CN116060052A - Hydrodesulfurization and denitrification catalyst grading system and hydrodesulfurization and denitrification method - Google Patents
Hydrodesulfurization and denitrification catalyst grading system and hydrodesulfurization and denitrification method Download PDFInfo
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- CN116060052A CN116060052A CN202111274364.5A CN202111274364A CN116060052A CN 116060052 A CN116060052 A CN 116060052A CN 202111274364 A CN202111274364 A CN 202111274364A CN 116060052 A CN116060052 A CN 116060052A
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- catalyst
- modified alumina
- alumina carrier
- pore
- metal element
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- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000011148 porous material Substances 0.000 claims abstract description 270
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 97
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- 230000002378 acidificating effect Effects 0.000 claims abstract description 28
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011574 phosphorus Substances 0.000 claims abstract description 18
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- -1 VIB metal oxide Chemical class 0.000 claims description 54
- 238000002360 preparation method Methods 0.000 claims description 37
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- 239000002243 precursor Substances 0.000 claims description 23
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- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J35/19—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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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
- 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
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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
Abstract
The invention relates to the field of hydrofining, and discloses a hydrodesulfurization and denitrification catalyst grading system and a hydrodesulfurization and denitrification method. The grading system comprises a first catalyst and a second catalyst which are sequentially arranged along the material flow direction; the first catalyst comprises a VIII group metal element, a VIB group metal element and a modified alumina carrier, and has a pore volume of 0.15-0.5cm 3 Per g, the average pore diameter is 6-15nm, and the pore diameter is in a bimodal pore distribution within the range of 2-6nm and 8-20nmThe method comprises the steps of carrying out a first treatment on the surface of the The second catalyst comprises a modified alumina carrier, VIII group metal element, VIB group metal element and phosphorus element which are loaded on the modified alumina carrier, and the pore volume is 0.3-0.55cm 3 And/g, wherein the average pore diameter is 7-15nm, and the pore diameter is in unimodal pore distribution within the range of 8-20 nm; the modified alumina supports of both catalysts contained weakly acidic components. The grading system has excellent desulfurization and denitrification effects.
Description
Technical Field
The invention relates to the field of hydrofining, in particular to a hydrodesulfurization and denitrification catalyst grading system and a hydrodesulfurization and denitrification method.
Background
In the great background of green low carbon development, the demand for fossil fuels is impacted and clean utilization of diesel is challenged. On the one hand, environmental regulations require that the quality standard of clean diesel be gradually improved, and refineries must use better hydrogenation catalysts or technologies to remove sulfur and nitrogen impurities. On the other hand, the atrophy of diesel demand places higher demands on clean-up utilization of diesel fractions, requiring high performance hydrogenation catalysts to provide support. Therefore, the development of high-performance desulfurization and denitrification hydrogenation catalysts and technologies has important significance for clean utilization of diesel oil. The industrial diesel hydrogenation device is an adiabatic reaction device, and the radial temperature rise of the reactor is higher due to the large heat release of the hydrogenation reaction. Therefore, catalysts matched with the reaction environment are selected in different reaction areas, and a hydrogenation catalyst grading system is developed, so that the hydrodesulfurization and denitrification performances of the diesel oil device can be better improved.
The patent application with the application number of 201811650785.1 discloses a deep hydrodenitrogenation method for low-grade high-nitrogen heavy distillate, wherein a first reaction zone is filled with a hydrogenation protection catalyst for removing impurities such as metal, colloid and the like, a second reaction zone is filled with a high hydrogenation activity type I hydrodenitrogenation catalyst, and a third reaction zone is filled with a high hydrogenolysis activity type II hydrodenitrogenation catalyst. By grading the hydrogenation catalysts with different functions, nitrogen compounds of the nitrogen heterocycle substituted by the polycyclic aromatic hydrocarbon are deeply removed, and low-nitrogen raw materials are provided for the hydrocracking catalysts and the catalyst cracking catalysts.
The patent application with application number 201110192780.0 discloses dividing a reactor into four reaction zones and respectively filling a first type of catalyst, a mixture of the first type of catalyst and a second type of catalyst, a second type of catalyst and a first type of catalyst, wherein the first type of catalyst is a Mo-Co catalyst, and the second type of catalyst is a W-Mo-Ni catalyst or W-Ni catalyst. The process treats the high-sulfur and high-nitrogen low-grade diesel oil through the grading of different catalysts.
The activity and stability of the existing diesel hydrodesulfurization and denitrification catalyst system still have certain defects, and in order to strengthen the comprehensive utilization of diesel, the hydrodesulfurization and hydrodenitrogenation performance of the diesel needs to be further promoted.
Disclosure of Invention
The invention aims to solve the problems of insufficient activity and stability of a hydrodesulfurization and denitrification catalyst grading system in the prior art, and provides a hydrodesulfurization and denitrification catalyst grading system and a hydrodesulfurization and denitrification method.
In order to achieve the above object, a first aspect of the present invention provides a hydrodesulfurization and denitrification catalyst grading system comprising a first catalyst and a second catalyst disposed in sequence in a stream direction;
The first catalyst comprises a VIII group metal element, a VIB group metal element and a modified alumina carrier, and has a pore volume of 0.15-0.5cm 3 Per g, average pore diameter of 6-15nm, whichWherein the pore diameter of the catalyst shows bimodal pore distribution in the range of 2-6nm and 8-20 nm;
the second catalyst comprises a modified alumina carrier, VIII group metal element, VIB group metal element and phosphorus element which are loaded on the modified alumina carrier, and the pore volume is 0.3-0.55cm 3 And/g, wherein the average pore diameter is 7-15nm, and the pore diameter of the second catalyst is in unimodal pore distribution within the range of 8-20 nm;
the modified alumina supports in the first catalyst and the second catalyst each independently contain a weakly acidic component.
In a second aspect, the present invention provides a method for hydrodesulphurisation and denitrification, comprising: and (3) reacting the distillate to be treated with the grading system in the first aspect under the condition of hydrodesulfurization and denitrification.
Through the technical scheme, the first catalyst and the second catalyst with specific structures and compositions are matched in a synergistic way, so that the catalyst is particularly suitable for hydrodesulfurization and denitrification in the clean production of diesel oil, and has excellent industrial value.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a grading system of a hydrodesulfurization and denitrification catalyst, which comprises a first catalyst and a second catalyst which are sequentially arranged along the flow direction;
the first catalyst comprises a VIII group metal element, a VIB group metal element and a modified alumina carrier, and has a pore volume of 0.15-0.5cm 3 And/g, wherein the average pore diameter is 6-15nm, and the pore diameter of the catalyst shows bimodal pore distribution in the range of 2-6nm and 8-20 nm;
the second catalyst comprises a modified alumina carrier, VIII group metal element, VIB group metal element and phosphorus element which are loaded on the modified alumina carrier, and the pore volume is 0.3-0.55cm 3 And/g, wherein the average pore diameter is 7-15nm, and the pore diameter of the second catalyst is in unimodal pore distribution within the range of 8-20 nm;
The modified alumina supports in the first catalyst and the second catalyst each independently contain a weakly acidic component.
In the present invention, the pore volume, average pore diameter and pore distribution of the catalyst were measured after the catalyst was calcined at 400 degrees for 3 hours.
According to the invention, the first catalyst containing the bimodal holes and the second catalyst containing the unimodal holes are adopted for grading arrangement, so that sulfides and nitrides with different sizes are better removed on the first catalyst, then the residual refractory sulfides and nitrides are removed again through the second catalyst in a high-temperature environment, the effect of playing the advantages of respective desulfurization and denitrification is achieved, the grading system has a good desulfurization and denitrification effect, and the method is more suitable for the adiabatic reaction environment of diesel hydrodesulfurization and denitrification.
In the present invention, the specific surface area, pore volume, average pore diameter and pore distribution of the catalyst are measured by the low temperature nitrogen adsorption method (BET) (see "petrochemical analysis method (RIPP test method)", yang Cuiding et al, scientific Press, 1990). Wherein the pore volume of 2-100nm is calculated according to the BET result.
In the present invention, when not specifically described, the 2-6nm hole means a hole having a diameter of 2nm or more and less than 6nm, the 2-4nm hole means a hole having a diameter of 2nm or more and less than 4nm, the 4-6nm hole means a hole having a diameter of 4nm or more and less than 6nm, and the 8-20nm hole means a hole having a diameter of 8nm or more and less than 20 nm.
In the invention, the pore diameter of the first catalyst shows double-peak pore distribution in the range of 2-6nm and 8-20nm, which means that the pore diameter distribution of the catalyst has peaks in the pore diameter range of 2-6nm and 8-20 nm. Typically, the support also has a certain number of pore size distributions at 2-6nm, but this portion of the pores of the support do not peak and do not form bimodal pores.
The modified alumina carriers of the first catalyst and the second catalyst of the present invention each independently contain a weakly acidic component, and the modified alumina carriers used for the two may be the same or different, and the weakly acidic components contained may also be the same or different, preferably the same. The modified alumina carrier selected by the first catalyst and the second catalyst at least contains a certain amount of acidic components, so that the dispersion of active components can be promoted, the hydrogenation activity of the catalyst is promoted, and the performance of the catalyst is more effectively improved in a limited space. The weakly acidic component can be added in any process of preparing the alumina carrier, for example, can be added in pseudo-boehmite powder, can be added in the process of preparing the carrier, and can also be added after the alumina carrier is molded. According to the present invention, the kind of the weakly acidic component in the first catalyst and the second catalyst is not particularly limited. Preferably, the weakly acidic component is selected from at least one of B, P, si, F and Ge elements; further preferably, the weakly acidic component is selected from at least one of B, P and Si element.
In the present invention, the content of the weakly acidic component is not particularly limited as long as the performance requirement of the catalyst can be satisfied. Preferably, the content of the weak acid component in the modified alumina carrier is 0.5 to 10% by weight, more preferably 1.5 to 8% by weight, in terms of oxide.
In the present invention, the weakly acidic component is provided by a compound containing a weakly acidic component. In a preferred embodiment, in the modified alumina carrier, B 2 O 3 In an amount of not more than 5% by weight, or P 2 O 5 Content of not more than 6% by weight, or SiO 2 At a content of not more than 10 wt%, or at a F content of not more than 5 wt%, or at a GeO content 2 The content is not more than 6% by weight.
In a particularly preferred embodiment, in the modified alumina carrier, B 2 O 3 In an amount of 1.5 to 5 wt.%, or P 2 O 5 In an amount of 2 to 6 wt.%, or SiO 2 In an amount of 6 to 10 wt.%, or F in an amount of 1 to 3 wt.%% or GeO 2 The content is 2-4 wt%.
In the present invention, the manner of introducing the weakly acidic component is not particularly limited, and methods conventional in the art are applicable to the present invention. For example, an impregnation method may be selected. In a preferred embodiment, the present invention employs a co-impregnation method to introduce the weakly acidic component.
In the present invention, the introduction timing of the weakly acidic component is not particularly limited as well, and it may be introduced during the preparation of the alumina carrier or after the preparation of the alumina carrier. Preferably, the following method may be employed: the weakly acidic component is introduced after the preparation of the alumina carrier, and then the modified alumina carrier is obtained by roasting.
In the present invention, when the weakly acidic component is introduced after the preparation of the alumina carrier, the weakly acidic component is provided by a compound containing the weakly acidic component. Preferably, the compound containing a weakly acidic component is selected from at least one of boric acid, silica sol, phosphoric acid, hypophosphorous acid, ammonium phosphate, monoammonium phosphate, ammonium fluoride, sodium germanate, and germanium hydroxide.
In the invention, the specific conditions for calcination are selected in a wide range. Preferably, the roasting temperature is 500-800 ℃ and the time is 2-10h.
In the present invention, when the weakly acidic component is introduced during the preparation of the alumina carrier, preferably, the weakly acidic component-containing compound may be directly added in the form of a precursor.
The preparation method of the alumina carrier in the present invention is not particularly limited, and the conventional preparation methods in the art are applicable to the present invention, and are not described herein.
In the present invention, alumina having specific physical properties is preferably selected as the support for the modified alumina. Preferably, the alumina in the modified alumina carrier has water absorption rate of more than 0.9mL/g and specific surface area of more than 250m 2 Preferably, the alumina has a water absorption of 0.9-1.1mL/g and a specific surface area of 250-360m 2 And/g, wherein the average pore diameter is 9-14nm, and the pore distribution form is unimodal. With such preferred embodimentsThe formula can fully exert the effect of active metals in smaller holes and larger holes, promote the reaction efficiency of the catalyst on reaction substrates with different sizes, and achieve the purpose of fully utilizing the active metals.
In a preferred embodiment, the alumina has a pore volume with a pore size distribution of from 2 to 6nm of not more than 10%, more preferably not more than 8%, still more preferably from 5 to 8% of the total pore volume of the modified alumina support.
In a preferred embodiment, the alumina has a pore volume with a pore size distribution of from 2 to 4nm of not more than 4%, preferably not more than 3% of the total pore volume of the alumina.
The use of the above-described preferred modified alumina carrier is more advantageous in supporting the active component to avoid the formation of agglomerated particles.
In a preferred embodiment, the pore volume of the first catalyst having a pore size distribution of from 2 to 6nm is no more than 7 to 15%, more preferably 8 to 13%, of the total pore volume of the catalyst.
In a preferred embodiment, the first catalyst and the second catalyst each independently further comprise P 2 O 5 P herein 2 O 5 Refers to P other than the compound containing the P weakly acidic component introduced into the modified alumina carrier 2 O 5 。
In the invention, the performance of the catalyst is exerted in order to better utilize the pore canal of the catalyst. Preferably, the first catalyst is prepared according to (Xi ai )·(Yi bi )·(Zi ci ) Sup, where Xi is the group VIB metal oxide, ai is the mass of Xi relative to 1 gram of the modified alumina support, yi is the group VIII metal oxide, bi is the mass of Yi relative to 1 gram of the modified alumina support, zi is P 2 O 5 Ci is relative to 1 g of modified alumina carrier P 2 O 5 Sup refers to the mass of the modified alumina support in the catalyst, calculated as 1 gram, which satisfies the following conditions: (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup Has a value of 0.4 to 1nm, preferably 0.4 to 0.85nm, ρ Xi 、ρ Yi 、ρ Zi Respectively the oxides of metals of group VIBGroup VIII metal oxide and P 2 O 5 Density, SA of sup Is the specific surface area of the modified alumina carrier.
Notably, ci is herein expressed relative to 1 gram of modified alumina carrier P 2 O 5 P in the mass of (2) 2 O 5 Means removing the weak acid component P in the modified alumina carrier 2 O 5 P outside 2 O 5 I.e. not comprising weakly acidic component P in the modified alumina support 2 O 5 。
In the present invention ρMoO 3 、ρWO 3 、ρNiO、ρCoO、ρP 2 O 5 According to the proportion of 4.69g/cm 3 、7.16g/cm 3 、6.67g/cm 3 、6.45g/cm 3 And 2.39g/cm 3 And (5) calculating.
In the present invention, the group VIII metal element includes, but is not limited to, at least one of Fe, co, and Ni, preferably Co and/or Ni.
In a preferred embodiment, the group VIB metal element includes, but is not limited to, at least one of Cr, mo, and W, preferably Mo and/or W.
In the present invention, for P 2 O 5 And the amount of the group VIB metal oxide is not particularly limited. Preferably, the molar ratio Zi/Xi in the first catalyst is from 0.1 to 0.4, more preferably from 0.1 to 0.35. The advantage of the preferred embodiment is that the metal components can better exert the synergistic effect of each other, so that the activity of the catalyst is optimized.
In the present invention, the second catalyst is also limited in composition. Preferably, the second catalyst is prepared according to (Xi ai )·(Yi bi )·(Zi ci ) Sup, where Xi is the group VIB metal oxide, ai is the mass of Xi relative to 1 gram of the modified alumina support, yi is the group VIII metal oxide, bi is the mass of Yi relative to 1 gram of the modified alumina support, zi is P 2 O 5 Ci is relative to 1 g of modified alumina carrier P 2 O 5 Sup refers to the mass of the modified alumina support in the catalyst, calculated as 1 gram, which satisfies the following conditions: (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup Has a value of 0.2-0.39nm, ρ Xi 、ρ Yi 、ρ Zi Respectively a group VIB metal oxide, a group VIII metal oxide and P 2 O 5 Density, SA of sup Is the specific surface area of the modified alumina carrier.
In the present invention, the kinds of the group VIII metal element and the group VIB metal element in the second catalyst are selected in the same range as the first catalyst, and will not be described herein.
In the present invention, P in the second catalyst 2 O 5 And the amount of the group VIB metal oxide is not particularly limited. Preferably, the molar ratio Zi/Xi in the catalyst is between 0.05 and 0.45:1, further preferably 0.2 to 0.38:1.
in the present invention, in order to improve the performance of the first catalyst and the second catalyst, the atomic concentrations of the group VIB metal elements in the first catalyst and the second catalyst are defined. Preferably, the atomic concentration of the VIB group metal element in the first catalyst on the surface of the modified alumina carrier is 4.5-14atom/nm 2 Preferably 5-12 atoms/nm 2 。
In a preferred case, the atom concentration of the VIB group metal element in the second catalyst on the surface of the modified alumina carrier is 2-5.5atom/nm 2 Preferably 3-4.5atom/nm 2 。
In the invention, the atomic concentration of the VIB group metal element on the surface of the modified alumina carrier in the first catalyst and the second catalyst refers to the average atomic concentration of the VIB group metal element on the surface of the modified alumina carrier, and the modified alumina carrier is obtained by measuring the metal load and calculating the specific surface area of the carrier, specifically, the modified alumina carrier is obtained by the following calculation: (ai/M) Xi )×N A /(1×SA sup ) Wherein N is A For the Avoder constant, ai is the mass, M, relative to 1 gram of modified alumina support Xi Xi Molecular weight of Xi, SA sup Is the specific surface area of the carrier.
In a preferred case, in order to further improve the performance of the first catalyst and the second catalyst, the atomic ratio of the group VIII metal element to the total amount of the group VIII metal element and the group VIB metal element in the first catalyst is 0.1 to 0.4, preferably 0.2 to 0.3.
In a preferred case, the atomic ratio of the group VIII metal element to the total of the group VIII metal element and the group VIB metal element in the second catalyst is 0.2 to 0.38, preferably 0.2 to 0.3.
In the present invention, preferably, the first catalyst and the second catalyst further each independently include an organic alcohol compound and/or a carboxylic acid compound. The types of the organic alcohol compound and/or the carboxylic acid compound in the first catalyst and the second catalyst may be the same or different, and the present invention is not particularly limited, but preferably the same.
In a preferred embodiment, the molar ratio of the organic alcohol compound and/or carboxylic acid compound to the group VIII metal element in the first catalyst is from 1 to 6, preferably from 2 to 5.
In a preferred embodiment, the molar ratio of the organic alcohol compound and/or carboxylic acid compound to the group VIII metal element in the second catalyst is from 1 to 4, preferably from 2 to 4.
The purpose of adopting the preferred embodiment is to ensure that the VIII group metal element has higher dispersivity, weaken the interaction force between the modified alumina carrier and metal and promote the generation of more active phases.
In a preferred embodiment, the organic alcohol compound may be at least one of monohydric alcohol, dihydric alcohol and polyhydric alcohol. In a particularly preferred embodiment, the organic alcohol compound is selected from one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, heptanol, ethylene glycol, glycerol, butanetetraol, polyethylene glycol, polyglycerol, pentaerythritol, xylitol, sorbitol and trimethylolethane. In a more particularly preferred embodiment, the organic alcohol compound is selected from at least one of glycerol, propanol and ethylene glycol.
In a preferred embodiment, the carboxylic acid compound is selected from one or more of formic acid, acetic acid, propionic acid, citric acid, caprylic acid, adipic acid, malonic acid, succinic acid, maleic acid, valeric acid, caproic acid, capric acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, valeric acid, caproic acid, capric acid, stearic acid and tartaric acid, and further preferably at least one of formic acid, citric acid and acetic acid.
In a particularly preferred embodiment, the first catalyst and the second catalyst each independently comprise one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, heptanol, ethylene glycol, glycerol, butanetetraol, polyethylene glycol, polyglycerol, pentaerythritol, xylitol, sorbitol, trimethylolethane and/or formic acid, acetic acid, propionic acid, citric acid, octanoic acid, adipic acid, malonic acid, succinic acid, maleic acid, valeric acid, hexanoic acid, decanoic acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, valeric acid, hexanoic acid, decanoic acid, octadecanoic acid, tartaric acid.
According to the present invention, the amounts of the first catalyst and the second catalyst in the gradation system are not particularly limited. Preferably, the loading volume ratio of the first catalyst to the second catalyst is 1:4-4:1, preferably 1:3-3:1.
According to the present invention, the sizes of the first catalyst and the second catalyst are not particularly limited as long as the use requirements can be satisfied. Preferably, the equivalent diameters of the first catalyst and the second catalyst are each independently 0.5 to 1.8mm, preferably 0.8 to 1.6mm.
According to the present invention, there is no particular limitation on the shape of the first catalyst and the second catalyst, and the shape of the catalyst conventional in the art is applicable to the present invention. Preferably, the shape of the first catalyst and the second catalyst are each independently cylindrical, clover, honeycomb or other irregular shape, further preferably butterfly.
According to the present invention, the preparation methods of the first catalyst and the second catalyst are not particularly limited. Preferably, the preparation method of the first catalyst and the second catalyst each independently includes: the method comprises the steps of introducing a VIII group metal precursor, a VIB group metal precursor, a phosphorus-containing compound and optionally an organic alcohol compound and/or a carboxylic acid compound into a modified alumina carrier by adopting an impregnation method, and then drying.
In the present invention, the "optionally organic alcohol compound and/or carboxylic acid compound" means that the organic alcohol compound and/or carboxylic acid compound may or may not be incorporated into the modified alumina support, and is preferably incorporated in the present invention.
In the present invention, the types of the group VIII metal, the group VIB metal, the organic alcohol compound and the carboxylic acid compound are already described above, and will not be described here.
In a preferred case, the group VIB metal precursor includes, but is not limited to, one or more of ammonium heptamolybdate, ammonium molybdate, ammonium phosphomolybdate, molybdenum oxide, ammonium metatungstate, ammonium ethyl metatungstate, and tungsten oxide.
In a preferred case, the group VIII metal precursor includes, but is not limited to, one or more of cobalt nitrate, basic cobalt carbonate, cobalt acetate, cobalt oxide, nickel nitrate, basic nickel carbonate, nickel acetate, and nickel oxide.
In a particularly preferred case, the group VIB metal and group VIII metal precursors include, but are not limited to, one or more of ammonium heptamolybdate, ammonium molybdate, ammonium phosphomolybdate, molybdenum oxide, ammonium metatungstate, ammonium ethyl metatungstate, tungsten oxide, cobalt nitrate, basic cobalt carbonate, cobalt acetate, cobalt oxide, nickel nitrate, basic nickel carbonate, nickel acetate, and nickel oxide.
In a preferred case, P 2 O 5 Provided by a phosphorus-containing compound. Further preferably, the phosphorus-containing compound includes, but is not limited to, one or more of phosphoric acid, hypophosphorous acid, ammonium phosphate, and monoammonium phosphate.
In a preferred case, the group VIII metal precursor, the group VIB metal precursor, and the phosphorus-containing compound are fed in amounts such that the catalyst obtained satisfies the above pair (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup Is required for the value of (2).
The preparation method according to the present invention is not particularly limited, and any impregnation method conventional in the art is applicable to the present invention. For example, one of co-impregnation, stepwise impregnation, saturated impregnation and supersaturated impregnation may be used. In a preferred embodiment, the catalyst is prepared by co-impregnation in the present invention. In a more preferred embodiment, the impregnation method comprises: impregnating the modified alumina support with an impregnating solution containing a group VIII metal precursor, a group VIB metal precursor, a phosphorus-containing compound, and optionally an organic alcohol compound and/or a carboxylic acid compound.
In the present invention, the order of addition of the group VIII metal precursor, the group VIB metal precursor, the phosphorus-containing compound, and optionally the organic alcohol compound and/or the carboxylic acid compound is not particularly limited as long as it is advantageous for uniformly mixing the components. In a preferred embodiment, the group VIII metal precursor, the group VIB metal precursor and the organic alcohol compound and/or carboxylic acid compound are added to an aqueous solution of a phosphorus-containing compound to produce the impregnation solution. In the present invention, the order of addition of the organic alcohol compound and/or carboxylic acid compound, phosphorus-containing compound, and metal precursor may be changed with each other.
According to the invention, the prepared catalyst has the structure and the composition according to the physical parameters of the modified alumina carrier and the dosage of each material. The present invention is not particularly limited thereto, and in order to facilitate understanding of the technical solution of the present invention, an exemplary description is now provided to embody the preparation method of the first catalyst of the present invention, and the method of the present invention includes, but is not limited to, this. For example, the first catalyst may be prepared by the following preparation method: (1) Determining the feeding amount of the VIB metal precursor relative to each g of the modified alumina carrier according to the surface concentration of the VIB metal element and the specific surface area of the modified alumina carrier; (2) Determining the feeding amount of the group VIII metal precursor relative to each g of modified alumina carrier according to the atomic ratio of the group VIII metal element to the total amount of the group VIII metal element and the group VIB metal element; (3) According to (ai/ρ Xi +bi/ρ Yi +ci/ρ Zi )/SA sup To calculate P 2 O 5 To determine the amount of phosphorus-containing compound per g of carrierThe material amount; (4) According to the mole ratio of the organic alcohol compound and/or carboxylic acid compound to the VIII group metal element, calculating the feeding amount of the organic alcohol compound and/or carboxylic acid compound; (5) According to the feeding amounts of the VIB group metal precursor, the VIII group metal precursor, the phosphorus-containing compound and the organic alcohol compound and/or the carboxylic acid compound, the modified alumina carrier is impregnated with the impregnating solution according to a pore saturated impregnation method, and then is dried. Specifically, firstly dissolving a phosphorus-containing compound in water to obtain a phosphorus-containing aqueous solution, then adding an organic alcohol compound and/or a carboxylic acid compound, a VIB group metal precursor and a VIII group metal precursor, stirring under heating until the phosphorus-containing compound is completely dissolved, and keeping the temperature constant to obtain an impregnating solution; (6) The water absorption of the modified alumina carrier is measured, and the liquid absorption of the modified alumina carrier is calculated according to the formula of the water absorption of the modified alumina carrier-0.1; (7) According to the liquid absorption rate of the modified alumina carrier, the impregnating solution is fixed to a corresponding volume (the liquid absorption rate of the modified alumina carrier is multiplied by the carrier mass), and the impregnating solution and the modified alumina carrier with corresponding mass are uniformly mixed and kept stand, and then dried, so that the first catalyst is prepared.
In the present invention, the range of selection of the drying conditions is wide. Preferably, the drying conditions include: the temperature is 80-200deg.C, and the time is 1-10h.
According to the present invention, the preparation methods of the second catalyst and the first catalyst may be the same, and no detailed description is given here.
In a second aspect, the present invention provides a method for hydrodesulphurisation and denitrification, comprising: under the condition of hydrodesulfurization and denitrification, the distillate to be treated is reacted with the grading system in the first aspect.
In a preferred embodiment, the first catalyst and the second catalyst are sulfided from the oxidized catalyst to the sulfided catalyst prior to the step system reaction. In the present invention, the vulcanization method is not particularly limited, and any vulcanization method conventional in the art is applicable to the present invention. Preferably, for example, one of dry vulcanization and wet vulcanization is possible. The kind of the vulcanizing agent is not particularly limited, and may be selected according to a conventional scheme in the art.
Preferably, the vulcanization conditions include: the vulcanization temperature is 280-420 ℃, the time is 10-48 hours, the pressure is 0.1-15MPa, and the volume airspeed is 0.5-20 hours -1 The volume ratio of the hydrogen oil is 100-2000:1, preferably at a heating rate of 5-60 ℃/hr.
The hydrodesulphurisation and denitrification process can be carried out in a hydrogenation unit, in which the above-mentioned grading system is provided. According to the present invention, the hydrogenation apparatus may be selected from any conventional reactors as long as the contact reaction of the raw materials with the first catalyst and the second catalyst in sequence can be achieved. For example, two reactors may be connected in series to form a first reaction zone and a second reaction zone, the first reaction zone being filled with a first catalyst and the second reaction zone being filled with a second catalyst, and the feed being passed through the first reactor and then introduced into the second reactor for reaction. The reactor can be divided into a first reaction zone and a second reaction zone which are arranged up and down, the two reaction zones are respectively filled with a first catalyst and a second catalyst, and raw materials are injected into the reactor from top to bottom for reaction.
In a preferred embodiment, 4000-15000ppm and 200-3000ppm nitrogen are contained in the distillate to be treated.
In a preferred embodiment, the hydrodesulphurisation and denitrification conditions comprise: the temperature is 300-420 ℃, the pressure is 5-15MPa, and the volume airspeed is 0.5-10 hours -1 The volume ratio of the hydrogen oil is 250-2500:1.
according to the present invention, the first catalyst is packed in a first reaction zone, the second catalyst is packed in a second reaction zone, and the conditions of the first reaction zone include: the temperature is 300-390 ℃, the pressure is 5-15MPa, and the volume airspeed is 0.5-10 hours -1 The volume ratio of hydrogen to oil is 250-2000:1, the conditions of the second reaction zone include: the temperature is 360-420 ℃, the pressure is 5-15MPa, and the volume airspeed is 0.5-10 hours -1 The volume ratio of the hydrogen oil is 250-2500:1, the adoption of the preferred embodiment is beneficial to the respective desulfurization and denitrification reactions of the first catalyst and the second catalyst, and promotes the stability of the integral catalyst grading system.
The present invention will be described in detail by examples. The performance of the catalyst system according to the invention is evaluated in the following manner: in the following examples, the hydrodesulfurization performance of the catalyst grading system was measured in a small-scale evaluation apparatus. The device is provided with two reactors connected in series, wherein the first reactor is filled with the first catalyst of the invention, and the second reactor is filled with the second catalyst of the invention. The oxidation state catalyst is directly converted into the sulfidation state catalyst by adopting a temperature programming sulfidation method. The vulcanization conditions are as follows: the vulcanization pressure is 6.4MPa, and the vulcanized oil contains CS 2 2% by weight kerosene, volume space velocity of 2 hours -1 The hydrogen-oil volume ratio is 300v/v, the constant temperature is kept for 6 hours at 230 ℃/h, then the temperature is raised to 360 ℃ for 8 hours of vulcanization, and the temperature raising rate of each stage is 10 ℃/h. After vulcanization, the reaction raw materials are switched to carry out hydrodesulphurisation denitrification activity test, wherein the reaction raw materials are distillate oil with the sulphur content of 10890ppm and the nitrogen content of 321 ppm. The test conditions were: the pressure was 6.4MPa and the total volume space velocity of the two reactors was 2 hours -1 The hydrogen oil volume ratio was 300v/v. The product properties were analyzed after 2 days of reaction stabilization. To examine the stability of the catalyst, the mass fraction of sulfur in the reaction product was maintained at 10ppm, the reaction temperature was adjusted every day, the operation was continued for 5 days, and the change in the reaction temperature before and after 5 days was compared to measure the stability of the catalyst.
The composition of the catalyst is calculated according to the feeding amount. The specific surface area, pore distribution, pore diameter and pore volume of the catalyst and the modified alumina carrier of 2-100nm are measured by adopting a low-temperature nitrogen adsorption method (see the methods of petrochemical analysis (RIPP test method), yang Cuiding, et al, published by scientific press, 1990). The mass fractions of sulfur and nitrogen in the product were analyzed using a sulfur-nitrogen analyzer (model TN/TS3000, manufactured by Sieimer, feidel).
Example 1
The preparation process and the properties of the first catalyst are as follows:
selecting a gamma-alumina carrier, and introducing 2 wt% of B into the carrier by adopting an impregnation method after the carrier is prepared 2 O 3 The modified alumina carrier is prepared, the water absorption rate of the modified alumina carrier is 1.02mL/g, and the specific surface area is 271m 2 /g，The average pore diameter is 12.5nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 7.4%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 3.2%, and the pore diameter distribution is mainly concentrated at 8-20nm.
MoO is carried out 3 Respectively adding basic nickel carbonate and glycerol into aqueous solution containing phosphoric acid, heating and stirring at 85 ℃ for 3 hours until the basic nickel carbonate and the glycerol are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the impregnated solution is dried for 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
The usage amount of the modified alumina carrier and each component is that the prepared catalyst meets the following conditions:
the atomic concentration of Mo in the catalyst was 6.7atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.29, P 2 O 5 /MoO 3 The molar ratio was 0.13, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of glycerol to Ni was 2 at 0.485 nm.
The catalyst was calcined at 400℃for 3 hours and analyzed for pore size distribution by low temperature nitrogen adsorption. The specific surface area of the catalyst was 161m 2 Per gram, pore volume of 0.36cm 3 And/g, wherein the average pore diameter is 8.9nm, the pore structure shows a double-peak pore distribution characteristic at 2-6nm and 8-20nm, and the proportion of the pore volume with the pore diameter of 2-6nm to the total pore volume is 10.5%.
The preparation process and the properties of the second catalyst are as follows:
selecting a gamma-alumina carrier, and introducing 2 wt% of B into the carrier by adopting an impregnation method after the carrier is prepared 2 O 3 The modified alumina carrier is prepared. The water absorption rate of the modified alumina carrier is 1.02mL/g, and the specific surface area is 271m 2 And/g, wherein the average pore diameter is 12.5nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 7.4%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 3.2%, and the pore diameter distribution is mainly 8-20nm.
To a certain amount of MoO 3 Respectively adding basic nickel carbonate and glycerol into aqueous solution containing phosphoric acid, heating and stirring at 85 ℃ for 3 hours until the basic nickel carbonate and the glycerol are completely dissolved, and obtaining impregnation solution containing active metals. Impregnating solutionMixing with carrier uniformly, standing for 3h, drying at 120deg.C for 5h to obtain catalyst with particle diameter of 1.6mm and butterfly shape.
The usage amount of the modified alumina carrier and each component is that the prepared catalyst meets the following conditions:
the atomic concentration of Mo in the catalyst was 4.3atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.25, P 2 O 5 /MoO 3 Molar ratio of 0.2, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of glycerol to Ni was 2 at 0.33 nm.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. The specific surface area of the catalyst was 188m 2 Per gram, pore volume of 0.43cm 3 And/g, wherein the average pore diameter is 9.1nm, and the pore diameter of the catalyst is unimodal pore distribution in the range of 8-20nm.
Performance test of catalyst grading system:
the first catalyst and the second catalyst are mixed according to the volume ratio of 1:1, wherein the reaction temperature of the first catalyst is 355 ℃ and the reaction temperature of the second catalyst is 380 ℃. After the reaction test, the sulfur content in the obtained product is 4.3ppm, and the nitrogen content is 1.3ppm. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 1.5 ℃ after 5 days of reaction.
Example 2
The preparation process and the properties of the first catalyst are as follows:
example 2 the same gamma alumina support as in example 1 was used. 4 wt% of P is introduced by impregnation after the preparation of the support 2 O 5 The modified alumina carrier is prepared, the water absorption rate of the modified alumina carrier is 0.96mL/g, and the specific surface area is 269m 2 And/g, wherein the average pore diameter is 11.9nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 7.5%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 3.6%, and the pore diameter distribution is mainly concentrated at 8-20nm.
MoO is carried out 3 Respectively adding basic nickel carbonate and glycerol into phosphoric acid-containing water solution, heating and stirring at 90deg.C for 3 hr to dissolve completely to obtain active metal-containing leaching solutionAnd (5) soaking the solution. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the impregnated solution is dried for 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
The modified alumina carrier and the usage amount of each component are that the prepared catalyst meets the following conditions:
the atomic concentration of Mo in the catalyst is 12atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.2, P 2 O 5 /MoO 3 Molar ratio of 0.1, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of glycerol to Ni was 5 at 0.785 nm.
The catalyst was calcined at 400℃for 3 hours and analyzed for pore size distribution by low temperature nitrogen adsorption. The specific surface area of the catalyst was 149m 2 Per gram, pore volume of 0.31cm 3 And/g, wherein the average pore diameter is 8.3nm, the pore structure shows a double-peak pore distribution characteristic at 2-6nm and 8-20nm, and the proportion of the pore volume with the pore diameter of 2-6nm to the total pore volume is 12.7%.
The preparation process and the properties of the second catalyst are as follows:
selecting a gamma-alumina carrier, and introducing 4 wt% of P into the carrier by adopting an impregnation method after the carrier is prepared 2 O 5 The modified alumina carrier is prepared. The water absorption rate of the modified alumina carrier is 0.96mL/g, and the specific surface area is 269m 2 And/g, wherein the average pore diameter is 11.9nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 7.5%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 3.6%, and the pore diameter distribution is mainly 8-20nm.
To a certain amount of MoO 3 Respectively adding basic nickel carbonate and glycerol into aqueous solution containing phosphoric acid, heating and stirring at 90 ℃ for 3 hours until the basic nickel carbonate and the glycerol are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the impregnated solution is dried for 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
The modified alumina carrier and the usage amount of each component are that the prepared catalyst meets the following conditions:
the atomic concentration of Mo in the catalyst was 3.2atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.3, P 2 O 5 /MoO 3 Molar ratio of 0.3, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of glycerol to Ni was 4 at 0.283 nm.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. The specific surface area of the catalyst was 205m 2 Per gram, pore volume of 0.48cm 3 And/g, wherein the average pore diameter is 9.4nm, and the pore diameter of the catalyst is unimodal pore distribution in the range of 8-20nm.
Performance test of catalyst grading system:
the first catalyst and the second catalyst are mixed according to a volume ratio of 2:1, the reaction temperature of the first catalyst is 359 ℃, and the reaction temperature of the second catalyst is 384 ℃. After the reaction test, the sulfur content in the obtained product is 3.2ppm, and the nitrogen content is 0.8ppm. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 1.9 ℃ after 5 days of reaction.
Example 3
The preparation process and the properties of the first catalyst are as follows:
example 3 the same gamma alumina support was used as in example 1. After the preparation of the support, 6% by weight of SiO was introduced by impregnation 2 The modified alumina carrier is prepared, the water absorption rate of the modified alumina carrier is 0.95mL/g, and the specific surface area is 275m 2 And/g, wherein the average pore diameter is 9.8nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 8%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 3%, and the pore diameter distribution is mainly concentrated at 8-20nm.
MoO is carried out 3 Respectively adding basic nickel carbonate and glycerol into aqueous solution containing phosphoric acid, heating and stirring at 95 ℃ for 2h until the basic nickel carbonate and the glycerol are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the impregnated solution is dried for 5 hours at 120 ℃ to prepare the butterfly catalyst with the particle size of 1.6 mm.
The modified alumina carrier and the usage amount of each component are that the prepared catalyst meets the following conditions:
the atomic concentration of Mo in the catalyst was 8.5atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.28, P 2 O 5 /MoO 3 Molar ratio of 0.2, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of glycerol to Ni was 3 at 0.66 nm.
The catalyst was calcined at 400℃for 3 hours and analyzed for pore size distribution by low temperature nitrogen adsorption. The specific surface area of the catalyst was 159m 2 Per gram, pore volume of 0.33cm 3 And/g, wherein the average pore diameter is 8.3nm, the pore structure shows a double-peak pore distribution characteristic at 2-6nm and 8-20nm, and the proportion of the pore volume with the pore diameter of 2-6nm to the total pore volume is 11.5%.
The preparation process and the properties of the second catalyst are as follows:
selecting a gamma-alumina carrier, and introducing 6 wt% of SiO into the carrier by adopting an impregnation method after the carrier is prepared 2 The modified alumina carrier is prepared. The water absorption rate of the modified alumina carrier is 0.95mL/g, and the specific surface area is 275m 2 And/g, wherein the average pore diameter is 9.8nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 8%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 3%, and the pore diameter distribution is mainly 8-20nm.
To a certain amount of MoO 3 Respectively adding basic nickel carbonate and glycerol into aqueous solution containing phosphoric acid, heating and stirring at 95 ℃ for 2h until the basic nickel carbonate and the glycerol are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the impregnated solution is dried for 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
The usage amount of the modified alumina carrier and each component is that the prepared catalyst meets the following conditions:
the atomic concentration of Mo in the catalyst was 3.6atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.28, P 2 O 5 /MoO 3 The molar ratio was 0.25, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of glycerol to Ni was 3 at 0.298 nm.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. The specific surface area of the catalyst was 198m 2 Per gram, pore volume of 0.45cm 3 Per g, average pore diameter of 9.1nm, pore diameter of 8-20nAnd the m range is in unimodal pore distribution.
Performance test of catalyst grading system:
the first catalyst and the second catalyst are mixed according to the volume ratio of 1:2, wherein the reaction temperature of the first catalyst is 351 ℃ and the reaction temperature of the second catalyst is 376 ℃. After the reaction test, the sulfur content in the obtained product is 6.5ppm, and the nitrogen content is 1.6ppm. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 2.1 ℃ after 5 days of reaction.
Example 4
The preparation process and the properties of the first catalyst are as follows:
example 4 the same gamma alumina support was used as in example 1. After the preparation of the support, 2% by weight of P was introduced by impregnation 2 O 5 The modified alumina carrier is prepared, the water absorption rate of the modified alumina carrier is 0.97mL/g, and the specific surface area is 265m 2 And/g, wherein the average pore diameter is 10.7nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 6.5%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 2%, and the pore diameter distribution is mainly concentrated at 8-20nm.
Respectively adding ammonium metatungstate, basic nickel carbonate and citric acid into aqueous solution containing phosphoric acid, heating and stirring for 3 hours at 90 ℃ until the ammonium metatungstate, the basic nickel carbonate and the citric acid are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 5 hours, and the impregnated solution is dried for 3 hours at 130 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
The modified alumina carrier and the usage amount of each component are that the prepared catalyst meets the following conditions:
the atomic concentration of W in the catalyst was 5.2atom/nm 2 Ni/(Ni+W) atomic ratio of 0.3, P 2 O 5 /WO 3 Molar ratio of 0.2, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup At 0.424nm, the molar ratio of citric acid to Ni was 2.
The catalyst was calcined at 400℃for 3 hours and analyzed for pore size distribution by low temperature nitrogen adsorption. The specific surface area of the catalyst was 156m 2 Per gram, pore volume of 0.37cm 3 /g, average pore diameter of 9.5nm, pore structureThe double-peak pore distribution characteristics are shown at 2-6nm and 8-20nm, and the proportion of the pore volume with the pore diameter of 2-6nm to the total pore volume is 8.5%.
The preparation process and the properties of the second catalyst are as follows:
selecting a gamma-alumina carrier, and introducing 2 wt% of P into the carrier by adopting an impregnation method after the carrier is prepared 2 O 5 The modified alumina carrier is prepared. The water absorption rate of the modified alumina carrier is 0.97mL/g, and the specific surface area is 265m 2 And/g, wherein the average pore diameter is 10.7nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 6.5%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 2%, and the pore diameter distribution is mainly 8-20nm.
Adding a certain amount of ammonium metatungstate, basic nickel carbonate and citric acid into the aqueous solution containing phosphoric acid respectively, heating and stirring for 3 hours at 90 ℃ until the ammonium metatungstate, the basic nickel carbonate and the citric acid are completely dissolved, and obtaining the impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the impregnated solution is dried for 3 hours at 130 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
The usage amount of the modified alumina carrier and each component is that the prepared catalyst meets the following conditions:
w in the catalyst had an atomic concentration of 4atom/nm 2 Ni/(Ni+W) atomic ratio of 0.3, P 2 O 5 /WO 3 The molar ratio was 0.35, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup At 0.385nm, the molar ratio of citric acid to Ni was 2.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. The specific surface area of the catalyst was 168m 2 Per gram, pore volume of 0.39cm 3 And/g, wherein the average pore diameter is 9.3nm, and the pore diameter of the catalyst is unimodal pore distribution in the range of 8-20nm.
Performance test of catalyst grading system:
the first catalyst and the second catalyst are mixed according to the volume ratio of 1:3, wherein the reaction temperature of the first catalyst is 349 ℃ and the reaction temperature of the second catalyst is 374 ℃. After the reaction test, the sulfur content in the obtained product is 5.3ppm, and the nitrogen content is 1.5ppm. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 1.7 ℃ after 5 days of reaction.
Example 5
The preparation process and the properties of the first catalyst are as follows:
selecting gamma-alumina carrier, introducing 8 wt% SiO in the carrier preparation process 2 The modified alumina carrier is prepared. The water absorption rate of the modified alumina carrier is 0.92mL/g, and the specific surface area is 258m 2 And/g, wherein the average pore diameter is 9.8nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 5%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 1%, and the pore diameter distribution is mainly concentrated at 8-20nm.
MoO is carried out 3 Respectively adding basic nickel carbonate and citric acid into aqueous solution containing phosphoric acid, heating and stirring at 90 ℃ for 3 hours until the basic nickel carbonate and the citric acid are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 2 hours, and the impregnated solution is dried for 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
The modified alumina carrier and the usage amount of each component are that the prepared catalyst meets the following conditions:
the atomic concentration of Mo in the catalyst was 9.3atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.25, P 2 O 5 /MoO 3 Molar ratio of 0.12, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of citric acid to Ni was 2 at 0.64 nm.
The catalyst was calcined at 400℃for 3 hours and analyzed for pore size distribution by low temperature nitrogen adsorption. The specific surface area of the catalyst was 152m 2 Per gram, pore volume of 0.36cm 3 And/g, wherein the average pore diameter is 9.5nm, the pore structure shows a double-peak pore distribution characteristic at 2-6nm and 8-20nm, and the proportion of the pore volume with the pore diameter of 2-6nm to the total pore volume is 10.2%.
The preparation process and the properties of the second catalyst are as follows:
selecting gamma-alumina carrier, introducing 8 wt% SiO in the carrier preparation process 2 The modified alumina carrier is prepared. The water absorption rate of the modified alumina carrier is 0.92mL/g, and the specific surface area is 258m 2 And/g, wherein the average pore diameter is 9.8nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 5%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 1%, and the pore diameter distribution is mainly concentrated at 8-20nm.
To a certain amount of MoO 3 Respectively adding basic nickel carbonate and citric acid into aqueous solution containing phosphoric acid, heating and stirring at 90 ℃ for 2h until the basic nickel carbonate and the citric acid are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the impregnated solution is dried for 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
The usage amount of the modified alumina carrier and each component is that the prepared catalyst meets the following conditions:
the atomic concentration of Mo in the catalyst was 3.8atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.32, P 2 O 5 /MoO 3 Molar ratio of 0.3, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of citric acid to Ni was 2 at 0.34 nm.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. The specific surface area of the catalyst was 183m 2 Per gram, pore volume of 0.47cm 3 And/g, wherein the average pore diameter is 10.3nm, and the pore diameter of the catalyst is unimodal pore distribution in the range of 8-20nm.
Performance test of catalyst grading system:
the first catalyst and the second catalyst are mixed according to a volume ratio of 3:1, wherein the reaction temperature of the first catalyst is 361 ℃ and the reaction temperature of the second catalyst is 386 ℃. After the reaction test, the sulfur content in the obtained product is 3.9ppm, and the nitrogen content is 0.9ppm. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 1.8 ℃ after 5 days of reaction.
Example 6
The preparation process and the properties of the first catalyst are as follows:
selecting gamma-alumina carrier, introducing 1.5 wt% of B in the carrier preparation process 2 O 3 The modified alumina carrier is prepared. The water absorption rate of the modified alumina carrier is 0.96mL/g, and the specific surface area is 274m 2 And/g, wherein the average pore diameter is 11.9nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 8%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 3%, and the pore diameter distribution is mainly concentrated at 8-20nm.
MoO is carried out 3 Respectively adding basic nickel carbonate and citric acid into aqueous solution containing phosphoric acid, heating and stirring at 90 ℃ for 4 hours until the basic nickel carbonate and the citric acid are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 2 hours, and the impregnated solution is dried for 3 hours at 160 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
The usage amount of the modified alumina carrier and each component is that the prepared catalyst meets the following conditions:
the atomic concentration of Mo in the catalyst was 9.8atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.28, P 2 O 5 /MoO 3 Molar ratio of 0.27, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of citric acid to Ni was 2 at 0.83 nm.
The catalyst was calcined at 400℃for 3 hours and analyzed for pore size distribution by low temperature nitrogen adsorption. The specific surface area of the catalyst was 133m 2 Per gram, pore volume of 0.26cm 3 And/g, wherein the average pore diameter is 7.8nm, the pore structure shows a double-peak pore distribution characteristic at 2-6nm and 8-20nm, and the proportion of the pore volume with the pore diameter of 2-6nm to the total pore volume is 10.8%.
The preparation process and the properties of the second catalyst are as follows:
selecting gamma-alumina carrier, introducing 1.5 wt% of B in the carrier preparation process 2 O 3 The modified alumina carrier is prepared. The water absorption rate of the modified alumina carrier is 0.96mL/g, and the specific surface area is 274m 2 And/g, wherein the average pore diameter is 11.9nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 8%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 3%, and the pore diameter distribution is mainly 8-20nm.
To a certain amount of MoO 3 Respectively adding basic nickel carbonate and citric acid into aqueous solution containing phosphoric acid, heating and stirring at 90 ℃ for 3 hours until the basic nickel carbonate and the citric acid are completely dissolved, and obtaining impregnation solution containing active metals. Impregnating solutionThe carrier is mixed uniformly and then stands for 3 hours, and the catalyst with the particle size of 1.6mm and the shape of butterfly is prepared by drying for 3 hours at 160 ℃.
The usage amount of the modified alumina carrier and each component is that the prepared catalyst meets the following conditions:
the atomic concentration of Mo in the catalyst was 4.0atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.2, P 2 O 5 /MoO 3 The molar ratio was 0.25, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of citric acid to Ni was 2 at 0.32 nm.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. The specific surface area of the catalyst was 188m 2 Per gram, pore volume of 0.47cm 3 And/g, wherein the average pore diameter is 10.0nm, and the pore diameter of the catalyst is unimodal pore distribution in the range of 8-20 nm.
Performance test of catalyst grading system:
the first catalyst and the second catalyst are mixed according to the volume ratio of 1:4, the reaction temperature of the first catalyst is 348 ℃, and the reaction temperature of the second catalyst is 373 ℃. After the reaction test, the sulfur content in the obtained product is 6.4ppm, and the nitrogen content is 1.5ppm. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 1.6 ℃ after 5 days of reaction.
Comparative example 1
The preparation process and the properties of the first catalyst are as follows:
the same modified alumina support as in example 1 was selected to prepare a catalyst. MoO is carried out 3 Respectively adding basic nickel carbonate and glycerol into aqueous solution containing phosphoric acid, heating and stirring at 85 ℃ for 3 hours until the basic nickel carbonate and the glycerol are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the impregnated solution is dried for 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
The usage amount of the modified alumina carrier and each component is that the prepared catalyst meets the following conditions:
the atomic concentration of Mo in the catalyst was 3.8atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.25, P 2 O 5 /MoO 3 Molar ratio of 0.28, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of glycerol to Ni was 2 at 0.322 nm.
The catalyst was calcined at 400℃for 3 hours and analyzed for pore size distribution by low temperature nitrogen adsorption. The specific surface area of the catalyst was 210m 2 Per gram, pore volume of 0.46cm 3 And/g, wherein the average pore diameter is 8.8nm, the pore diameter distribution of the catalyst is a unimodal pore, and the appearance position of the unimodal pore is 11.4nm.
The preparation process and the properties of the second catalyst are as follows:
the same modified alumina support as in example 1 was selected to prepare a catalyst. To a certain amount of MoO 3 Respectively adding basic nickel carbonate and glycerol into aqueous solution containing phosphoric acid, heating and stirring at 85 ℃ for 3 hours until the basic nickel carbonate and the glycerol are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the impregnated solution is dried for 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
The usage amount of the modified alumina carrier and each component is that the prepared catalyst meets the following conditions:
the atomic concentration of Mo in the catalyst was 1.9atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.19, P 2 O 5 /MoO 3 Molar ratio of 0.3, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of glycerol to Ni was 2 at 0.161 nm.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. The specific surface area of the catalyst was 233m 2 Per gram, pore volume of 0.6cm 3 And/g, wherein the average pore diameter is 10.3nm, and the pore diameter of the catalyst is unimodal pore distribution in the range of 8-20 nm.
Performance test of catalyst grading system:
the first catalyst and the second catalyst are mixed according to the volume ratio of 1:1, wherein the reaction temperature of the first catalyst is 355 ℃ and the reaction temperature of the second catalyst is 380 ℃. After the reaction test, the sulfur content in the obtained product is 26.5ppm, and the nitrogen content is 4.6ppm. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 2.6 ℃ after 5 days of reaction.
Comparative example 2
The preparation process and the properties of the first catalyst are as follows:
the same modified alumina support as in example 1 was selected to prepare a catalyst. MoO is carried out 3 Respectively adding basic nickel carbonate and glycerol into aqueous solution containing phosphoric acid, heating and stirring at 90 ℃ for 4 hours until the basic nickel carbonate and the glycerol are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the impregnated solution is dried for 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
The usage amount of the modified alumina carrier and each component is that the prepared catalyst meets the following conditions:
the atomic concentration of Mo in the catalyst was 6.0atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.13, P 2 O 5 /MoO 3 Molar ratio of 0.1, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of glycerol to Ni was 2 at 0.38 nm.
The catalyst was calcined at 400℃for 3 hours and analyzed for pore size distribution by low temperature nitrogen adsorption. The specific surface area of the catalyst was 186m 2 Per gram, pore volume of 0.46cm 3 And/g, wherein the average pore diameter is 9.9nm, the pore structure shows unimodal pore distribution characteristics, and the unimodal pores appear at 12.1 nm.
The preparation process and the properties of the second catalyst are as follows:
the same modified alumina support as in example 1 was selected to prepare a catalyst. To a certain amount of MoO 3 Respectively adding basic nickel carbonate and glycerol into aqueous solution containing phosphoric acid, heating and stirring at 90 ℃ for 3 hours until the basic nickel carbonate and the glycerol are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the impregnated solution is dried for 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
The usage amount of the modified alumina carrier and each component is that the prepared catalyst meets the following conditions:
the atomic concentration of Mo in the catalyst was 2.3atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.21, P 2 O 5 /MoO 3 Molar ratio of 0.22, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The atomic ratio of glycerol to Ni was 2 at 0.178 nm.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. The specific surface area of the catalyst was 225m 2 Per gram, pore volume of 0.54cm 3 And/g, wherein the average pore diameter is 9.6nm, and the pore diameter of the catalyst is unimodal pore distribution in the range of 8-20 nm.
Performance test of catalyst grading system:
the first catalyst and the second catalyst are mixed according to a volume ratio of 2:1, the reaction temperature of the first catalyst is 359 ℃, and the reaction temperature of the second catalyst is 384 ℃. After the reaction test, the sulfur content in the obtained product is 19.3ppm, and the nitrogen content is 3.5ppm. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 3.2 ℃ after 5 days of reaction.
The catalyst grading system provided by the invention has higher hydrodesulfurization and denitrification performances and has good industrial application prospect as shown in the examples and the comparative examples.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A hydrodesulphurisation denitrification catalyst grading system, which comprises a first catalyst and a second catalyst which are sequentially arranged along the flow direction;
the first catalyst comprises a VIII group metal element, a VIB group metal element and a modified alumina carrier, and has a pore volume of 0.15-0.5cm 3 And/g, the average pore diameter is 6-15nm, wherein the pore diameter of the catalyst shows a bimodal pore distribution in the range of 2-6nm and 8-20nm；
The second catalyst comprises a modified alumina carrier, VIII group metal element, VIB group metal element and phosphorus element which are loaded on the modified alumina carrier, and the pore volume is 0.3-0.55cm 3 And/g, wherein the average pore diameter is 7-15nm, and the pore diameter of the second catalyst is in unimodal pore distribution within the range of 8-20 nm;
the modified alumina supports in the first catalyst and the second catalyst each independently contain a weakly acidic component.
2. The grading system according to claim 1, wherein the weakly acidic component is selected from at least one of B, P, si, F and Ge elements;
preferably, the content of the weakly acidic component in the modified alumina carrier is 0.5 to 10 wt% in terms of oxide;
preferably, in the modified alumina carrier, B 2 O 3 In an amount of not more than 5% by weight, or P 2 O 5 Content of not more than 6% by weight, or SiO 2 At a content of not more than 10 wt%, or at a F content of not more than 5 wt%, or at a GeO content 2 The content is not more than 6% by weight;
preferably, the alumina in the modified alumina carrier has water absorption rate of more than 0.9mL/g and specific surface area of more than 250m 2 And/g, wherein the average pore diameter is more than 9nm, and the pore distribution form is unimodal pore distribution;
preferably, in the modified alumina carrier, the pore volume with the pore diameter distribution of 2-6nm accounts for not more than 10%, preferably not more than 8% of the total pore volume of the modified alumina carrier;
preferably, in the modified alumina support, the pore volume having a pore size distribution of from 2 to 4nm comprises no more than 4%, preferably no more than 3% of the total pore volume of the modified alumina support.
3. A grading system according to claim 1 or 2, wherein in the first catalyst the pore volume with a pore size distribution of 2-6nm is 7-15%, preferably 8-13% of the total pore volume of the catalyst.
4. A grading system according to any of claims 1-3, wherein the first catalyst composition is according to (Xi ai )·(Yi bi )·(Zi ci ) Sup, where Xi is the group VIB metal oxide, ai is the mass of Xi relative to 1 gram of the modified alumina support, yi is the group VIII metal oxide, bi is the mass of Yi relative to 1 gram of the modified alumina support, zi is P 2 O 5 Ci is relative to 1 g of modified alumina carrier P 2 O 5 Sup refers to the mass of the modified alumina support in the catalyst, calculated as 1 gram, which satisfies the following conditions: (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup Has a value of 0.4 to 1nm, preferably 0.4 to 0.85nm, ρ Xi 、ρ Yi 、ρ Zi Respectively a group VIB metal oxide, a group VIII metal oxide and P 2 O 5 Density, SA of sup The specific surface area of the modified alumina carrier;
preferably, the molar ratio Zi/Xi in the first catalyst is from 0.1 to 0.4, preferably from 0.1 to 0.35.
5. A grading system according to any of claims 1-3, wherein the second catalyst composition is according to (Xi ai )·(Yi bi )·(Zi ci ) Sup, where Xi is the group VIB metal oxide, ai is the mass of Xi relative to 1 gram of the modified alumina support, yi is the group VIII metal oxide, bi is the mass of Yi relative to 1 gram of the modified alumina support, zi is P 2 O 5 Ci is relative to 1 g of modified alumina carrier P 2 O 5 Sup refers to the mass of the modified alumina support in the catalyst, calculated as 1 gram, which satisfies the following conditions: (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup Has a value of 0.2-0.39nm, ρ Xi 、ρ Yi 、ρ Zi Respectively a group VIB metal oxide, a group VIII metal oxide and P 2 O 5 Density, SA of sup The specific surface area of the modified alumina carrier;
preferably, the molar ratio Zi/Xi in the second catalyst is between 0.05 and 0.45:1, preferably 0.2-0.38:1.
6. The grading system according to any of claims 1 to 5, wherein the atomic concentration of the group VIB metal element in the first catalyst on the surface of the modified alumina carrier is 4.5-14 atoms/nm 2 Preferably 5-12 atoms/nm 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or the atomic concentration of the VIB group metal element in the second catalyst on the surface of the modified alumina carrier is 2-5.5atom/nm 2 Preferably 3-4.5atom/nm 2 ；
Preferably, the atomic ratio of the group VIII metal element to the total of the group VIII metal element and the group VIB metal element in the first catalyst is 0.1 to 0.4, preferably 0.2 to 0.3; and/or the atomic ratio of the group VIII metal element to the total amount of the group VIII metal element and the group VIB metal element in the second catalyst is 0.2 to 0.38, preferably 0.2 to 0.3.
7. The grading system according to any of claims 1-6, wherein the first catalyst and the second catalyst each independently further comprise an organic alcohol compound and/or a carboxylic acid compound;
preferably, in the first catalyst, the molar ratio of the organic alcohol compound and/or carboxylic acid compound to the group VIII metal element is 1 to 6, preferably 2 to 5;
preferably, in the second catalyst, the molar ratio of the organic alcohol compound and/or carboxylic acid compound to the group VIII metal element is 1 to 4, preferably 2 to 4.
8. The grading system according to any of claims 1 to 8, wherein the loading volume ratio of the first catalyst and the second catalyst is 1:4-4:1, preferably 1:3-3:1, a step of;
preferably, the equivalent diameters of the first catalyst and the second catalyst are each independently 0.5 to 1.8mm, preferably 0.8 to 1.6mm;
preferably, the first and second catalysts are each independently cylindrical, clover, honeycomb or other irregular shape in shape.
9. The grading system according to any of claims 1-8, wherein the preparation process of the first catalyst and the second catalyst each independently comprises: the method comprises the steps of introducing a VIII group metal precursor, a VIB group metal precursor, a phosphorus-containing compound and optionally an organic alcohol compound and/or a carboxylic acid compound into a modified alumina carrier by adopting an impregnation method, and then drying.
10. A method of hydrodesulphurisation and denitrification, the method comprising: reacting the distillate to be treated with the grading system according to any one of claims 1-8 under hydrodesulphurisation denitrification conditions;
preferably, in the distillate to be treated, the sulfur content is 4000-15000ppm, and the nitrogen content is 200-3000ppm;
Preferably, the hydrodesulfurization and denitrification conditions include: the temperature is 300-420 ℃, the pressure is 5-15MPa, and the volume airspeed is 0.5-10 hours -1 The volume ratio of hydrogen to oil is 250-2000:1.
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