CN114456837A - Method for reducing polycyclic aromatic hydrocarbon in diesel oil - Google Patents
Method for reducing polycyclic aromatic hydrocarbon in diesel oil Download PDFInfo
- Publication number
- CN114456837A CN114456837A CN202011136700.5A CN202011136700A CN114456837A CN 114456837 A CN114456837 A CN 114456837A CN 202011136700 A CN202011136700 A CN 202011136700A CN 114456837 A CN114456837 A CN 114456837A
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- Prior art keywords
- reaction zone
- hydrogenation
- hydrogenation reaction
- catalyst
- phase
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Links
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- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 title claims abstract description 39
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 37
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 148
- 239000003054 catalyst Substances 0.000 claims abstract description 84
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
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- 239000007791 liquid phase Substances 0.000 claims abstract description 28
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
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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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
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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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
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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
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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Abstract
The invention discloses a method for reducing polycyclic aromatic hydrocarbon in diesel oil, which comprises the following steps: the gas-phase components of the diesel raw material after flash evaporation enter a first hydrogenation reaction zone for hydrogenation reaction; the liquid phase components after flash evaporation enter a second hydrogenation reaction zone for hydrodesulfurization and denitrification reaction, the effluent of the second hydrogenation reaction zone downwards enters a third hydrogenation reaction zone for polycyclic aromatic hydrocarbon hydrogenation saturation reaction, and the product of the third hydrogenation reaction zone is discharged from the bottom of the reactor; the second hydrogenation reaction zone is filled with a semi-vulcanized type hydrogenation catalyst which comprises a VIB group metal sulfide, a VIII group metal oxide and Al2O3And an auxiliary agent; based on the weight of the bulk phase hydrofining catalyst, the content of VIB group metal sulfide is 40-70%, and the content of VIII group metal oxide is 3-25%. The method produces the high-quality diesel oil blending component with ultra-low sulfur and low polycyclic aromatic hydrocarbon by using the poor diesel oil mixed oil as the raw material through the matching of the catalyst and the process flow under the conditions of simple flow, low energy consumption and low cost.
Description
Technical Field
The invention belongs to the field of clean oil refining, and particularly relates to a method for reducing polycyclic aromatic hydrocarbons in diesel oil.
Background
With the requirement of diesel oil quality upgrading, the diesel oil in China has finished the quality upgrading of the national VI standard at present, wherein the sulfur content is not more than 10ppm, and the polycyclic aromatic hydrocarbon content is not more than 7%. According to the foreign diesel quality standard, the requirement for polycyclic aromatic hydrocarbon content in diesel oil in individual areas in the United states is lower, and further reduction of polycyclic aromatic hydrocarbon content in diesel oil is an important development direction for upgrading the diesel oil quality.
CN 102465021B discloses a diesel oil combined hydrogenation process method. The method comprises the steps of cutting a diesel raw material into light components and heavy components, enabling the light components to enter a liquid phase hydrogenation reactor for reaction, enabling the heavy components to enter a gas phase circulation hydrogenation reactor for reaction, separating a gas phase hydrogenation product (or the gas phase hydrogenation product and the liquid phase hydrogenation product), enabling the obtained liquid to be taken as a product to be directly discharged out of a device or to be circulated to the liquid phase hydrogenation reactor, and enabling the liquid phase hydrogenation product to be taken as the product to be discharged out of the device. According to the method, raw oil is cut and then respectively subjected to hydrotreating, sulfur-containing compounds and polycyclic aromatic hydrocarbons which are difficult to remove are mainly in heavy components, the heavy components enter a gas phase circulation hydrogenation reactor to react, in order to remove sulfides and polycyclic aromatic hydrocarbons, the reaction pressure and temperature need to be increased, the hydrogen-oil ratio needs to be increased, a large amount of hydrogen and energy are consumed, and the increase of the temperature is not used for hydrogenation saturation of the polycyclic aromatic hydrocarbons. Meanwhile, the method cuts the diesel raw material into light and heavy components, needs to add fractionation equipment, increases the equipment investment cost, performs liquid phase hydrogenation reaction on the light components, reduces the temperature of the cut light components to convert the light components into liquid phase, increases the energy consumption and causes energy waste.
CN 102311794B discloses a diesel hydrogenation process method. The method comprises the following steps: the diesel raw material enters a conventional gas phase circulation hydrogenation reactor for reaction, and the effluent is subjected to gas-liquid separation; after the obtained liquid phase is saturated and dissolved with hydrogen, the liquid phase enters a liquid phase circulating hydrogenation reactor for hydrogenation, and liquid phase circulating oil is circulated back to the inlet of the liquid phase hydrogenation reactor after passing through a dehydrosulfurization reactor; the raw oil is pretreated by gas-phase circular hydrogenation, and the sulfur content in the generated oil is reduced to below 500 mu g/g. Wherein the process conditions of the conventional gas phase circulation hydrogenation reactor are as follows: the reaction temperature is 280-400 ℃, the reaction pressure is 3.0-10.0 MPa, and the liquid hourly space velocity is 1.0h-1~6.0h-1The volume ratio of hydrogen to oil is 100-1000; the process conditions of the liquid phase circulation hydrogenation reactor are as follows: the reaction temperature is 300-420 ℃, the reaction pressure is 3.0-10.0 MPa, and the liquid hourly space velocity is 1.0-6.0 h-1. In the method, most of sulfur-containing compounds in raw oil are removed in a gas-phase circulating hydrogenation reactor, and macromolecular sulfur-containing compounds and polycyclic aromatic hydrocarbons which are difficult to remove are removed in a liquid-phase circulating hydrogenation reactor.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for reducing polycyclic aromatic hydrocarbon in diesel oil. The method can produce the high-quality diesel oil blending component with ultra-low sulfur and low polycyclic aromatic hydrocarbon by using the poor diesel oil mixed oil as the raw material under the conditions of simple process, low energy consumption and low cost through the matching of the catalyst and the process flow.
The method for reducing polycyclic aromatic hydrocarbon in diesel oil comprises the following steps: the diesel raw material enters a flash evaporation zone of a fixed bed reactor, the gas-phase components after flash evaporation enter a first hydrogenation reaction zone upwards for hydrogenation reaction, and the reaction product is discharged from the top of the reactor; the liquid phase components after flash evaporation downwards enter a second hydrogenation reaction zone for hydrodesulfurization and denitrification reaction, the effluent of the second hydrogenation reaction zone downwards enters a third hydrogenation reaction zone for polycyclic aromatic hydrocarbon hydrogenation saturation reaction, and the product of the third hydrogenation reaction zone is discharged from the bottom of the reactor; wherein hydrogen enters from the second hydrogenation reaction zone and the third hydrogenation reaction zone of the reactor; the second hydrogenation reaction zone is filled with a semi-vulcanized molded phase hydrogenation catalyst which comprises VIB group metal sulfide, VIII group metal oxide and Al2O3And an auxiliary agent, wherein the VIB group metal is preferably Mo and/or W, the VIII group metal is preferably Co and/or Ni, and the auxiliary agent is one or more of B, P, F, Mg, Zr or Si; based on the weight of the bulk phase hydrofining catalyst, the content of VIB group metal sulfide is 40% -70%, preferably 50% -65%, the content of VIII group metal oxide is 3% -25%, preferably 3% -15%, the content of the auxiliary agent is 3% -15%, preferably 3% -10%, calculated by oxide, Al2O3From 24% to 54%, preferably from 25% to 42%; the group VIB metal sulfide is distributed in a bulk phase and a surface phase of the catalyst, the weight ratio of the group VIB metal sulfide in the surface phase to the group VIB metal sulfide in the bulk phase is 2.5: 1-7.5: 1, and the group VIII metal oxide is distributed in the surface phase of the catalyst; the bulk phase VIB group metal sulfide is characterized by SEM energy spectrum and TEM electron microscope, and the surface phase VIB group metal sulfide and VIII group metal oxide are analyzed by XPS energy spectrum; and a noble metal hydrogenation catalyst is filled in the third hydrogenation reaction zone.
In the method, the diesel raw material is one or more of straight-run diesel, catalytic cracking diesel, coking diesel and boiling bed residual oil hydrogenated diesel; the distillation range of the diesel raw material is 220-400 ℃, the sulfur content is no more than 15000 mu g/g, the nitrogen content is no more than 1000 mu g/g, and the cetane number is no less than 35.
In the method, the flash evaporation zone is used for separating light fraction below 280 ℃ from the raw material and enabling the light fraction to enter a first hydrogenation reaction zone as a gas-phase component, and the heavy fraction above 280 ℃ enters a second hydrogenation reaction zone as a liquid-phase component.
In the method, the first hydrogenation reaction zone is used for the desulfurization and denitrification reaction of gas phase components (light fraction), and Mo-Ni and/or Mo-Co type light distillate oil hydrogenation catalysts, such as FH-40 series light distillate oil hydrogenation special catalysts developed by FRIPP, are filled in the first hydrogenation reaction zone. The process conditions of the first hydrogenation reaction zone are as follows: the pressure is 1.0-12.0 MPa, preferably 2.0-8.0 MPa, wherein the proportion of hydrogen partial pressure in the total pressure is preferably 40-70%; the volume airspeed is 0.1-10.0 h-1Preferably 0.5 to 6.0 hours-1(ii) a The feeding temperature is 150-330 ℃, preferably 180-300 ℃; hydrogen-oil volume ratio 10: 1-800: 1, preferably 100: 1-400: 1.
in the method, the second hydrogenation reaction zone is used for carrying out deep desulfurization and denitrification on liquid phase components (heavy fractions). The process conditions of the second hydrogenation reaction zone are as follows: the pressure is 1.0-12.0 MPa, preferably 6.0-10.0 MPa, wherein the hydrogen partial pressure accounts for 50-90% of the total pressure; the volume airspeed is 0.1-10.0 h-1Preferably 0.5 to 3.0 hours-1(ii) a The reaction temperature is 200-400 ℃, preferably 280-350 ℃; hydrogen-oil volume ratio 10: 1-800: 1, preferably 100: 1-400: 1.
the preparation method of the semi-vulcanized bulk phase hydrogenation catalyst comprises the following steps:
(1) preparing a mixed solution A containing a VIB group metal and an aluminum source, and carrying out parallel flow gelling reaction on the mixed solution A and a precipitator to generate slurry I containing the VIB group metal and aluminum precipitates;
(2) pulping and uniformly mixing the slurry I obtained in the step (1) and an auxiliary agent precursor, filtering, washing, drying and forming to obtain a catalyst precursor I;
(3) drying and roasting the catalyst precursor I obtained in the step (2), and then carrying out vulcanization treatment to obtain a catalyst precursor II containing a VIB group metal sulfide;
(4) and (3) impregnating the catalyst precursor II obtained in the step (3) with an impregnating solution containing a VIII group metal, and then drying and roasting the impregnated catalyst precursor II in an inert atmosphere to obtain a semi-vulcanized bulk phase hydrogenation catalyst.
In the mixed solution A in the step (1), the weight concentration of the VIB group metal calculated by oxide is 10-100 g/L, preferably 20-90 g/L, and Al is Al2O3The weight concentration is 2-60 g/L, preferably 8-40 g/L. When preparing the mixed solution A, one or more of phosphate or ammonium salt of VIB group metal is generally adopted; the aluminum source can be one or more of aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum acetate and the like.
The precipitator in the step (1) is one or more of sodium carbonate, sodium bicarbonate, ammonia water, sodium hydroxide, potassium carbonate or potassium bicarbonate water solution, and the concentration of the precipitator is 0.5-3.0 mol/L.
In the step (1), the temperature of the parallel-flow gelling reaction is 30-90 ℃, and preferably 40-80 ℃. And controlling the pH value to be 6.0-11.0, preferably 7.0-9.0, and controlling the gelling time to be 0.2-4.0 hours, preferably 0.5-3.0 hours when the gel is formed in a parallel flow mode.
In the step (2), the precursor of the auxiliary agent is one or more of boric acid, phosphoric acid, ammonium hydrofluoric acid, magnesium nitrate, water glass or zirconium nitrate, and the concentration of the aqueous solution of the auxiliary agent is 1.0-3.0 mol/L; and after the auxiliary agent and the slurry I are uniformly mixed, controlling the pH value to be 7.0-9.0.
The washing, drying and shaping of step (2) may be carried out by methods conventional in the art. The washing is generally carried out by washing with deionized water or a solution containing decomposable salts (such as ammonium acetate, ammonium chloride, ammonium nitrate, etc.) until the solution is neutral. The drying conditions were as follows: drying the mixture for 3 to 6 hours at a temperature of between 90 and 200 ℃. In the forming process, conventional forming aids, such as one or more of peptizers, extrusion aids, and the like, can be added as required. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and the like, the extrusion aid is a substance which is beneficial to extrusion forming, such as one or more of sesbania powder, carbon black, graphite powder, citric acid and the like, and the amount of the extrusion aid accounts for 1-10 wt% of the total dry basis of the materials.
The drying conditions in the step (3) are as follows: the drying temperature is 90-200 ℃, the drying time is 3-6 hours, and the roasting conditions are as follows: the roasting temperature is 400-800 ℃, and the roasting time is 3-6 hours.
The vulcanization treatment in step (3) is well known to those skilled in the art, and usually adopts dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or two of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide; the vulcanization pressure is 3.2-6.4 MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 h.
The second step of (4)
The preparation method of the dipping solution of the group metal is well known to those skilled in the art, for example, nitrate, acetate, sulfate solution and the like are generally adopted, the mass concentration of the dipping solution is 0.1 g/mL-1.0 g/mL, an equal-volume dipping mode can be adopted, and the second step is
The group metals are preferably Ni and/or Co.
The inert atmosphere in the step (4) is N2And an inert gas; the drying temperature is 20-90 ℃, and the drying time is 4-16 hours; the roasting temperature is 200-500 ℃, and the roasting time is 2-5 hours.
In the method, the third hydrogenation reaction zone is used for carrying out polycyclic aromatic hydrocarbon hydrogenation saturation reaction of heavy fractions, and the noble metal hydrogenation catalyst in the third hydrogenation reaction zone comprises a carrier, an active component and an auxiliary agent, wherein the carrier is alumina, the active component is Pt and/or Pd and the auxiliary agent is Ni and/or Co based on the weight of the carrier. Based on the weight of the catalyst, the active component is 0.05 to 5.0 weight percent, preferably 0.1 to 0.3 weight percent, the auxiliary agent is 1 to 10 weight percent, preferably 3 to 6 weight percent, and the balance is the carrier. The specific surface area of the catalyst is 300-400m2Per g, pore volume of 0.4-0.6cm3The crushing strength is 150-250N/cm. The noble metal catalyst may be a commercially available product, if necessary, or may be prepared by a method conventional in the art. The process conditions of the third hydrogenation reaction zone are as follows: the pressure is 1.0-12.0 MPa, preferably 4.0-6.0 MPa, and the pure solution is obtainedIn the phase reaction zone, the volume ratio of standard hydrogen to oil is 2-50, preferably 10-30; the volume airspeed is 0.1-8.0 h-1Preferably 0.5 to 6.0 hours-1(ii) a The reaction temperature is 150-300 ℃, and preferably 180-250 ℃; hydrogen-oil volume ratio 10: 1-800: 1, preferably 100: 1-400: 1.
compared with the prior diesel hydrogenation technology, the method provided by the invention effectively reduces the content of polycyclic aromatic hydrocarbon in the diesel and produces high-quality diesel. After raw oil enters a flash evaporation zone, light distillate enters a first hydrogenation reaction zone, and basic nitrides such as mercaptan, thioether and pyridine in the light distillate are subjected to hydrogenation removal reaction, so that the occupation of the compounds on the hydrogenation reaction active site of the polycyclic aromatic hydrocarbon can be reduced. After raw oil enters a flash evaporation zone, heavy fraction enters a second hydrogenation reaction zone, macromolecular sulfur-containing compounds and nitrogen-containing compounds are subjected to hydrogenation removal reaction in the reaction zone, the heat release in the reaction process is serious, the high-activity semi-sulfurized hydrogenation catalyst can be subjected to hydrodesulfurization and denitrification at a lower reaction temperature, and in addition, the reaction zone is a gas-liquid countercurrent reaction environment, so that heat generated by the reaction can be taken away in time, and the macromolecular compounds such as polycyclic aromatic hydrocarbon and the like are prevented from coking reaction on the catalyst in a high-temperature environment; meanwhile, the semi-vulcanized state bulk phase catalyst in the second hydrogenation reaction zone has high activity site content of the second type of active center with high hydrogenation activity, and can hydrogenate macromolecular compounds in time to prevent the macromolecular compounds from coking on the surface of the catalyst; the catalyst does not need to be subjected to sulfurization treatment, the metal oxide which is difficult to sulfurize is sulfurized in advance, the hydrogen sulfide generated along with the reaction product can gradually sulfurize the metal oxide which is easy to sulfurize in the semi-sulfurized catalyst, the temperature runaway caused by overhigh activity in the initial reaction stage can be weakened, and meanwhile, the semi-sulfurized catalyst can keep higher reaction activity. In addition, in the initial reaction stage, sulfides (mainly unremoved sulfides, such as benzothiophene) in the product of the second reaction zone can passivate the noble metal catalyst in the third reaction zone, so that the noble metal catalyst is prevented from being too high in activity in the initial reaction stage to cause temperature runaway; with the improvement of the activity of the catalyst in the second reaction zone, the sulfide in the product in the second reaction zone is reduced, the noble metal catalyst cannot be continuously passivated, and the process condition can be matched with the activity of the noble metal catalyst. In addition, the macromolecular sulfur-containing compound and the macromolecular nitrogen-containing compound need to be removed after hydrogenation, and form a competitive reaction with the polycyclic aromatic hydrocarbon hydrogenation saturation, the removal of the sulfur-containing compound and the nitrogen-containing compound in the reaction zone is favorable for the hydrogenation saturation of the polycyclic aromatic hydrocarbon, and simultaneously the noble metal catalyst in the hydrogenation reaction zone III is protected. The third hydrogenation reaction zone has low reaction temperature and high saturated hydrogen content, is favorable for the hydrogenation saturation of the polycyclic aromatic hydrocarbon, and the noble metal catalyst has high hydrogenation activity on the polycyclic aromatic hydrocarbon, thereby preventing the over saturation of the polycyclic aromatic hydrocarbon and inhibiting the reduction of the condensation point of the diesel oil product.
Drawings
FIG. 1 is a schematic diagram of the process for reducing diesel polycyclic aromatic hydrocarbons of the present invention.
In the figure: 1-raw material, 2-hydrogen, 3 a first hydrogenation reaction zone, 4-a flash evaporation zone, 5-a second hydrogenation reaction zone, 6-a third hydrogenation reaction zone, 7-low-sulfur low-nitrogen light diesel oil component, 8-low-sulfur low-nitrogen low-polycyclic aromatic hydrocarbon heavy diesel oil component and 9-low-polycyclic aromatic hydrocarbon high-quality diesel oil.
Detailed Description
The invention is described in detail below with reference to the figures and examples, but the invention is not limited thereby.
The preparation method of the noble metal hydrogenation catalyst comprises the following steps:
(1) and (2) dipping the solution containing the palladium compound and/or the platinum compound into an alumina carrier, and drying and roasting to obtain the catalyst precursor.
(2) And (2) soaking the solution containing the auxiliary agent into the catalyst precursor prepared in the step (1), and drying, roasting and reducing to obtain the catalyst.
In the preparation method of the noble metal hydrogenation catalyst, the palladium-containing compound in the step (1) is selected from palladium chloride, palladium nitrate, palladium acetate, sodium tetrachloropalladate, palladium dichlorotetraammine, palladium trifluoroacetate, palladium diacetylacetonate or palladium hexafluoroacetylacetonate, and the concentration of the solution is 0.001-0.5g/mL calculated by palladium element.
In the preparation method of the noble metal hydrogenation catalyst, the platinum-containing compound in the step (1) is selected from chloroplatinic acid, dichlorotetraammineplatinum, ammonium chloroplatinate, platinum trichloride, platinum tetrachloride, dicarbonyl platinum dichloride, dinitrodiaminoplatinum or sodium tetranitroplatinate, and the concentration of the solution is 0.001-0.5g/mL calculated by platinum element.
In the preparation method of the noble metal hydrogenation catalyst, the drying conditions in the step (1) are as follows: drying at 80-150 ℃ for 3-6h, wherein the roasting condition is as follows: roasting at 400-600 ℃ for 3-8 h.
In the preparation method of the noble metal hydrogenation catalyst, the assistant solution in the step (2) is one or more of cobalt nitrate, cobalt acetate, nickel nitrate and nickel acetate, and the concentration of the assistant solution is 0.01-1.0 g/mL calculated by oxide.
In the preparation method of the noble metal hydrogenation catalyst, the drying temperature in the step (2) is 20-90 ℃, and the drying time is 4-16 hours; the roasting temperature is 200-500 ℃, and the roasting time is 2-5 hours; the reduction treatment conditions are as follows: reducing for 3-10h at 600 ℃ and 0.1-3.0MPa in hydrogen atmosphere.
A noble metal catalyst was prepared in example 1:
example 1
Dissolving chloroplatinic acid into deionized water, wherein the concentration of platinum is 0.002g/mL, soaking the chloroplatinic acid solution into an alumina carrier in the same volume, drying at 120 ℃ for 6h, and then roasting at 450 ℃ for 5 h.
Dissolving nickel nitrate into deionized water, wherein the concentration of nickel oxide is 0.02g/mL, soaking a nickel nitrate solution in the catalyst precursor in the same volume, drying at 90 ℃ for 5h, roasting at 250 ℃ for 3h, and reducing at 400 ℃ and 3.0MPa in a hydrogen atmosphere for 6h to obtain the noble metal catalyst C3-1, wherein the content of metal platinum is 0.25% and the content of nickel is 3.5%.
Semi-sulfided catalysts were prepared in examples 2-5:
example 2
Dissolving ammonium metatungstate and aluminum chloride in deionized water to prepare a mixed solution A, wherein WO is contained in the mixed solution A3Has a weight concentration of 80g/L and Al2O3The weight concentration of (B) is 50 g/L. To a concentration of 1.0mol/LAnd slowly adding sodium hydroxide into 1L of the solution A under stirring, keeping the gelling temperature at 75 ℃, controlling the pH value at 7-8 after finishing gelling, and controlling the gelling time at 60 minutes to generate a tungsten-aluminum-containing precipitate slurry I.
And (3) uniformly mixing 160mL of 1.0mol/L magnesium nitrate solution with the slurry I, then adjusting the pH value to 7-8 by using ammonia water, then washing the mixture for three times by using deionized water, filtering the mixture, and drying the filtered mixture for 5 hours at 110 ℃ to obtain mixed powder. Then 150g of mixed powder is uniformly mixed with 5g of nitric acid, 5g of starch and 60g of deionized water, then the mixture is kneaded, extruded into strips and molded, dried for 3 hours at 100 ℃, roasted for 3 hours at 550 ℃, and then the mixture is roasted for 3 hours by adopting the mixed powder containing 1.5 percent of H2Sulfurizing S hydrogen at 320 deg.C under 6.0MPa for 8 hr, and adding N2And cooling to room temperature in the atmosphere to obtain a catalyst precursor II.
42.2g of Ni (NO)3)2•6H2Dissolving O into 50mL of deionized water, soaking the solution into a precursor II in equal volume, and then adding the solution into N2Drying at 80 ℃ for 4h in the atmosphere, and roasting at 330 ℃ for 3h to obtain the catalyst C2-1.
Example 3
Dissolving ammonium molybdate and aluminum sulfate in deionized water to prepare a mixed solution A, wherein MoO is contained in the mixed solution A3Has a weight concentration of 80g/L and Al2O3The weight concentration of (B) is 50 g/L. Slowly adding sodium hydroxide with the concentration of 1.0mol/L into 1L of the solution A under stirring, keeping the gelling temperature at 70 ℃, controlling the pH value at 7-8 after finishing gelling, and controlling the gelling time at 90 minutes to generate molybdenum-aluminum-containing precipitate slurry I.
And (3) uniformly mixing 100mL of 1.0mol/L zirconium nitrate solution with the slurry I, then adjusting the pH value to 7-8 by using ammonia water, then washing the mixture for three times by using deionized water, filtering the mixture, and drying the filtered mixture for 4 hours at 120 ℃ to obtain mixed powder. Then 150g of mixed powder is uniformly mixed with 10g of phosphoric acid, 5g of starch and 60g of deionized water, then the mixture is kneaded, extruded into strips and molded, dried for 3 hours at 110 ℃, roasted for 2 hours at 650 ℃, and then the mixture is roasted for 2 hours by adopting the mixed powder containing 1.5 percent of H2Sulfurizing S hydrogen at 330 deg.C under 5.6MPa for 6 hr, and adding N2Cooling to room temperature in an atmosphere to obtainAnd (3) a catalyst precursor II.
42.2g of Ni (NO)3)2•6H2Dissolving O into 50mL of deionized water, soaking the solution into a precursor II in equal volume, and then adding the solution into N2Drying at 100 ℃ for 4h in the atmosphere, and roasting at 300 ℃ for 3h to obtain the catalyst C2-2.
Example 4
Dissolving ammonium molybdate and aluminum sulfate in deionized water to prepare a mixed solution A, wherein MoO is contained in the mixed solution A3Has a weight concentration of 80g/L and Al2O3The weight concentration of (B) is 50 g/L. Slowly adding sodium hydroxide with the concentration of 1.0mol/L into 1L of the solution A under stirring, keeping the gelling temperature at 70 ℃, controlling the pH value at 7-8 after finishing gelling, and controlling the gelling time at 90 minutes to generate molybdenum-aluminum-containing precipitate slurry I.
And (3) uniformly mixing 160mL of 1.0mol/L zirconium nitrate solution with the slurry I, then adjusting the pH value to 7-8 with ammonia water, then washing with deionized water for three times, filtering, and drying at 100 ℃ for 10 hours to obtain mixed powder. And then 150g of the mixed powder is uniformly mixed with 10g of phosphoric acid, 5g of starch and 60g of deionized water, and then the mixture is kneaded, extruded into strips and formed, dried for 3 hours at the temperature of 110 ℃ and roasted for 2 hours at the temperature of 550 ℃. Then using 3wt% CS2Carrying out vulcanization treatment on the aviation kerosene at the airspeed of 1.0h-1Hydrogen-oil volume ratio of 500:1, under the operating pressure of 6.0MPa, sulfurizing for 8h, then adding N2And cooling to room temperature in the atmosphere to obtain a catalyst precursor II.
32.2g of Co (NO)3)2•6H2Dissolving O into 50mL of deionized water, soaking the solution into a precursor II in equal volume, and then adding the solution into N2Drying at 100 ℃ for 4h in the atmosphere, and roasting at 300 ℃ for 4h to obtain the catalyst C2-3.
Example 5
Dissolving ammonium metatungstate and aluminum chloride in deionized water to prepare a mixed solution A, wherein WO is contained in the mixed solution A3Has a weight concentration of 80g/L and Al2O3The weight concentration of (B) is 50 g/L. Slowly adding sodium hydroxide with the concentration of 1.0mol/L into 1L of the solution A under stirring, keeping the gelling temperature at 70 ℃, controlling the pH value at 7-8 when the gelling is finished, controlling the gelling time at 60 minutes,and generating a tungsten and aluminum containing precipitate slurry I.
And (3) uniformly mixing 160mL of 1.0mol/L magnesium nitrate solution with the slurry I, then adjusting the pH value to 7-8 by using ammonia water, then washing the mixture for three times by using deionized water, filtering the mixture, and drying the filtered mixture for 5 hours at 110 ℃ to obtain mixed powder. Then 150g of mixed powder is uniformly mixed with 5g of nitric acid, 5g of starch and 60g of deionized water, then the mixture is kneaded, extruded into strips and molded, dried for 3 hours at 120 ℃, roasted for 3 hours at 550 ℃, and then the mixture is roasted for 3 hours by adopting the mixed powder containing 1.5 percent of H2Sulfurizing S hydrogen at 340 deg.C under 6.0MPa for 6 hr, and adding N2And cooling to room temperature in the atmosphere to obtain a catalyst precursor II.
15.6g of Ni (NO)3)2•6H2O and 20.9g of Co (NO)3)2•6H2Dissolving O into 50mL of deionized water, soaking the solution into a precursor II in equal volume, and then adding the solution into N2Drying at 100 ℃ for 4h in the atmosphere, and roasting at 250 ℃ for 3h to obtain the catalyst C2-4.
Comparative example 1
Dissolving ammonium metatungstate, nickel nitrate and aluminum chloride in deionized water to prepare a mixed solution A, wherein WO is contained in the mixed solution A3Has a weight concentration of 80g/L, a weight concentration of NiO of 8g/L and Al2O3The weight concentration of (B) is 50 g/L. Slowly adding sodium hydroxide with the concentration of 1.0mol/L into 1L of the solution A under stirring, keeping the gelling temperature at 75 ℃, controlling the pH value at 7-8 after finishing gelling, and controlling the gelling time at 60 minutes to generate a precipitate slurry I containing tungsten and aluminum.
And (3) uniformly mixing 160mL of 1.0mol/L magnesium nitrate solution with the slurry I, then adjusting the pH value to 7-8 by using ammonia water, then washing the mixture for three times by using deionized water, filtering the mixture, and drying the filtered mixture for 5 hours at 110 ℃ to obtain mixed powder. And then, uniformly mixing 150g of the mixed powder with 5g of nitric acid, 5g of starch and 60g of deionized water, kneading, extruding into strips, forming, drying at 110 ℃ for 3h, and roasting at 550 ℃ for 3h to obtain the catalyst. Then using a catalyst containing 1.5% H2Sulfurizing S hydrogen at 340 deg.C under 5.0MPa for 8 hr, and adding N2And cooling to room temperature in the atmosphere to obtain the catalyst DC-1.
The method for reducing polycyclic aromatic hydrocarbon in diesel oil of the invention is illustrated by the accompanying figure 1: the reaction raw material 1 enters a flash evaporation area 4 under certain temperature and pressure conditions, and is separated into a gas phase and a liquid phase in the flash evaporation area 4. The vapor phase flows upward into the first hydrogenation reaction zone 3 and the liquid phase flows downward into the second hydrogenation reaction zone 5. Hydrogen 2 enters the reactor between the second hydrogenation reaction zone 5 and the third hydrogenation reaction zone 6, and after the hydrogen 2 is mixed and contacted with the liquid phase material flowing out downwards in the second hydrogenation reaction zone 5, the excessive hydrogen continues to flow upwards to enter the second hydrogenation reaction zone 5, and the dissolved liquid phase material carrying the hydrogen flows downwards to enter the third hydrogenation reaction zone 6.
The first hydrogenation reaction zone 3 is subjected to gas phase reaction, mainly subjected to hydrodesulfurization and hydrodenitrogenation reactions of the light diesel oil component, and a low-sulfur low-nitrogen hydrogen diesel oil component 7 is generated. The second hydrogenation reaction zone 5 has gas-liquid two-phase reaction, the liquid phase is heavy diesel oil fraction flowing downwards, the gas phase is hydrogen flowing upwards, and the gas-liquid reverse contact has deep hydrodesulfurization and denitrification reaction. Hydrogen sulfide and low molecular hydrocarbon generated by the reaction flow upward along with the gas phase material flow, enter the first hydrogenation reaction zone 3 and then flow out of the device from the top of the reactor. The liquid phase material flow after hydrogenation flows downwards to enter a third hydrogenation reaction zone 6, and polycyclic aromatic hydrocarbon liquid phase hydrogenation reaction is carried out to generate a low polycyclic aromatic hydrocarbon heavy diesel oil component 8. The low-sulfur low-nitrogen hydrogen diesel oil component 7 and the low polycyclic aromatic hydrocarbon heavy diesel oil component 8 are mixed to generate the low polycyclic aromatic hydrocarbon high-quality diesel oil.
Examples 6 to 10
In the embodiment, the first, second and third hydrogenation reaction zones are all provided with a catalyst bed layer. The first hydrogenation reaction zone was charged with Ni-Mo type hydrofining catalyst C1-1, the second hydrogenation reaction zone was charged with one of the semi-sulfided catalysts C2-1 to C2-4 prepared in examples 2-5, and the third hydrogenation reaction zone was charged with the noble metal catalyst C3-1 prepared in example 1. The filling ratio of the first catalyst bed layer, the second catalyst bed layer and the third catalyst bed layer is 3:5:2, the inlet temperature of the raw oil is 350 ℃, and the temperature of the reaction bed layer in each reaction zone in the reaction process is stable and controllable. The properties of the catalyst are shown in table 1, the raw oil is the mixed oil of straight diesel, catalytic diesel and coke diesel, and the proportion of the three is 40: 30: 30, the properties of the raw oil are shown in Table 2, and the reaction process conditions and results are shown in Table 3.
Comparative example 2
The first, second and third hydrogenation reaction zones of this comparative example are all provided with a catalyst bed. The first hydrogenation reaction zone was charged with Ni-Mo type hydrofining catalyst C1-1, the second hydrogenation reaction zone was charged with catalyst DC-1 prepared in comparative example 1, and the third hydrogenation reaction zone was charged with noble metal catalyst C3-1 prepared in example 1. The filling ratio of the first catalyst bed layer, the second catalyst bed layer and the third catalyst bed layer is 3:5:2, the inlet temperature of the raw oil is 350 ℃, and the temperature of the reaction bed layer in each reaction zone in the reaction process is stable and controllable. The properties of the catalyst are shown in Table 1, the properties of the raw oil are the same as those of the examples, and the reaction conditions and results are shown in Table 3.
Comparative example 3
The process method for reducing polycyclic aromatic hydrocarbon in diesel oil by adopting the prior art is characterized in that raw materials are sequentially introduced into a hydrotreating reactor (a first hydrogenation reaction zone is filled with a catalyst C1-1), a hydrodesulfurization and denitrification reaction zone (a second hydrogenation reaction zone is filled with a catalyst C2-1) and a hydrodearomatization reaction zone (a third hydrogenation reaction zone is filled with a catalyst C3-1), and then the diesel oil blending component is obtained by fractionation. Hydrogen enters at the bottom of the third hydrogenation reaction zone. The filling ratio of the first catalyst bed layer, the second catalyst bed layer and the third catalyst bed layer is 3:5:2, the inlet temperature of the raw oil is 350 ℃, and the temperature of the reaction bed layer in each reaction zone in the reaction process is stable and controllable. The properties of the raw oil are as in example, and the reaction conditions and results are shown in Table 3.
TABLE 1 physicochemical Properties of the catalyst
| Catalyst numbering | C2-1 | C2-2 | C2-3 | C2-4 | DC-1 | C1-1 | C3-1 |
| Tungsten sulfide content, wt% | 53.2 | ______ | ______ | 56 | 53.6 | ______ | ______ |
| Molybdenum sulfide content, wt% | ______ | 54.6 | 52.3 | ______ | ______ | ______ | ______ |
| Watch phase IWPhase/bulk phase IW | 4.42 | ______ | ______ | 3.76 | 2.16 | ______ | ______ |
| Watch phase IMoPhase/bulk phase IMo | ______ | 4.56 | 5.51 | ______ | ______ | ______ | ______ |
| NiO content, wt% | 5.3 | 5.7 | ______ | 2.1 | ______ | 5.2 | ______ |
| CoO content, wt% | ______ | ______ | 4.8 | 3.4 | ______ | ______ | ______ |
| MoO3Content, wt% | ______ | ______ | ______ | ______ | ______ | 16.8 | ______ |
| Pt content, wt% | ______ | ______ | ______ | ______ | ______ | ______ | 0.25 |
| Ni content, wt% | ______ | ______ | ______ | ______ | ______ | ______ | 3.5 |
| Nickel sulfide content, wt% | ______ | ______ | ______ | ______ | 6.3 | ______ | ______ |
TABLE 2 Properties of the feed oils
| Oil quality | |
| Density (20 ℃ C.), g.cm-3 | 0.86 |
| Range of distillation range, deg.C | 220~380 |
| S,μg·g-1 | 14800 |
| N,μg·g-1 | 885 |
| Polycyclic aromatic hydrocarbon, m% | 22.5 |
TABLE 3 hydrogenation process conditions and results
| Example 6 | Example 7 | Example 8 | Example 9 | Comparative example 2 | Comparative example 3 | |
| Partial pressure of hydrogen, MPa | ||||||
| Inlet port | 6.5 | 6.5 | 6.5 | 6.5 | 6.5 | |
| The first hydrogenation reaction zone | 3.5 | 4.0 | 4.0 | 4.0 | 4.0 | 6.5 |
| Second hydrogenation reaction zone | 6.0 | 6.0 | 6.0 | 6.0 | 6.0 | 6.5 |
| Third hydrogenation reaction zone | Standard hydrogen-to-oil ratio of 25 | Standard hydrogen-to-oil ratio of 25 | Standard hydrogen-to-oil ratio of 25 | Standard hydrogen-to-oil ratio of 25 | Standard hydrogen-to-oil ratio of 25 | 6.5 |
| Volumetric space velocity h-1 | ||||||
| The first hydrogenation reaction zone | 4.5 | 4.5 | 4.5 | 4.5 | 4.5 | 3.2 |
| Second hydrogenation reaction zone | 2.5 | 2.5 | 2.5 | 2.0 | 2.0 | 2.5 |
| Third hydrogenation reaction zone | 5.5 | 5.5 | 5.5 | 5.5 | 5.5 | 4.5 |
| Hydrogen to oil ratio, v/v | 400 | 400 | 400 | 400 | 400 | 400 |
| Reaction temperature of | ||||||
| The first hydrogenation reaction zone | 250 | 250 | 270 | 270 | 270 | 320 |
| Second hydrogenation reaction zone | 355 | 355 | 360 | 360 | 380 | 380 |
| Third hydrogenation reaction zone | 200 | 200 | 210 | 210 | 230 | 340 |
| Diesel oil | ||||||
| Sulfur,. mu.g/g | 8.2 | 7.2 | 3.6 | 2.3 | 6.9 | 9.8 |
| Nitrogen,. mu.g/g | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Polycyclic aromatic hydrocarbon, m% | 6.7 | 5.8 | 4.9 | 3.8 | 6.2 | 8.6 |
As can be seen from Table 3, the present invention can produce a high quality diesel component with low polycyclic aromatic hydrocarbon under the conditions of simple flow and mild conditions, compared with comparative example 2 and comparative example 3.
Claims (21)
1. The method for reducing polycyclic aromatic hydrocarbon in diesel oil is characterized by comprising the following steps: the diesel raw material enters a flash evaporation zone of a fixed bed reactor, the gas-phase components after flash evaporation enter a first hydrogenation reaction zone upwards for hydrogenation reaction, and the reaction product is discharged from the top of the reactor; the liquid phase components after flash evaporation downwards enter a second hydrogenation reaction zone for hydrodesulfurization and denitrification reaction, the effluent of the second hydrogenation reaction zone downwards enters a third hydrogenation reaction zone for polycyclic aromatic hydrocarbon hydrogenation saturation reaction, and the product of the third hydrogenation reaction zone is discharged from the bottom of the reactor; wherein hydrogen enters from the second hydrogenation reaction zone and the third hydrogenation reaction zone of the reactor; the second hydrogenation reaction zone is filled with a semi-vulcanized molded body phase hydrogenation catalyst; and a noble metal hydrogenation catalyst is filled in the third hydrogenation reaction zone.
2. The method of claim 1, wherein: a semi-sulfided bulk phase hydrogenation catalyst.
3. Comprises a VIB group metal sulfide, a VIII group metal oxide and Al2O3And an auxiliary agent; based on the weight of the bulk phase hydrofining catalyst, the content of VIB group metal sulfide is 40-70%, the content of VIII group metal oxide is 3-25%, the content of auxiliary agent is 3-15% calculated by oxide, and Al is2O3Is 24% -54%.
4. The method of claim 2, wherein: the group VIB metal sulfide is distributed in a bulk phase and a surface phase of the catalyst, the weight ratio of the group VIB metal sulfide in the surface phase to the group VIB metal sulfide in the bulk phase is 2.5: 1-7.5: 1, and the group VIII metal oxide is distributed in the surface phase of the catalyst; the bulk phase of group VIB metal sulfide by SEM energy spectrum and TEM electron microscope characterization, surface phase of group VIB metal sulfide and group VIII metal oxide by XPS energy spectrum analysis.
5. The method of claim 2, wherein: wherein the VIB group metal is Mo and/or W, the VIII group metal is Co and/or Ni, and the auxiliary agent is one or more of B, P, F, Mg, Zr or Si.
6. The method of claim 1, wherein: the diesel oil raw material is one or more of straight-run diesel oil, catalytic cracking diesel oil, coking diesel oil and boiling bed residual oil hydrogenated diesel oil.
7. The method of claim 1, wherein: the distillation range of the diesel raw material is 220-400 ℃, the sulfur content is no more than 15000 mu g/g, the nitrogen content is no more than 1000 mu g/g, and the cetane number is no less than 35.
8. The method of claim 1, wherein: the flash evaporation zone is used for separating light fraction below 280 ℃ from the raw material and enabling the light fraction to enter a first hydrogenation reaction zone as a gas-phase component, and the heavy fraction above 280 ℃ enters a second hydrogenation reaction zone as a liquid-phase component.
9. The method of claim 1, wherein: the first hydrogenation reaction zone is used for gas phase components to generate desulfurization and denitrification reaction, and Mo-Ni and/or Mo-Co type light distillate oil hydrogenation catalysts are filled in the first hydrogenation reaction zone; the process conditions of the first hydrogenation reaction zone are as follows: the pressure is 1.0-12.0 MPa, wherein the hydrogen partial pressure accounts for 40-70% of the total pressure; the volume airspeed is 0.1-10.0 h-1Feeding temperature is 150-330 ℃, and the volume ratio of hydrogen to oil is 10: 1-800: 1.
10. the method of claim 1, wherein: the second hydrogenation reaction zone is used for carrying out deep desulfurization and denitrification on liquid-phase components; the process conditions of the second hydrogenation reaction zone are as follows: the pressure is 1.0-12.0 MPa, wherein the proportion of hydrogen partial pressure in the total pressure is preferably 50-90%; the volume airspeed is 0.1-10.0 h-1The reaction temperature is 200-400 ℃, and the volume ratio of hydrogen to oil is 10: 1-800: 1.
11. the method of claim 1, wherein: the preparation method of the semi-vulcanized bulk phase hydrogenation catalyst comprises the following steps: (1) preparing a mixed solution A containing a VIB group metal and an aluminum source, and carrying out parallel flow gelling reaction on the mixed solution A and a precipitator to generate a slurry I containing a VIB group metal and aluminum precipitate; (2) pulping and uniformly mixing the slurry I obtained in the step (1) and an auxiliary agent precursor, filtering, washing, drying and forming to obtain a catalyst precursor I; (3) drying and roasting the catalyst precursor I obtained in the step (2), and then carrying out vulcanization treatment to obtain a catalyst precursor II containing a VIB group metal sulfide; (4) and (3) impregnating the catalyst precursor II obtained in the step (3) with an impregnating solution containing a VIII group metal, and then drying and roasting the impregnated catalyst precursor II in an inert atmosphere to obtain a semi-vulcanized bulk phase hydrogenation catalyst.
12. The method of claim 10, wherein: in the mixed solution A in the step (1), the weight concentration of VIB group metal in terms of oxide is 10-100 g/L, and Al is Al2O3The weight concentration is 2-60 g/L.
13. The method of claim 10, wherein: the precipitator in the step (1) is one or more of sodium carbonate, sodium bicarbonate, ammonia water, sodium hydroxide, potassium carbonate or potassium bicarbonate water solution, and the concentration of the precipitator is 0.5-3.0 mol/L.
14. The method of claim 10, wherein: in the step (1), the parallel-flow gelatinizing reaction temperature is 30-90 ℃, the pH value is controlled to be 6.0-11.0, and the gelatinizing time is 0.2-4.0 hours.
15. The method of claim 10, wherein: in the step (2), the precursor of the auxiliary agent is one or more of boric acid, phosphoric acid, ammonium hydrofluoric acid, magnesium nitrate, water glass or zirconium nitrate; the concentration of the assistant water solution is 1.0-3.0 mol/L; and after the auxiliary agent and the slurry I are uniformly mixed, controlling the pH value to be 7.0-9.0.
16. The method of claim 10, wherein: the drying conditions in the step (3) are as follows: drying at 90-200 ℃ for 3-6 hours; the roasting conditions are as follows: the roasting temperature is 400-800 ℃, and the roasting time is 3-6 hours.
17. The method of claim 10, wherein: the vulcanization treatment in the step (3) adopts dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or two of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide; the vulcanization pressure is 3.2-6.4 MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 h.
18. The method of claim 10, wherein: the mass concentration of the impregnation liquid of the VIII group metal in the step (4) is 0.1-1.0 g/mL, and an equal-volume impregnation mode is adopted.
19. The method of claim 10, wherein: the inert atmosphere in the step (4) is N2And an inert gas; the drying temperature is 20-90 ℃, and the drying time is 4-16 hours; the roasting temperature is 200-500 ℃, and the roasting time is 2-5 hours.
20. The method of claim 1, wherein: the third hydrogenation reaction zone is used for carrying out polycyclic aromatic hydrocarbon hydrogenation saturation reaction of heavy fractions, and the noble metal hydrogenation catalyst in the third hydrogenation reaction zone comprises a carrier, an active component and an auxiliary agent, wherein the carrier is alumina, the active component is Pt and/or Pd and the auxiliary agent is Ni and/or Co on the basis of the weight of the carrier; based on the weight of the catalyst, the active component is 0.05 to 5.0 weight percent, the auxiliary agent is 1 to 10 weight percent, and the balance is a carrier; the specific surface area of the catalyst is 300-400m2Per g, pore volume of 0.4-0.6cm3The crushing strength is 150-250N/cm.
21. The method of claim 1, wherein: the process conditions of the third hydrogenation reaction zone are as follows: the pressure is 1.0-12.0 MPa, the reaction zone is a pure liquid phase reaction zone, the volume ratio of standard hydrogen to oil is 2-50, and the volume airspeed is 0.1-8.0 h-1The reaction temperature is 150-300 ℃, and the volume ratio of hydrogen to oil is 10: 1-800: 1.
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| CN108014781A (en) * | 2016-10-31 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and its preparation method and application |
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