metal is 60-90%; the hydrodesulfurization catalyst B comprises a first hydrogenation active metal, a second hydrogenation active metal and a hydrogenation catalyst carrier; the first hydrogenation active metal is Mo and/or W, Co and/or Ni and Fe, and exists in a sulfuration state; the second hydrogenation active component is Co and/or Ni and exists in an oxidation state; MoS based on the total weight of the catalyst2And/or WS29 to 47 weight percent of Co9S8And/or Ni3S21 to 4 percent, 3.0 to 18.0 percent of FeS and 0.6 to 2.5 percent of CoO and/or NiO.
2. The method of claim 1, wherein: the diesel raw material is one or more of direct current diesel, coking diesel or catalytic diesel.
3. The method of claim 1, wherein: the hydrodesulfurization catalyst A is analyzed by X-ray photoelectron spectroscopy, wherein the molar proportion of the +4 valence VIB group metal content in the total VIB group metal content is 60-90%.
4. The method of claim 1, wherein: the hydrodesulfurization catalyst A and the active phase MoS2The average length of the platelets is 4-7 nm, the average number of the platelets in a single stack layer is 1-5, and the proportion of the stack layers with the number of 3-5 layers is 40% -90% based on the total number of the stack layers.
5. The method of claim 1, wherein: the hydrodesulfurization catalyst A is composed of 9-47 wt% of VIB group metal sulfide and 4.5-25 wt% of VIII group metal sulfide, and the balance is a hydrogenation catalyst carrier, based on the total weight of the catalyst.
6. The method of claim 1, wherein: after the hydrodesulfurization catalyst B is vulcanized, the average length of the active phase is 4-7 nm, and the average number of the platelets in a single stack layer is 1-5.
7. The method of claim 1, wherein: after the hydrodesulfurization catalyst B is vulcanized, the proportion of stacked layers with the number of 3-5 layers is 40% -90% on the basis of the total number of the stacked layers.
8. The method of claim 1, wherein: after the hydrodesulfurization catalyst B is vulcanized, the proportion of Co-Mo-S phase in all Co species is 60-90% of Co (Co-Mo-S)/Co (total).
9. The method of claim 1, wherein: the hydrogenation catalyst carrier is porous inorganic refractory oxide, and is selected from one or more of oxides of elements in II group, III group, IV group and IVB group in the periodic table.
10. The method of claim 1, wherein: the hydrogenation reaction conditions are as follows: the pressure is 6.0-8.0 MPa, and the airspeed is 1.0-2.5 h-1The temperature is 300-390 ℃, and the volume ratio of hydrogen to oil is 100-800.
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