CN117427647A - Catalyst grading method and hydrofining method of catalyst in distillate oil - Google Patents
Catalyst grading method and hydrofining method of catalyst in distillate oil Download PDFInfo
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- CN117427647A CN117427647A CN202210814381.1A CN202210814381A CN117427647A CN 117427647 A CN117427647 A CN 117427647A CN 202210814381 A CN202210814381 A CN 202210814381A CN 117427647 A CN117427647 A CN 117427647A
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- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- NAVSKFYJNZQECG-UHFFFAOYSA-N nickel;propanoic acid Chemical compound [Ni].CCC(O)=O NAVSKFYJNZQECG-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- GJPYYNMJTJNYTO-UHFFFAOYSA-J sodium aluminium sulfate Chemical compound [Na+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GJPYYNMJTJNYTO-UHFFFAOYSA-J 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- UAIHPMFLFVHDIN-UHFFFAOYSA-K trichloroosmium Chemical compound Cl[Os](Cl)Cl UAIHPMFLFVHDIN-UHFFFAOYSA-K 0.000 description 1
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of catalysts, and discloses a catalyst grading method and a hydrofining method of a catalyst in distillate oil. The method comprises the following steps: a first catalyst and a second catalyst which are sequentially filled along the material flow direction; the first catalyst comprises at least one of a group VIB metal element, a co-active component, a phosphorus element, a first carrier, and at least two of an organic alcohol compound, a carboxylic acid compound, and an organic amine compound; the co-active component comprises nickel and optionally at least one of the elements subway, ruthenium and osmium; the second catalyst comprises a second catalyst comprising cobalt element and optionally one of the other group VIII metal elements, at least one group VIB metal element, phosphorus element, a second support and at least two of an organic alcohol compound, a carboxylic acid compound and an organic amine compound; the volume ratio of the first catalyst to the second catalyst is 1:2-5:1. it can treat the distillate oil with the proportion of 10-30 wt% of the secondary hydrogenated diesel oil.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst grading method and a hydrofining method of a catalyst in distillate oil.
Background
In recent years, the quality standard of diesel oil in China is rapidly improved. The national six-diesel quality standard requires that the sulfur content and the polycyclic aromatic hydrocarbon in the diesel are respectively reduced to 10mg/kg and 7 percent. On the other hand, the energy consumption of the diesel hydrogenation device is further reduced. Under the operating conditions of low carbon and low energy consumption, higher requirements are put on the activity, stability and hydrogen consumption of the diesel hydrogenation catalyst. However, it is difficult for a single catalyst to meet both low carbon and long cycle stability production requirements, and the selection of an appropriate catalyst grading system is one of the important solutions. The performance of the existing diesel hydrogenation catalyst grading system is not high or the grading system is complex, so that the low-carbon high-efficiency diesel hydrogenation requirement is difficult to meet.
The 201811650785.1 patent discloses a catalyst system packed in a three reaction zone. The first reaction zone is filled with a hydrogenation protecting catalyst for removing impurities such as metal, colloid and the like, the second reaction zone is filled with a type I hydrodenitrogenation catalyst with high hydrogenation activity, and the third reaction zone is filled with a type II hydrodenitrogenation catalyst with high hydrogenation activity. 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 with the application number of 201210409647.0 discloses a hydrodesulfurization method for distillate oil, which adopts at least two catalysts for grading, wherein the catalysts take Mo and Ni and/or Co as active metal components, P is an auxiliary agent, the catalyst contains alkali metal salt of heteropolyacid, and the content of the alkali metal salt of the heteropolyacid in the graded catalyst is sequentially increased along the flow direction of fluid. The patent with the application number of 201010221051.9 discloses a diesel hydrodesulfurization method with graded filling of a catalyst, wherein two or more catalyst beds are arranged, a mixed catalyst bed is formed by a Mo-Co type catalyst and a Mo-Ni type catalyst, and the proportion of the Mo-Ni catalyst in the mixed catalyst bed is gradually increased. The patent with application number 201110192780.0 divides the reactor into four reaction areas, and fills a first type catalyst, a mixture of the first type catalyst and a second type catalyst, a second type catalyst and a first type catalyst respectively, wherein the first type catalyst is a Mo-Co catalyst, and the second type catalyst is a W-Mo-Ni catalyst or a W-Ni catalyst. The process treats the high-sulfur and high-nitrogen low-grade diesel oil through the grading of different catalysts.
The research and the invention of the diesel hydrodesulfurization catalyst improve the properties of the catalyst from many angles, but the prior art still has difficulty in solving the problem of low-carbon and high-efficiency operation of a diesel hydrogenation device, and the preparation flow or the grading system is relatively complex, the implementation cost and the convenience of the diesel hydrodesulfurization catalyst have certain defects, and the future requirements of the diesel hydrogenation device are difficult to meet.
Disclosure of Invention
The invention aims to solve the problems of poor desulfurization activity, poor stability and high hydrogen consumption in the prior art, and provides a catalyst grading method and a hydrofining method of a catalyst in distillate oil.
In order to achieve the above object, a first aspect of the present invention provides a catalyst gradation method comprising: a first catalyst and a second catalyst which are sequentially filled along the material flow direction;
the first catalyst comprises at least one VIB group metal element, a co-active component, a phosphorus element, a first carrier and at least two of an organic alcohol compound, a carboxylic acid compound and an organic amine compound; the co-active component comprises nickel, optionally at least one of the elements subway, ruthenium and osmium; the pore size distribution of the first catalyst at 100-300nm accounts for no more than 20% of the pore volume of the catalyst; wherein the first catalyst comprises at least two COs in the temperature-programmed oxidation process 2 Releasing spectral peaks, wherein the temperature of the first releasing spectral peak is 210-280 ℃, the temperature of the second releasing spectral peak is 320-380 ℃, and the ratio of the height of the spectral peak to the peak value is 0.5-4:1, a step of;
the second catalyst comprises cobalt element and optionally one of other metal elements of group VIII, at least one metal element of group VIB, phosphorus element, a second carrier and at least two of an organic alcohol compound, a carboxylic acid compound and an organic amine compound; wherein the second catalyst comprises at least two COs in the temperature-programmed oxidation process 2 Releasing the spectral peak, wherein the temperature of the third releasing spectral peak is 200-300 ℃, the temperature of the fourth releasing spectral peak is 300-400 ℃, and the ratio range of the height of the spectral peak to the peak is 1-5:1, a step of;
wherein the loading volume ratio of the first catalyst to the second catalyst is 1:2-5:1.
preferably, the loading volume ratio of the first catalyst to the second catalyst is 1:1-4:1.
preferably, in the first catalyst and the second catalyst, the molar ratio of the organic alcohol compound to the group VIB metal element is each independently 0.2 to 4:1.
preferably, in the first catalyst, the molar ratio of the carboxylic acid compound and/or the organic amine compound to the auxiliary active component is 0.3-1.5:1.
Preferably, in the second catalyst, the molar ratio of the carboxylic acid compound and/or the organic amine compound to the cobalt element and optionally other metal elements of group VIII is 0.1-4:1.
in a second aspect, the present invention provides a process for hydrofining a catalyst in a distillate, wherein the process comprises: under the hydrofining condition, filling a first catalyst and a second catalyst in a hydrofining device according to the grading method of the first aspect, and injecting distillate oil to be treated into the hydrofining device for reaction;
preferably, the proportion of the secondary hydrogenated diesel oil in the distillate to be treated is 10-30 wt%.
According to the invention, the first catalyst and the second catalyst with the composition are subjected to filling grading according to a specific filling volume ratio, so that the two catalysts can be matched in a synergistic way, wherein nickel and phosphorus elements in the first catalyst are matched with more than two different types of organic compounds to improve the activity of the first catalyst, meanwhile, partial phosphorus elements are introduced into a carrier to improve the dispersity of active metal components, so that the activity of the first catalyst is improved, and further, the pore size distribution of the first catalyst in a range of 100-300nm accounts for not more than 20% of the pore volume of the catalyst, so that the activity and stability of the hydrogenation catalyst are improved more favorably; more than two different types of organic compounds are introduced into the second catalyst to be matched with cobalt and phosphorus elements, and preferably, when the atomic ratio of the cobalt element to the total amount of cobalt element and optional other metal elements in the VIII group is not less than 0.8, the second catalyst has lower reaction hydrogen consumption; the method is applied to clean production of diesel oil, so that the reaction system has good activity and stability, is particularly suitable for secondary processing of distillate oil with the diesel oil proportion of 10-30 wt%, gives full play to the grading effect of the two catalysts, can effectively remove sulfur and aromatic hydrocarbon in the distillate oil, has lower reaction hydrogen consumption, and has potential industrial value.
Drawings
FIG. 1 is a first bed catalyst temperature programmed CO of example 1 2 A release profile;
FIG. 2 is a second bed catalyst temperature programmed CO of example 1 2 A release profile.
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.
In the present invention, it is understood that "optionally" means that it may or may not be included.
The first aspect of the present invention provides a catalyst sizing method comprising: a first catalyst and a second catalyst which are sequentially filled along the material flow direction;
the first catalyst comprises at least one VIB group metal element, a co-active component, a phosphorus element, a first carrier and at least two of an organic alcohol compound, a carboxylic acid compound and an organic amine compound; the co-active component comprises nickel, optionally at least one of the elements subway, ruthenium and osmium; the pore size distribution of the first catalyst at 100-300nm accounts for no more than 20% of the pore volume of the catalyst; wherein the first catalyst comprises at least two COs in the temperature-programmed oxidation process 2 Releasing spectral peaks, wherein the temperature of the first releasing spectral peak is 210-280 ℃, the temperature of the second releasing spectral peak is 320-380 ℃, and the ratio of the height of the spectral peak to the peak value is 0.5-4:1, a step of;
the second catalyst comprises cobalt element and optionally one of other metal elements of group VIIIAt least two of at least one group VIB metal element, phosphorus element, a second carrier, an organic alcohol compound, a carboxylic acid compound and an organic amine compound; wherein the second catalyst comprises at least two COs in the temperature-programmed oxidation process 2 Releasing the spectral peak, wherein the temperature of the third releasing spectral peak is 200-300 ℃, the temperature of the fourth releasing spectral peak is 300-400 ℃, and the ratio range of the height of the spectral peak to the peak is 1-5:1, a step of;
wherein the loading volume ratio of the first catalyst to the second catalyst is 1:2-5:1.
in the invention, the first release spectrum peak temperature is 210-280 ℃ and refers to a specific temperature value when the peak value of the first release spectrum peak appears between 210-280 ℃, and the second release spectrum peak temperature is 320-380 ℃ and refers to a specific temperature value when the peak value of the second release spectrum peak appears between 320-380 ℃; the third release peak temperature and the fourth release peak temperature have the same meaning as the first release peak temperature and the second release peak temperature, and will not be described in detail herein.
In the present invention, in the first catalyst, the "spectral peak height ratio" means a ratio of the peak height of the first released spectral peak to the peak height of the second released spectral peak, i.e., spectral peak height ratio=peak height of the first released spectral peak/peak height of the second released spectral peak. The "ratio of the heights of the spectral peaks" in the second catalyst is the same as the "ratio of the heights of the spectral peaks" in the first catalyst.
In the present invention, it is understood that CO 2 The peak temperature of the release spectrum has an error of + -2 ℃.
In the present invention, in the first catalyst and the second catalyst, CO 2 The release spectrum peak is analyzed on a NETZSCH STA 409PC/PG instrument, the catalyst to be tested is heated up under the air atmosphere (the heating rate is 10 ℃/min), and the gas outlet of the instrument is monitored by a mass spectrometer, so that the CO generated by the decomposition of the catalyst is obtained 2 Curve as a function of temperature.
In the invention, the first catalyst has a specific pore diameter structure, and the activity of the catalyst is obviously improved by introducing more than two different types of organic compounds into the first catalyst, and the catalyst has good activity and stability.
In the invention, more than two different types of organic compounds are introduced into the second catalyst, so that the activity of the catalyst is obviously improved, and the catalyst has good activity and reaction hydrogen consumption.
According to the invention, the first catalyst and the second catalyst are filled according to a specific volume ratio, so that the two catalysts are matched in a synergistic way, and the ratio of the two catalysts to the secondary processing diesel oil in the distillate oil to be treated is 10-30 wt%, so that the catalyst has good activity and reaction hydrogen consumption and has excellent industrial value.
In the present invention, preferably, the loading volume ratio of the first catalyst to the second catalyst is 1: 1-4:1. the catalyst system has higher desulfurization activity, aromatic saturation activity and lower hydrogen consumption by adopting the preferred embodiment.
In the present invention, the content of the co-active component is preferably 1 to 15 wt%, more preferably 2 to 12 wt%, still more preferably 3 to 8 wt%, in terms of oxide, based on the total amount of the first catalyst; the content of the group VIB metal element is 12 to 50 wt.%, and the content of the group VIB metal element is 15 to 40 wt.%, and more preferably 20 to 35 wt.%. An advantage of using such a preferred embodiment is that the first catalyst has a higher activity and stability.
According to a preferred embodiment of the invention, the atomic ratio of nickel to the total amount of co-active components is not less than 0.8, preferably 0.85-1. The advantage of using this preferred embodiment is that the catalyst activity is increased and the reaction hydrogen consumption is reduced.
According to a preferred embodiment of the present invention, P 2 O 5 The phosphorus content in the first catalyst is 3 to 10% by weight, more preferably 3.5 to 9% by weight, still more preferably 4 to 8% by weight. The advantage of using such a preferred embodiment is that the first catalyst is more active.
According to a preferred embodiment of the invention, the first catalyst comprises at least two CO during the temperature-programmed oxidation 2 Releasing spectral peak, the first releasing spectral peak temperature is 230-260 deg.C, the second releasing spectral peak temperature is 320-360 deg.C, and the spectral peak height ratioThe example range is 0.7-3.5:1. an advantage of using such a preferred embodiment is that the catalyst is able to maintain higher activity and stability.
According to a preferred embodiment of the invention, the pore size distribution of the first catalyst at 100-300nm is 5-20%, more preferably 8-15% of the catalyst pore volume. The larger pore diameter in the reaction process of the preferred embodiment promotes the diffusion of larger reaction molecules, so that the generation of carbon deposit on the surface of the catalyst can be reduced, and the stability of the catalyst is promoted.
In the invention, the synergistic effect of the co-active component and the VIB group metal element is exerted by limiting the dosage of the co-active component and the VIB group metal element, so that the catalytic performance of the catalyst is improved. Preferably, the atomic ratio of the co-active component to the total of co-active component and group VIB metal element is from 0.1 to 0.5, preferably from 0.2 to 0.35.
In the present invention, the selection range of the group VIB metal element types in the first catalyst and the second catalyst is wide. Preferably, the group VIB metal elements in the first catalyst and the second catalyst are each independently selected from at least one of chromium, molybdenum and tungsten, and further preferably molybdenum.
In the present invention, the content of cobalt element and optionally other group VIII metal element is preferably 1 to 15 wt%, more preferably 2 to 12 wt%, still more preferably 3 to 7 wt%, in terms of oxide, based on the total amount of the second catalyst; the content of the group VIB metal element is 12 to 50 wt%, preferably 15 to 45 wt%, and more preferably 18 to 40 wt%. The advantage of using such a preferred embodiment is that the catalyst has higher hydrodesulphurisation activity and stability.
According to a preferred embodiment of the present invention, the atomic ratio of cobalt element to the total amount of cobalt element and optionally other group VIII metal elements is not less than 0.8, more preferably 0.85 to 1, still more preferably 0.9 to 1. The advantage of using this preferred embodiment is that the second catalyst activity is increased and the reaction hydrogen consumption is reduced.
According to a preferred embodiment of the present invention, P 2 O 5 The phosphorus content in the second catalyst is 3-10 weight percentThe amount is more preferably 3.5 to 9% by weight, still more preferably 4 to 8% by weight. An advantage of using such a preferred embodiment is that the second catalyst has a higher activity.
According to a preferred embodiment of the invention, the catalyst comprises at least two CO during the temperature-programmed oxidation 2 Releasing spectral peaks, wherein the temperature of the first releasing spectral peak is 220-280 ℃, the temperature of the second releasing spectral peak is 320-380 ℃, and the ratio range of the spectral peak heights is 1.5-3:1. an advantage of using such a preferred embodiment is that the second catalyst is able to maintain higher activity and stability.
In the present invention, the group VIII other metal element is preferably at least one selected from the group consisting of iron, ruthenium, rhodium, nickel and palladium, and further preferably nickel.
In the present invention, the amounts of cobalt element and optionally other group VIII and group VIB metal elements are not particularly limited as long as the performance of the catalyst can be satisfied. Preferably, the atomic ratio of cobalt element and optionally other group VIII metal elements to the total of cobalt element and optionally other group VIII metal elements and group VIB metal elements is 0.1-0.5, preferably 0.2-0.35. An advantage of using this preferred embodiment is that the group VIII metal element and the group VIB metal element remain in good synergy to exert higher catalytic performance.
In the present invention, the selection range of the kind of the first carrier is wide, and the conventional carriers in the art are suitable for the present invention. Preferably, the first support is a first alumina support.
In the present invention, the selection range of the kind of the second vector is wide, and the vectors conventional in the art are suitable for the present invention. Preferably, the second support is a second alumina support.
In the present invention, preferably, the phosphorus element in both the first catalyst and the second catalyst is derived from both parts. Taking a first catalyst as an example, one part of the catalyst is introduced from a first alumina carrier, and the other part of the catalyst is introduced in the preparation process of the active component impregnating solution.
According to a preferred embodiment of the present invention, the first alumina support and the second alumina support each contain a phosphorus element, hereinafter referred to as a first phosphorus-containing alumina and a second phosphorus-containing alumina, respectively. The advantage of using this preferred embodiment is that the presence of specific amounts of phosphorus in both the first alumina and the second alumina significantly promotes the activity of the catalyst.
According to a preferred embodiment of the present invention, P 2 O 5 The phosphorus element in the first alumina carrier and the second alumina carrier each independently accounts for 10-40 wt%, preferably 20-30 wt%, of the total phosphorus content in the first catalyst and the second catalyst. The advantage of adopting this kind of preferred embodiment is that the content of phosphorus element in reasonable control first alumina carrier and the second alumina carrier can further promote the load degree of active component on the alumina carrier, promotes the dispersity of active component.
In the present invention, the manner and timing of introducing the phosphorus element in the first alumina carrier and the second alumina carrier are not particularly limited, and the phosphorus element may be introduced in the same manner, and preferably, the first alumina carrier is taken as an example, and the phosphorus element may be introduced in the first alumina carrier after molding, may be introduced during the molding of the first alumina carrier, and may be introduced during the preparation of the first alumina carrier precursor. Preferably during the preparation of the first alumina carrier precursor, when introduced during the preparation of the first alumina precursor, the phosphorus element may be introduced by adding a phosphorus-containing compound during the preparation of the first alumina precursor using the aluminum sulfate-sodium meta-aluminate method, specifically, phosphoric acid or a phosphate is introduced as a raw material or at any step during the preparation of the first alumina precursor. By introducing phosphorus element into the first alumina precursor, the structural property of the first alumina carrier is improved, and the dispersing capability of the active component is promoted.
In the present invention, phosphorus element in the first phosphorus-containing alumina carrier and the second phosphorus-containing alumina carrier is provided by the first alumina carrier precursor and the second alumina carrier, respectively. In a preferred embodiment, the precursors of the first alumina carrier and the second alumina carrier are pseudo-boehmite, and the pseudo-boehmite contains phosphorus element.
Typically, sodium-containing precursors are used in the preparation of pseudo-boehmite, and such materials remain in the pseudo-boehmite. In a preferred embodiment, the sodium oxide content of the pseudo-boehmite is not more than 0.08% by weight, preferably not more than 0.05% by weight. The advantage of adopting this kind of preferred embodiment is that the content of sodium oxide in pseudo-boehmite is controlled, further reduces the basicity center, makes the catalyst have good activity, promotes the hydrogenation effect of catalyst.
In the present invention, the preparation methods of the first phosphorus-containing alumina carrier and the second phosphorus-containing alumina carrier are not particularly limited, and any conventional preparation method in the art is applicable to the present invention, for example, extrusion molding can be used to prepare the first phosphorus-containing alumina carrier and the second phosphorus-containing alumina carrier, and the specific manner is not described herein.
In the present invention, in order to further improve the performance of the first catalyst, a carrier having a specific composition and structure is selected as the carrier of the first catalyst. Preferably, the water absorption rate of the first alumina carrier is more than 0.9mL/g, more preferably 0.95-1.3mL/g, and the specific surface area is more than 260m 2 Preferably 270-320m 2 And/g, the average pore diameter is more than 8nm, more preferably 10 to 15nm. The advantage of using such a preferred embodiment is that the first alumina carrier is able to provide a larger pore size, promoting sufficient contact of the reactive molecules with the active components, improving the activity and stability of the catalyst.
According to a preferred embodiment of the invention, the pore size distribution of the first alumina support at 100-300nm is 5-15%, preferably 7-13% of the pore volume of the first alumina support.
In the present invention, the structural parameters of the second alumina carrier are not particularly limited. Preferably, the water absorption rate of the second alumina carrier is more than 0.9mL/g, more preferably 0.95-1.3mL/g, and the specific surface area is more than 260m 2 Preferably 270-320m 2 And/g, the average pore diameter is greater than 8nm, more preferably 9 to 15nm. The advantage of using this preferred embodiment is that the choice has multiple poresThe carrier with the structure can be contacted with the active center of the catalyst to react, so that the activity of the catalyst is improved.
According to a preferred embodiment of the present invention, in the second alumina support, the pore volume having a pore size distribution of 2 to 6nm is not more than 10%, preferably not more than 8%, further preferably 3 to 6% of the total pore volume of the alumina support.
According to a preferred embodiment of the present invention, in the second alumina support, the pore volume having a pore size distribution of 2 to 4nm is not more than 4%, preferably not more than 2%, further preferably 0 to 1% of the total pore volume of the alumina support.
In the present invention, the specific surface area, pore volume, pore diameter and pore distribution of the first alumina carrier and the second alumina carrier are measured by a low temperature nitrogen adsorption method (BET) and a mercury intrusion method (see "petrochemical analysis method (RIPP test method)", edited by Yang Cuiding et al, scientific Press, 1990). Wherein the pore volume of 2-100nm is calculated according to BET result, and the pore volume of 100-300nm is calculated according to mercury intrusion determination result.
According to a particularly preferred embodiment of the present invention, the first catalyst and the second catalyst each comprise an organic alcohol compound and a carboxylic acid compound and/or an organic amine compound. The advantage of using such preferred embodiments is that the selection of more than two organic compounds can significantly increase the activity of the catalyst.
According to a particularly preferred embodiment of the present invention, the molar ratio of the organic alcohol compound to the group VIB metal element in the first catalyst and the second catalyst is each independently from 0.2 to 4:1, preferably 0.5-2.5:1, further preferably 0.6 to 2.2:1.
According to a particularly preferred embodiment of the invention, the molar ratio of carboxylic acid compound and/or organic amine compound to co-active component in the first catalyst is between 0.3 and 1.5:1, preferably 0.4-1.2: 1, further preferably 0.5 to 1.1:1. the advantage of using such a preferred embodiment is that the active component in the catalyst is kept highly dispersed to increase the activity and stability of the catalyst.
According to a preferred embodiment of the present invention, in the second catalyst, the molar ratio of the carboxylic acid compound and/or the organic amine compound to the cobalt element and optionally other metal elements of group VIII is between 0.1 and 4:1, preferably 0.2-3.5:1, further preferably 0.5 to 3:1.
in the present invention, the selection range of the kind of the organic alcohol compound in the first catalyst and the second catalyst is wide. Preferably, in the first catalyst and the second catalyst, the organic alcohol compound is selected from at least one of monohydric alcohol, dihydric alcohol and polyhydric alcohol. Further preferably, in the first catalyst and the second catalyst, the organic alcohol compound is at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, heptanol, ethylene glycol, glycerol, butanetetraol, polyethylene glycol, polyglycerol, pentaerythritol, xylitol, sorbitol, and trimethylolethane, and still further preferably at least one of butanol, glycerol, propanol, and ethylene glycol, independently of each other.
In the present invention, the kind of carboxylic acid compound in the first catalyst and the second catalyst is not particularly limited. Preferably, in the first catalyst and the second catalyst, the carboxylic acid compound is each independently selected from at least one of formic acid, acetic acid, propionic acid, citric acid, octanoic acid, adipic acid, malonic acid, succinic acid, maleic acid, valeric acid, caproic acid, capric acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, stearic acid and tartaric acid, and more preferably at least one of formic acid, citric acid and acetic acid.
In the present invention, the kind of the organic amine compound in the first catalyst and the second catalyst is not particularly limited. Preferably, in the first catalyst and the second catalyst, the organic amine compound is at least one selected from ethylenediamine, ethylenediamine tetraacetic acid, ethanolamine, triethanolamine and cyclohexanediamine tetraacetic acid, and further preferably triethanolamine and/or cyclohexanediamine tetraacetic acid.
In the present invention, the sizes of the first catalyst and the second catalyst are not particularly limited. Preferably, the equivalent diameter of the first catalyst and the second catalyst is 0.5 to 1.8mm, more preferably 0.8 to 1.6mm.
In the present invention, the shapes of the first catalyst and the second catalyst are not particularly limited, and the shapes of the catalysts conventional in the art are applicable to the present invention. Preferably, the shape of the first catalyst and the second catalyst are each independently cylindrical, clover, dish, honeycomb or other irregular shape, further preferably butterfly.
In the present invention, the method for producing the first catalyst is not particularly limited. Preferably, the preparation method of the first catalyst comprises the following steps: the method comprises the steps of introducing a co-active component precursor, a VIB group metal precursor, a phosphorus compound, and at least two compounds of an organic alcohol compound, a carboxylic acid compound and an organic amine compound into a first carrier by adopting an impregnation method, and then drying.
In the present invention, the types of the first carrier, the co-active ingredient, the group VIB metal, the organic alcohol compound, the carboxylic acid compound, and the organic amine compound are described in the foregoing, and no description is given here.
According to a preferred embodiment of the invention, in the first catalyst, the co-active component precursor is selected from the respective soluble salts or chlorides.
In a preferred embodiment, the co-active component precursor is selected from at least one of nickel nitrate, basic nickel carbonate, nickel acetate, nickel propionate, iron nitrate, iron chloride, iron acetate, ruthenium nitrate, ruthenium chloride, ruthenium acetate, osmium nitrate, and osmium trichloride.
In a preferred embodiment, the group VIB metal precursor is selected from at least one of ammonium heptamolybdate, ammonium molybdate, ammonium phosphomolybdate, ammonium metatungstate, and ammonium ethyl metatungstate.
In a preferred embodiment, the phosphorus-containing compound is selected from at least one of phosphoric acid, hypophosphorous acid, ammonium phosphate and monoammonium phosphate.
The impregnation 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 first catalyst is prepared by co-impregnation in the present invention. In a more preferred embodiment, the impregnation method comprises: impregnating the first carrier with an impregnating solution containing at least two of a co-active component precursor, a group VIB metal precursor, a phosphorus-containing compound, an organic alcohol compound, a carboxylic acid compound, and an organic amine compound.
In the invention, the addition sequence of the auxiliary active component precursor, the VIB group metal precursor, the phosphorus-containing compound, the organic alcohol compound, the carboxylic acid compound and the organic amine compound is not particularly limited, so long as the components are uniformly mixed. In a preferred embodiment, at least two (preferably an organic alcohol compound and a carboxylic acid compound and/or an organic amine compound), a co-active component precursor, and a group VIB metal precursor are added to the aqueous solution of the phosphorus-containing compound, respectively, to provide the impregnation fluid. In the present invention, the order of addition of the organic alcohol compound, carboxylic acid compound and/or organic amine compound, phosphorus compound and metal precursor may be changed with each other.
In the invention, the first catalyst can be prepared by the following preparation method: firstly, dissolving a phosphorus-containing compound in water to obtain a phosphorus-containing aqueous solution, then adding at least two of an organic alcohol compound, a carboxylic acid compound and an organic amine compound (preferably an organic alcohol compound, a carboxylic acid compound and/or an organic amine compound), a VIB group metal precursor and an auxiliary active component precursor, stirring under heating until the VIB group metal precursor and the auxiliary active component precursor are completely dissolved, keeping the temperature to obtain an impregnating solution, measuring the water absorption rate of a first alumina carrier, and calculating the liquid absorption rate of the first alumina carrier according to a formula of the water absorption rate-0.1 of the first alumina carrier; according to the liquid absorption rate of the first alumina carrier, the impregnating solution is fixed to a corresponding volume (the liquid absorption rate of the first alumina carrier is multiplied by the carrier mass), and the impregnating solution and the first 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 method for producing the second catalyst is not particularly limited. Preferably, the preparation method of the second catalyst comprises the following steps: and introducing a cobalt element precursor, optionally at least two of a group VIII other metal precursor, a group VIB metal precursor, a phosphorus-containing compound and an organic alcohol compound, a carboxylic acid compound and an organic amine compound into a second carrier by adopting the same impregnation method as the first catalyst, and then drying.
In the present invention, the types of the second carrier, the group VIII other metal, the group VIB metal, the organic alcohol compound, the carboxylic acid compound, and the organic amine compound are described in the foregoing, and no description is given here.
According to a preferred embodiment of the present invention, the cobalt element precursor is selected from at least one of cobalt nitrate, basic cobalt carbonate and cobalt acetate.
In the present invention, the other metals of group VIII, the types of the precursors of the metals of group VIB, and the types of the phosphorus-containing compounds may be selected from the precursors of the corresponding substances in the first catalyst, and will not be described herein.
In the present invention, the second catalyst and the first catalyst may be prepared by the same method, and specific operation modes and conditions are already described in the foregoing, and will not be described herein.
In the preparation method of the first catalyst and the second catalyst in the present invention, the condition of stirring is not particularly limited. Preferably, in the preparation method of the first catalyst and the second catalyst, the stirring each independently includes: the temperature is 40-100deg.C, and the time is 1-8h.
In the preparation method of the first catalyst and the second catalyst in the present invention, the choice of drying conditions is not particularly limited. Preferably, in the preparation method of the first catalyst and the second catalyst, the drying conditions each independently include: the temperature is 60-200deg.C, and the time is 2-10h.
According to a preferred embodiment of the present invention, the first catalyst and the second catalyst are prepared by a non-calcination treatment. The advantage of using this preferred embodiment is that the organic matter is retained in the catalyst, promoting the formation of more active sites, allowing the catalyst to maintain a higher initial activity.
In a second aspect, the present invention provides a process for hydrofining a catalyst in a distillate, wherein the process comprises: under the hydrofining condition, filling the first catalyst and the second catalyst in the hydrofining device according to the grading method of the first aspect, and injecting the distillate to be treated into the hydrofining device for reaction.
In the present invention, the catalyst in the hydrorefining unit is the first catalyst and the second catalyst according to the first aspect of the present invention.
The amounts of the first catalyst and the second catalyst used in the present invention have already been described in the first aspect and will not be described here.
According to the present invention, the hydrorefining apparatus may be selected from any conventional reactors as long as contact reaction of the raw materials with the first catalyst and the second catalyst in sequence can be achieved. For example, two hydrogenation reactors can be connected in series to form a first reaction zone and a second reaction zone, the first reaction zone is filled with a first catalyst, the second reaction zone is filled with a second catalyst, and the raw materials flow through the first reactor and then are introduced into the second reactor for reaction; the second mode is to divide the reactor into a first reaction zone and a second reaction zone which are arranged up and down, wherein 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.
According to a particularly preferred embodiment of the invention, the proportion of secondary hydrogenated diesel oil in the distillate to be treated is between 10 and 30% by weight. The advantage of adopting this preferred embodiment is that clean diesel meeting the national sixth standard can be produced under milder conditions, also with lower hydrogen consumption during the reaction.
According to a preferred embodiment of the invention, the fraction oil to be treated has a straight-run diesel content of 75-85% by weight, a catalytic diesel content of 15-25% by weight, a sulfur content of 2000-18000ppm and an aromatic content of 15-45% by weight.
In the invention, the secondary hydrogenation diesel oil refers to catalytic diesel oil.
In the present invention, preferably, the reaction conditions include: the temperature is 300-450 ℃, the pressure is 3-20MPa, and the volume airspeed is 0.5-3 hours -1 The volume ratio of the hydrogen oil is 100-2000:1.
according to the present invention, the first catalyst is packed in a first reaction zone, and the second catalyst is packed in a second reaction zone, preferably, the conditions of the first reaction zone include: the temperature is 320-420 ℃, the pressure is 6-20MPa, and the volume airspeed is 0.5-3 hours -1 The hydrogen oil volume ratio is 300-1500:1, a step of; preferably, the conditions of the second hydrogenation reaction zone include: the temperature is 320-400 ℃, the pressure is 3-8MPa, and the volume airspeed is 0.5-3 hours -1 The volume ratio of the hydrogen oil is 100-500:1, the advantage of using the preferred embodiment described above is better performance of the first reaction zone and second reaction zone catalysts.
According to a preferred embodiment of the present invention, the first catalyst and the second catalyst are used in a state where the oxidation state catalyst is sulfided to a sulfided state catalyst prior to use. 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.
In the present invention, preferably, the sulfiding conditions of the first catalyst and the second catalyst include: the temperature rising rate is 5-60 ℃/h, the vulcanizing temperature is 280-420 ℃, the vulcanizing time is 8-48h, the vulcanizing pressure is 0.1-15MPa, and the volume airspeed is 0.5-20 h -1 The volume ratio of the hydrogen oil is 100-2000:1.
the invention will be further illustrated by the following examples.
In the examples below, the hydrogenation performance of the catalyst was carried out in a high throughput hydrogenation reaction unit. The device is provided with a reactor which is divided into an upper bed layer and a lower bed layer, the first catalyst is filled in a first reaction zone, and the second catalyst is filled in a second reaction zone. Firstly, adopting a programmed temperature vulcanization method to convert the oxidation state catalyst Is a catalyst in a sulfided state. 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 2h -1 The hydrogen-oil ratio is 300v/v, the temperature is firstly kept constant at 230 ℃ for 6h, then the temperature is raised to 360 ℃ for 8h of vulcanization, and the temperature raising rate of each stage is 10 ℃/h. After vulcanization, the reaction raw materials are switched to carry out hydrodesulfurization activity test, wherein the content of straight-run diesel oil in the distillate to be treated is 80% by weight, the content of catalytic diesel oil is 20% by weight, the sulfur content is 10890ppm, and the aromatic hydrocarbon content is 37.4% by weight, and the test conditions are as follows: the pressure was 6.4MPa and the total volume space velocity of the reactor was 1.5 hours -1 The hydrogen-oil ratio was 300v/v and the reaction temperature was 360 ℃. The reaction was stably carried out for 12 days, and the ratio of the change in the reaction rate constant after the reaction was run for 12 days was calculated, specifically, the ratio of the rate constant after the reaction was stabilized to the initial reaction rate constant was referred to as the activity retention degree to express the stability of the catalyst. The higher the retention of activity, the better the stability of the catalyst.
The composition of the catalyst is calculated according to the feeding amount. The pore distribution, pore diameter and pore volume of the catalyst and carrier are measured by a low-temperature nitrogen adsorption method (see petrochemical analysis method (RIPP test method), yang Cuiding et al, scientific press, 1990, publication), and the pore distribution, pore diameter and pore volume of the catalyst and carrier are measured by mercury intrusion method. The sulfur mass fraction in the product was analyzed by a sulfur-nitrogen analyzer (model TN/TS3000, manufactured by Siemens, inc.), and the content of aromatic hydrocarbon was analyzed by near infrared spectroscopy.
CO 2 The release profile peak was measured by temperature programmed oxidation. Analyzing on NETZSCH STA 409PC/PG instrument, heating the sample in air atmosphere (heating rate of 10deg.C/min), monitoring at instrument gas outlet with mass spectrometer to obtain sample decomposition to generate CO 2 Curve as a function of temperature.
The calculation formula of the reaction hydrogen consumption is as follows: c (C) f /C p ×H p -H f +16×(S f -C f /C p ×S p )×10 -6 +5.67×(N f -C f /C p ×N p )×10 -6 Wherein C f 、C p Respectively are provided withFor carbon content, H, of raw materials and products f 、H p The H content and the S content of the raw materials and the products respectively f 、S p Sulfur content, N of raw material and product respectively f 、N p The nitrogen content of the raw material and the product respectively.
The reaction rate constant is calculated as follows:LHSV is reaction space velocity, n is reaction progression (calculated as n=1.2), S f 、S p Sulfur content of the raw material and the product, respectively.
Example 1
First bed catalyst: to a certain amount of MoO 3 Respectively adding basic nickel carbonate, ethylene glycol and citric acid into aqueous solution containing phosphoric acid, heating and stirring at 85 ℃ for 3h until the basic nickel carbonate, the ethylene glycol 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 dried for 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly, wherein the pore size distribution of the catalyst at 100-300nm accounts for 15% of the pore volume of the catalyst.
The carrier used for preparing the catalyst is gamma-alumina carrier, the water absorption rate is 1.08mL/g, and the specific surface area is 280m 2 And/g, wherein the average pore diameter is 14.8nm, the proportion of the pore volume with the pore diameter of 100-300nm to the total pore volume is 12%, and the content of sodium oxide in the carrier is 0.05 wt%. The alumina carrier used for preparing the catalyst contains phosphorus element, wherein the phosphorus element in the carrier is from pseudo-boehmite powder used for preparing the carrier, and the phosphorus-containing pseudo-boehmite powder is prepared by introducing a certain amount of phosphoric acid in the preparation process of the pseudo-boehmite powder. The phosphorus-containing pseudo-boehmite powder is molded and baked for 3 hours at 600 ℃ to obtain the phosphorus-containing alumina carrier.
MoO in the preparation of the catalyst 3 30.0 wt.%, 4.5 wt.% NiO, 0.22 Ni/(Ni+Mo) atomic ratio, P 2 O 5 The content was 7.0 wt%, of which 30 wt% of P 2 O 5 From the carrier. The molar ratio of ethylene glycol to the group VIB metal element is 1.5:1, the mole ratio of citric acid to nickel element is 1:1. the catalyst adoptsTemperature programmed oxidation test as shown in FIG. 1, CO was present at 238℃and 345℃respectively 2 The spectral peaks were released with a ratio of the heights of the spectral peaks of 3.5.
Second bed catalyst:
to a certain amount of MoO 3 Respectively adding basic cobalt carbonate, ethylene glycol and citric acid into aqueous solution containing phosphoric acid, heating and stirring at 85 ℃ for 3h until the basic cobalt carbonate, the ethylene glycol and the citric acid are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and dried for 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
The carrier used for preparing the catalyst is gamma-alumina carrier, the water absorption rate is 1.02mL/g, and the specific surface area is 275m 2 And/g, wherein the average pore diameter is 12.5nm, the proportion of the pore volume with the pore diameter of 2-6nm to the total pore volume is 6.0%, and the proportion of the pore volume with the pore diameter of 2-4nm to the total pore volume is 2.0%. The sodium oxide content in the carrier was 0.05%. The alumina carrier used for preparing the catalyst contains phosphorus element, wherein the phosphorus element in the carrier is from pseudo-boehmite powder used for preparing the carrier, and the phosphorus-containing pseudo-boehmite powder is prepared by introducing a certain amount of phosphoric acid in the preparation process of the pseudo-boehmite powder. The phosphorus-containing pseudo-boehmite powder is molded and baked for 3 hours at 600 ℃ to obtain the phosphorus-containing alumina carrier.
MoO in the preparation of the catalyst 3 28.0 wt%, coO 4.9 wt%, co/(Co+Mo) 0.25, P 2 O 5 The content was 5.0 wt%, wherein 30 wt% of P 2 O 5 From the carrier. The molar ratio of ethylene glycol to the group VIB metal element is 1:1, the mole ratio of citric acid to cobalt element is 0.8:1. the catalyst was tested by temperature programmed oxidation, as shown in FIG. 2, with CO at 255℃and 340℃respectively 2 The spectral peak was released, and the ratio of their peak heights was 2.2.
Performance test of catalyst system:
the volume ratio of the first bed catalyst to the second bed catalyst is 1:1, and the reaction temperature of the two beds is 360 ℃. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 8.9ppm, the aromatic hydrocarbon content is 27.0 wt%, the reaction hydrogen consumption is 0.97%, the reaction conditions are kept stable, and the activity retention degree is 88.5% after 12 days of reaction.
Example 2
First bed catalyst: to a certain amount of MoO 3 Respectively adding basic nickel carbonate, glycerol and acetic acid into aqueous solution containing phosphoric acid, heating and stirring at 85 ℃ for 3 hours until the basic nickel carbonate, the glycerol and the acetic acid are completely dissolved, and obtaining impregnation solution containing active metals. Uniformly mixing the impregnating solution and the carrier, standing for 3h, and drying at 120 ℃ for 5h to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly, wherein the pore size distribution of the catalyst at 100-300nm accounts for 15% of the pore volume of the catalyst.
The first bed catalyst of example 2 was the same support as the first bed catalyst of example 1.
MoO in the preparation of the catalyst 3 The content was 24.0 wt%, the NiO content was 7.0 wt%, the Ni/(Ni+Mo) atomic ratio was 0.36, and P 2 O 5 The content was 6.5 wt%, of which 20 wt% of P 2 O 5 From the carrier. The molar ratio of glycerol to group VIB metal was 1.2:1, the molar ratio of acetic acid to nickel element is 1.5:1. the catalyst adopts a temperature programming oxidation test, and CO appears at 240 ℃ and 340 ℃ respectively 2 The spectral peaks were released with a ratio of the heights of the spectral peaks of 3.3.
Second bed catalyst:
to a certain amount of MoO 3 Respectively adding basic cobalt carbonate, glycerol and acetic acid into aqueous solution containing phosphoric acid, heating and stirring at 90 ℃ for 3 hours until the basic cobalt carbonate, glycerol and acetic acid are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed, and then the mixture is stood for 5 hours, and 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 second bed catalyst of example 2 was the same support as the second bed catalyst of example 1.
MoO in the preparation of the catalyst 3 15.0 wt.%, coO 3.8 wt.%, co/(Co+Mo) 0.33, P 2 O 5 The content was 8.0 wt%, of which 30 wt% of P 2 O 5 From the carrier. Glycerol and group VIB metalsThe molar ratio of (2): 1, the molar ratio of acetic acid to cobalt element is 3:1. the catalyst adopts a temperature programming oxidation test, and CO appears at 245 ℃ and 325 ℃ respectively 2 The spectral peaks were released with a ratio of their peak heights of 3.5.
Performance test of catalyst system:
the volume ratio of the first bed catalyst to the second bed catalyst is 3:1, and the reaction temperature of the two beds is 360 ℃. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 6.3ppm, the aromatic hydrocarbon content is 25.6 wt%, the reaction hydrogen consumption is 1.15 wt%, the reaction conditions are kept stable, and the activity retention degree is 86.6% after 12 days of reaction.
Example 3
First bed catalyst: to a certain amount of MoO 3 Respectively adding basic nickel carbonate, butanol and acetic acid into aqueous solution containing phosphoric acid, heating and stirring at 85 ℃ for 3h until the basic nickel carbonate, butanol and acetic acid are completely dissolved, and obtaining impregnation solution containing active metals. Uniformly mixing the impregnating solution and the carrier, standing for 3h, and drying at 120 ℃ for 5h to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly, wherein the pore size distribution of the catalyst at 100-300nm accounts for 15% of the pore volume of the catalyst.
Example 3 the same support as the first bed catalyst of example 1 was used.
MoO in the preparation of the catalyst 3 38.0 wt.%, 6.5 wt.% NiO, 0.25 Ni/(Ni+Mo) atomic ratio, P 2 O 5 The content is 5.0 wt%, of which 10 wt% of P 2 O 5 From the carrier. The molar ratio of butanol to group VIB metal was 0.6:1, the mole ratio of citric acid to nickel element is 1.2:1. the catalyst adopts a temperature programming oxidation test, and CO appears at 230 ℃ and 348 ℃ respectively 2 The spectral peaks were released with a ratio of the heights of the spectral peaks of 1.9.
Second bed catalyst:
to a certain amount of MoO 3 Respectively adding basic cobalt carbonate, butanol and acetic acid into aqueous solution containing phosphoric acid, heating and stirring at 95 ℃ for 3h until the basic cobalt carbonate, butanol and acetic acid are completely dissolved, and obtaining impregnation solution containing active metals. Will impregnate The solution and the carrier are uniformly mixed and then are kept stand for 5 hours, and the catalyst with the particle size of 1.6mm and the shape of a butterfly is prepared by drying for 5 hours at 120 ℃. Example 3 the same support as the second bed catalyst of example 1 was used.
MoO in the preparation of the catalyst 3 24.0 wt.%, coO 6.0 wt.%, co/(Co+Mo) 0.32, P 2 O 5 The content is 5.0 wt%, of which 10 wt% of P 2 O 5 From the carrier. The molar ratio of butanol to group VIB metal is 1:1, the molar ratio of acetic acid to cobalt element is 1.6:1. the catalyst adopts a temperature programming oxidation test, and CO appears at 230 ℃ and 325 ℃ respectively 2 The spectral peaks were released with a ratio of their peak heights of 4.2.
Performance test of catalyst system:
the volume ratio of the first bed catalyst to the second bed catalyst is 3:1, and the reaction temperature of the two beds is 360 ℃. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 7.5ppm, the aromatic hydrocarbon content is 25.9 wt%, the reaction hydrogen consumption is 1.1%, the reaction conditions are kept stable, and the activity retention degree is 83.8% after 12 days of reaction.
Example 4
First bed catalyst:
to a certain amount of MoO 3 Respectively adding basic nickel carbonate, butanol and triethanolamine into aqueous solution containing phosphoric acid, heating and stirring at 85deg.C for 3 hr to dissolve completely to obtain impregnation solution containing active metal. Uniformly mixing the impregnating solution and the carrier, standing for 3h, and drying at 120 ℃ for 5h to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly, wherein the pore size distribution of the catalyst at 100-300nm accounts for 15% of the pore volume of the catalyst.
Example 4 the same support as the first bed catalyst of example 1 was used.
MoO in the preparation of the catalyst 3 26.0 wt.%, 5.5 wt.% NiO, 0.29 Ni/(Ni+Mo) atomic ratio, P 2 O 5 The content was 4.5 wt%, of which 10 wt% of P 2 O 5 From the carrier. The molar ratio of butanol to group VIB metal is 1:1, the mol ratio of triethanolamine to nickel element is 1:1. the catalyst adopts a temperature programming oxidation test, and CO appears at 230 ℃ and 332 ℃ respectively 2 The spectral peaks were released with a ratio of the heights of the spectral peaks of 2.7.
Second bed catalyst:
to a certain amount of MoO 3 Respectively adding basic cobalt carbonate, butanol and triethanolamine into aqueous solution containing phosphoric acid, heating and stirring at 85deg.C for 3 hr to dissolve completely to obtain impregnation solution containing active metal. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 4 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. Example 4 the same support as the second bed catalyst of example 1 was used.
MoO in the preparation of the catalyst 3 24.0 wt.%, coO 6.0 wt.%, co/(Co+Mo) 0.32, P 2 O 5 The content was 7.0 wt%, of which 10 wt% of P 2 O 5 From the carrier. The molar ratio of butanol to group VIB metal is 2:1, the mol ratio of triethanolamine to cobalt element is 1:1. the catalyst adopts a temperature programming oxidation test, and CO appears at 245 ℃ and 335 ℃ respectively 2 The spectral peaks were released with a ratio of their peak heights of 4.5.
Performance test of catalyst system:
the volume ratio of the first bed catalyst to the second bed catalyst is 2:1, and the reaction temperature of the two beds is 360 ℃. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 8.5ppm, the aromatic hydrocarbon content is 26.3 weight percent, the reaction hydrogen consumption is 1.05%, the reaction conditions are kept stable, and the activity retention degree is 85% after 12 days of reaction.
Example 5
The first bed catalyst and the second bed catalyst were the same as the first and second bed catalysts in example 1, respectively.
Performance test of catalyst system:
the volume ratio of the first bed catalyst to the second bed catalyst is 1:2, and the reaction temperature of the two beds is 360 ℃. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 8.6ppm, the aromatic hydrocarbon content is 27.5 wt%, the reaction hydrogen consumption is 0.92%, the reaction conditions are kept stable, and the activity retention degree is 88.6% after 12 days of reaction.
Example 6
First bed catalyst:
to a certain amount of MoO 3 Respectively adding basic nickel carbonate, ethylene glycol and citric acid into aqueous solution containing phosphoric acid, heating and stirring at 95 ℃ for 3 hours until the basic nickel carbonate, the ethylene glycol and the citric acid are completely dissolved, and obtaining impregnation solution containing active metals. Uniformly mixing the impregnating solution and the carrier, standing for 3h, and drying at 120 ℃ for 5h to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly, wherein the pore size distribution of the catalyst at 100-300nm accounts for 10% of the pore volume of the catalyst.
The carrier used for preparing the catalyst is gamma-alumina carrier, the water absorption rate is 1.04mL/g, and the specific surface area is 285m 2 And/g, wherein the average pore diameter is 12.6nm, and the proportion of the pore volume with the pore diameter of 100-300nm to the total pore volume is 8%. The sodium oxide content of the support was 0.03 wt%. The alumina carrier used for preparing the catalyst does not contain phosphorus element.
MoO in the preparation of the catalyst 3 26.0 wt.%, 5.5 wt.% NiO, 0.29 Ni/(Ni+Mo) atomic ratio, P 2 O 5 The content was 5.9% by weight. The molar ratio of ethylene glycol to the group VIB metal element is 0.8:1, the mole ratio of citric acid to nickel element is 1:1. the catalyst adopts a temperature programming oxidation test, and CO appears at 240 ℃ and 345 ℃ respectively 2 The spectral peaks were released with a ratio of their spectral peak heights of 1.2.
Second bed catalyst:
to a certain amount of MoO 3 Respectively adding basic cobalt carbonate, butanol and acetic acid into aqueous solution containing phosphoric acid, heating and stirring at 95 ℃ for 3h until the basic cobalt carbonate, butanol and acetic 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 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
For preparing catalystsThe carrier is gamma-alumina carrier, the water absorption rate is 0.97mL/g, and the specific surface area is 280m 2 And/g, wherein the average pore diameter is 11.7nm, the proportion of the pore volume with the pore diameter of 2-6nm to the total pore volume is 7.2%, and the proportion of the pore volume with the pore diameter of 2-4nm to the total pore volume is 2.5%. The sodium oxide content in the carrier was 0.05%. The alumina carrier used for preparing the catalyst does not contain phosphorus element.
MoO in the preparation of the catalyst 3 24.0 wt.%, coO 6.0 wt.%, co/(Co+Mo) 0.32, P 2 O 5 The content was 5.0 wt%. The molar ratio of butanol to group VIB metal is 1:1, the molar ratio of acetic acid to cobalt element is 1:1. the catalyst adopts a temperature programming oxidation test, and CO appears at 230 ℃ and 325 ℃ respectively 2 The spectral peaks were released with a ratio of their peak heights of 2.1.
Performance test of catalyst system:
the volume ratio of the first bed catalyst to the second bed catalyst is 1:1, and the reaction temperature of the two beds is 360 ℃. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 7.5ppm, the aromatic hydrocarbon content is 27.6 wt%, the reaction hydrogen consumption is 0.95%, the reaction conditions are kept stable, and the activity retention degree after 12 days of reaction is 86.5%.
Example 7
The first bed catalyst was the same as the first bed catalyst in example 1.
Second bed catalyst:
to a certain amount of MoO 3 Respectively adding basic cobalt carbonate, basic nickel carbonate, ethylene glycol and citric acid into aqueous solution containing phosphoric acid, heating and stirring at 85 ℃ for 3 hours until the basic cobalt carbonate, the basic nickel carbonate, the ethylene glycol 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 carrier used for preparing the catalyst is gamma-alumina carrier, the water absorption rate is 1.02mL/g, and the specific surface area is 275m 2 Per g, average pore diameter of 12.5nm, pore volume of 2-6nm in proportion to total pore volume of 6.0%, pore volume of 2-4nm in proportion to total The proportion of pore volume was 2%. The sodium oxide content of the support was 0.05% by weight. The alumina carrier used for preparing the catalyst contains phosphorus element, wherein the phosphorus element in the carrier is from pseudo-boehmite powder used for preparing the carrier, and the phosphorus-containing pseudo-boehmite powder is prepared by introducing a certain amount of phosphoric acid in the preparation process of the pseudo-boehmite powder. The phosphorus-containing pseudo-boehmite powder is molded and baked for 3 hours at 600 ℃ to obtain the phosphorus-containing alumina carrier.
MoO in the preparation of the catalyst 3 28.0 wt%, coO 3 wt%, niO 2 wt%, co+Ni/Co+Ni+Mo atomic ratio of 0.256, co/(Co+Ni) atomic ratio of 0.6, P 2 O 5 The content was 5.0 wt%, wherein 30 wt% of P 2 O 5 From the carrier. The molar ratio of ethylene glycol to the group VIB metal element is 1.5:1, the mole ratio of citric acid to the sum of cobalt element and nickel element is 0.8:1. the catalyst adopts a temperature programming oxidation test, and CO appears at 255 ℃ and 340 ℃ respectively 2 The spectral peak was released, and the ratio of their peak heights was 4.3.
Performance test of catalyst system:
the volume ratio of the first bed catalyst to the second bed catalyst is 1:1, and the reaction temperature of the two beds is 360 ℃. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 7.3ppm, the aromatic hydrocarbon content is 26.5 wt%, the reaction hydrogen consumption is 1.05%, the reaction conditions are kept stable, and the activity retention degree after 12 days of reaction is 84.2%.
Example 8
First bed catalyst:
to a certain amount of MoO 3 Respectively adding basic nickel carbonate, ethylene glycol and citric acid into aqueous solution containing phosphoric acid, heating and stirring at 85 ℃ for 3h until the basic nickel carbonate, the ethylene glycol and the citric acid are completely dissolved, and obtaining impregnation solution containing active metals. Uniformly mixing the impregnating solution and the carrier, standing for 3h, and drying at 120 ℃ for 5h to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly, wherein the pore size distribution of the catalyst at 100-300nm accounts for 15% of the pore volume of the catalyst. The support is the same as the support of the first bed catalyst in example 1.
MoO in the preparation of the catalyst 3 30.0 wt.%, 4.5 wt.% NiO, 0.22 Ni/(Ni+Mo) atomic ratio, P 2 O 5 The content was 7.0 wt%, of which 30 wt% of P 2 O 5 From the carrier. The molar ratio of ethylene glycol to the group VIB metal element is 0.3:1, the mole ratio of citric acid to nickel element is 1:1. the catalyst adopts a temperature programming oxidation test, and CO appears at 243 ℃ and 342 ℃ respectively 2 The spectral peaks were released with a ratio of their spectral peak heights of 0.73.
The second bed catalyst was the same as the second bed catalyst in example 1.
The volume ratio of the first bed catalyst to the second bed catalyst is 1:1, and the reaction temperature of the two beds is 360 ℃. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 9.0ppm, the aromatic hydrocarbon content is 28.2 wt%, the reaction hydrogen consumption is 0.88%, the reaction conditions are kept stable, and the activity retention degree after 12 days of reaction is 85.4%.
Example 9
First bed catalyst: the procedure of example 1 was followed for the first bed catalyst, except that the molar ratio of citric acid to nickel element was 0.2:1.
the second bed catalyst was the same as the second bed catalyst of example 1.
Performance test of catalyst system:
the volume ratio of the first bed catalyst to the second bed catalyst is 1:1, and the reaction temperature of the two beds is 360 ℃. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 10.5ppm, the aromatic hydrocarbon content is 28.5 wt%, the reaction hydrogen consumption is 0.78%, the reaction conditions are kept stable, and the activity retention degree is 87.2% after 12 days of reaction.
Example 10
First bed catalyst: a catalyst was prepared as in the first bed catalyst of example 1, the pore size distribution of the catalyst being 2% of the catalyst pore volume at 100-300 nm.
Wherein the carrier used for preparing the catalyst is gamma-alumina carrier, the water absorption rate is 0.99mL/g,specific surface area of 286m 2 And/g, wherein the average pore diameter is 11.8nm, the proportion of the pore volume with the pore diameter of 100-300nm to the total pore volume is 1%, and the content of sodium oxide in the carrier is 0.05 wt%. The alumina carrier used for preparing the catalyst contains phosphorus element, wherein the phosphorus element in the carrier is from pseudo-boehmite powder used for preparing the carrier, and the phosphorus-containing pseudo-boehmite powder is prepared by introducing a certain amount of phosphoric acid in the preparation process of the pseudo-boehmite powder. The phosphorus-containing pseudo-boehmite powder is molded and baked for 3 hours at 600 ℃ to obtain the phosphorus-containing alumina carrier.
Second bed catalyst: the same as the second bed catalyst in example 1.
Performance test of catalyst system:
the volume ratio of the first bed catalyst to the second bed catalyst is 1:1, and the reaction temperature of the two beds is 360 ℃. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 10.2ppm, the aromatic hydrocarbon content is 27.2 wt%, the reaction hydrogen consumption is 0.95%, the reaction conditions are kept stable, and the activity retention degree is 82.1% after 12 days of reaction.
Comparative example 1
First bed catalyst:
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 95 ℃ for 2h until the basic nickel carbonate and the citric acid are completely dissolved, and obtaining impregnation solution containing active metals. Uniformly mixing the impregnating solution and the carrier, standing for 3h, and drying at 120 ℃ for 5h to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly, wherein the pore size distribution of the catalyst at 100-300nm accounts for 15% of the pore volume of the catalyst. The support is the same as the support of the first bed catalyst of example 1.
MoO in the preparation of the catalyst 3 30.0 wt.%, 4.5 wt.% NiO, 0.22 Ni/(Ni+Mo) atomic ratio, P 2 O 5 The content was 7.0 wt%, of which 30 wt% of P 2 O 5 From the carrier. The mole ratio of citric acid to nickel element is 0.8:1. the catalyst adopts a temperature programming oxidation test, and CO appears at 360 DEG C 2 The spectral peaks were released.
Second bed catalyst:
to a certain amount of MoO 3 Respectively adding basic cobalt carbonate, basic nickel carbonate and citric acid into aqueous solution containing phosphoric acid, heating and stirring at 95 ℃ for 2h until the basic cobalt carbonate, 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 phosphorus-containing alumina support was chosen to be the same as the support in the second bed catalyst of example 1.
MoO in the preparation of the catalyst 3 28.0 wt%, 2.0 wt% CoO, 4.0 wt% NiO, 0.29 (Co+Ni)/(Co+Ni+Mo), 0.33 (Co/(Co+Ni) and P) 2 O 5 The content was 5.0 wt%, of which 30 wt% of P 2 O 5 From the carrier. The molar ratio of citric acid to group VIII metal was 0.8:1. the catalyst adopts a temperature programming oxidation test, and CO appears at 375 DEG C 2 The spectral peaks were released.
Performance test of catalyst system:
the volume ratio of the first bed catalyst to the second bed catalyst is 1:1, and the reaction temperature of the two beds is 360 ℃. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 26.0ppm, the aromatic hydrocarbon content is 29.5 wt%, the reaction hydrogen consumption is 0.86%, the reaction conditions are kept stable, and the activity retention degree is 77.2% after 12 days of reaction.
Comparative example 2
First bed 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 95 ℃ for 2h until the basic nickel carbonate and the glycerol are completely dissolved, and obtaining impregnation solution containing active metals. Uniformly mixing the impregnating solution and the carrier, standing for 3h, and drying at 120 ℃ for 5h to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly, wherein the pore size distribution of the catalyst at 100-300nm accounts for 15% of the pore volume of the catalyst.
The support is the same as the support of the first bed catalyst of example 1.
Preparation of the catalystMiddle MoO 3 The content was 24.0 wt%, the NiO content was 7 wt%, the Ni/(Ni+Mo) atomic ratio was 0.36, and P 2 O 5 The content was 6.5 wt%, of which 20 wt% of P 2 O 5 From the carrier. The molar ratio of glycerol to nickel element is 1.2:1.
the catalyst adopts a temperature programming oxidation test, and CO appears at 235 DEG C 2 The spectral peaks were released.
Second bed 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 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 phosphorus-containing alumina support was chosen to be the same as the support in the second bed catalyst of example 1.
MoO in the preparation of the catalyst 3 The content was 24.0 wt%, the NiO content was 6.0 wt%, the Ni/(Ni+Mo) atomic ratio was 0.33, and P 2 O 5 The content was 8.0 wt%, of which 15 wt% of P 2 O 5 From the carrier. The molar ratio of glycerol to group VIB metal is 1:1. the catalyst adopts a temperature programming oxidation test, and CO appears at 260 DEG C 2 The spectral peaks were released.
Performance test of catalyst system:
the volume ratio of the first bed catalyst to the second bed catalyst is 3:1, and the reaction temperature of the two beds is 360 ℃. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 28.5ppm, the aromatic hydrocarbon content is 29.8 wt%, the reaction hydrogen consumption is 0.84%, the reaction conditions are kept stable, and the activity retention degree after 12 days of reaction is 76.0%.
Comparative example 3
First bed catalyst:
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 95 ℃ for 2h until the basic nickel carbonate and the citric acid are completely dissolved, and obtaining impregnation solution containing active metals. Mixing the impregnating solution with a carrierMixing uniformly, standing for 3h, and drying at 120deg.C for 5h to obtain the catalyst with particle diameter of 1.6mm and butterfly shape, wherein the pore size distribution of the catalyst at 100-300nm accounts for 30% of the pore volume of the catalyst.
The procedure for the preparation of the selected support was the same as that for the first catalyst support in example 1. The carrier is gamma-alumina carrier, the water absorption rate is 1.3mL/g, and the specific surface area is 270m 2 And/g, the average pore diameter is 16.5nm, and the proportion of the pore volume with the pore diameter of 100-300nm to the total pore volume is 25%. The sodium oxide content of the support was 0.05% by weight.
MoO in the preparation of the catalyst 3 30.0 wt.%, 4.5 wt.% NiO, 0.22 Ni/(Ni+Mo) atomic ratio, P 2 O 5 The content was 7.0 wt%, of which 30 wt% of P 2 O 5 From the carrier. The mole ratio of citric acid to nickel element is 0.8:1. the catalyst adopts a temperature programming oxidation test, and CO appears at 365 DEG C 2 The spectral peaks were released.
Second bed catalyst:
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 95 ℃ 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 phosphorus-containing alumina support was chosen to be the same as the support in the second catalyst bed of example 1.
MoO in the preparation of the catalyst 3 28.0 wt.%, 4.9 wt.% NiO, 0.25 Ni/(Ni+Mo) atomic ratio, P 2 O 5 The content is 5.0%, wherein 15% by weight of P 2 O 5 From the carrier. The mole ratio of citric acid to the group VIII metal element is 1:1. the catalyst adopts a temperature programming oxidation test, and CO appears at 360 DEG C 2 The spectral peaks were released.
Performance test of catalyst system:
the volume ratio of the first bed catalyst to the second bed catalyst is 2:1, and the reaction temperature of the two beds is 360 ℃. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 35ppm, the aromatic hydrocarbon content is 27.5 wt%, the reaction hydrogen consumption is 1.03%, the reaction conditions are kept stable, and the activity retention degree after 12 days of reaction is 75.4%.
Comparative example 4
The first and second bed catalysts were the same as the first and second bed catalysts of example 1, respectively, except that the volume ratio of the first bed catalyst to the second bed catalyst was 1:8. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content in the product is 27.0ppm, the aromatic hydrocarbon content is 30.5 wt%, the reaction hydrogen consumption is 0.73%, the reaction conditions are kept stable, and the activity retention degree after 12 days of reaction is 79.5%.
In the invention, two specific catalysts are selected for grading, so that the catalyst has good desulfurization and dearomatization effects and lower reaction hydrogen consumption.
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 method of catalyst sizing, the method comprising: a first catalyst and a second catalyst which are sequentially filled along the material flow direction;
the first catalyst comprises at least one VIB group metal element, a co-active component, a phosphorus element, a first carrier and at least two of an organic alcohol compound, a carboxylic acid compound and an organic amine compound; the co-active component comprises nickel, optionally at least one of the elements subway, ruthenium and osmium; the pore size distribution of the first catalyst at 100-300nm accounts for no more than 20% of the pore volume of the catalyst; wherein the first catalyst comprises at least two COs in the temperature-programmed oxidation process 2 A release peak, a first release peak temperature of 210-280 ℃ and a second release peak temperatureAt 320-380 ℃, and the ratio of the peak height of the spectrum peak to the peak height is 0.5-4:1, a step of;
The second catalyst comprises cobalt element and optionally one of other metal elements of group VIII, at least one metal element of group VIB, phosphorus element, a second carrier and at least two of an organic alcohol compound, a carboxylic acid compound and an organic amine compound; wherein the second catalyst comprises at least two COs in the temperature-programmed oxidation process 2 Releasing the spectral peak, wherein the temperature of the third releasing spectral peak is 200-300 ℃, the temperature of the fourth releasing spectral peak is 300-400 ℃, and the ratio range of the height of the spectral peak to the peak is 1-5:1, a step of;
wherein the loading volume ratio of the first catalyst to the second catalyst is 1:2-5:1.
2. the method of claim 1, wherein the loading volume ratio of the first catalyst to the second catalyst is 1:1-4:1, a step of;
and/or, the content of the auxiliary active component is 1-15 wt% based on the total amount of the first catalyst, and the content of the group VIB metal element is 12-50 wt% based on oxide;
preferably, the atomic ratio of nickel to the total amount of the co-active components is not less than 0.8, more preferably 0.85 to 1;
preferably in P 2 O 5 The phosphorus content in the first catalyst is 3-10 wt%;
preferably, the first catalyst comprises at least two CO during the temperature-programmed oxidation process 2 Releasing spectral peaks, wherein the temperature of the first releasing spectral peak is 230-260 ℃, the temperature of the second releasing spectral peak is 320-360 ℃, and the ratio range of the spectral peak heights is 0.7-3.5:1, a step of;
preferably, the pore size distribution of the first catalyst at 100-300nm accounts for 5-20% of the pore volume of the first catalyst;
preferably, the atomic ratio of the co-active component to the total of co-active component and group VIB metal element is 0.1-0.5, further preferably 0.2-0.35;
and/or, the group VIB metal elements in the first catalyst and the second catalyst are each independently selected from at least one of chromium, molybdenum, and tungsten.
3. The process according to claim 1, wherein the content of cobalt element and optionally other group VIII metal elements is 1-15 wt%, and the content of group VIB metal element is 12-50 wt%, calculated as oxides, based on the total amount of the second catalyst;
preferably, the atomic ratio of the cobalt element to the total amount of the cobalt element and optionally other group VIII metal elements is not less than 0.8, further preferably 0.85 to 1;
preferably in P 2 O 5 The phosphorus content of the second catalyst is 3-10 wt%;
preferably, the second catalyst comprises at least two CO during the temperature-programmed oxidation process 2 Releasing spectral peak, the third releasing spectral peak temperature is 220-280 ℃, the fourth releasing spectral peak temperature is 320-380 ℃, and the spectral peak height ratio range is 1.5-3:1, a step of;
preferably, the atomic ratio of the cobalt element and optionally the group VIII other metal element to the total of cobalt element and optionally the group VIII other metal element and the group VIB metal element is 0.1 to 0.5, further preferably 0.2 to 0.35.
4. A method according to any one of claims 1-3, wherein the first support is a first alumina support;
and/or the second carrier is a second alumina carrier;
preferably, the first alumina carrier and the second alumina carrier both contain phosphorus element;
preferably in P 2 O 5 The phosphorus element in the first alumina carrier and the second alumina carrier independently accounts for 10-40 wt% of the total phosphorus content in the first catalyst and the second catalyst, and more preferably 20-30 wt%;
preferably, the precursors of the first alumina carrier and the second alumina carrier are respectively and independently pseudo-boehmite, and the pseudo-boehmite contains phosphorus element;
preferably, the sodium oxide content in the pseudo-boehmite is not more than 0.08% by weight, further preferably not more than 0.05% by weight.
5. The method of claim 4, wherein the first alumina support has a water absorption greater than 0.9mL/g and a specific surface area greater than 260m 2 /g, average pore size greater than 8nm;
preferably, the pore size distribution of the first alumina carrier at 100-300nm accounts for 5-15% of the pore volume of the first alumina carrier;
and/or the water absorption rate of the second alumina carrier is more than 0.9mL/g, and the specific surface area is more than 260m 2 /g, average pore size greater than 8nm;
preferably, in the second alumina carrier, the pore volume with the pore diameter distribution of 2-6nm accounts for not more than 10%, and more preferably not more than 8% of the total pore volume of the second alumina carrier;
preferably, in the second alumina support, the pore volume having a pore size distribution of from 2 to 4nm comprises no more than 4%, more preferably no more than 2% of the total pore volume of the second alumina support.
6. The process according to any one of claims 1 to 3, wherein the molar ratio of organic alcohol compound to group VIB metal element in the first and second catalysts is each independently 0.2 to 4:1, a step of;
preferably, in the first catalyst, the molar ratio of the carboxylic acid compound and/or the organic amine compound to the auxiliary active component is 0.3-1.5:1, a step of;
Preferably, in the second catalyst, the molar ratio of the carboxylic acid compound and/or the organic amine compound to the cobalt element and optionally other metal elements of group VIII is 0.1-4:1, a step of;
preferably, in the first catalyst and the second catalyst, the organic alcohol compound is each independently selected from at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, heptanol, ethylene glycol, glycerol, butanetetraol, polyethylene glycol, polyglycerol, pentaerythritol, xylitol, sorbitol, and trimethylolethane, further preferably at least one of butanol, glycerol, propanol, and ethylene glycol;
preferably, in the first catalyst and the second catalyst, the carboxylic acid compound is each independently selected from at least one of formic acid, acetic acid, propionic acid, citric acid, octanoic acid, adipic acid, malonic acid, succinic acid, maleic acid, valeric acid, caproic acid, capric acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, stearic acid and tartaric acid, and further preferably at least one of formic acid, citric acid and acetic acid;
preferably, in the first catalyst and the second catalyst, the organic amine compound is at least one selected from ethylenediamine, ethylenediamine tetraacetic acid, ethanolamine, triethanolamine and cyclohexanediamine tetraacetic acid.
7. A process according to any one of claims 1 to 3, wherein the equivalent diameters of the first and second catalysts are each independently 0.5 to 1.8mm, preferably 0.8 to 1.6mm;
and/or the shape of the first catalyst and the second catalyst are each independently butterfly, cylindrical, clover, honeycomb or other irregular shape.
8. The method of any of claims 1-7, wherein the first catalyst is prepared by a process comprising: introducing at least two of a co-active component precursor, a VIB group metal precursor, a phosphorus-containing compound, an organic alcohol compound, a carboxylic acid compound and an organic amine compound into a first carrier by adopting an impregnation method, and then drying;
and/or, the preparation method of the second catalyst comprises the following steps: introducing a cobalt element precursor, optionally at least two of a group VIII other metal precursor, a group VIB metal precursor, a phosphorus-containing compound and an organic alcohol compound, a carboxylic acid compound and an organic amine compound into a second carrier by adopting the same impregnation method as the first catalyst, and then drying;
preferably, in the preparation method of the first catalyst and the second catalyst, the drying conditions each independently include: the temperature is 60-200deg.C, and the time is 2-10h.
9. A process for hydrofining a catalyst in a distillate, wherein the process comprises: filling a first catalyst and a second catalyst in a hydrofining device according to the grading method of any one of claims 1-8 under hydrofining conditions, and injecting distillate to be treated into the hydrofining device for reaction;
preferably, the proportion of the secondary hydrogenated diesel oil in the distillate to be treated is 10-30 wt%.
10. The process according to claim 9, wherein the fraction oil to be treated has a straight run diesel content of 75-85% by weight, a catalytic diesel content of 15-25% by weight, a sulfur content of 2000-18000ppm and an aromatic content of 15-45% by weight;
preferably, the reaction conditions include: the temperature is 300-450 ℃, the pressure is 3-20MPa, and the volume airspeed is 0.5-3 hours -1 The volume ratio of the hydrogen oil is 100-2000:1, a step of;
preferably, the sulfiding conditions of the first catalyst and the second catalyst comprise: the temperature rising rate is 5-60 ℃/h, the vulcanizing temperature is 280-420 ℃, the vulcanizing time is 8-48h, the vulcanizing pressure is 0.1-15MPa, and the volume airspeed is 0.5-20 h -1 The volume ratio of the hydrogen oil is 100-2000:1.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210814381.1A CN117427647A (en) | 2022-07-12 | 2022-07-12 | Catalyst grading method and hydrofining method of catalyst in distillate oil |
| PCT/CN2023/106677 WO2024012422A1 (en) | 2022-07-12 | 2023-07-11 | Hydrogenation catalyst, preparation method therefor, and use thereof |
| TW112125781A TW202402391A (en) | 2022-07-12 | 2023-07-11 | Hydrogenation catalyst, preparation method therefor, and use thereof |
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