CN109569664B - Vulcanized hydrogenation catalyst, and preparation method and application thereof - Google Patents
Vulcanized hydrogenation catalyst, and preparation method and application thereof Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group metals
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The invention relates to the field of hydrorefining and discloses a vulcanized hydrogenation catalyst as well as a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) preparing a solution A containing a VIB group metal salt, a sulfur source and an optional water-soluble organic dispersant, wherein the pH value of the solution A is 1-8; (2) aging the solution A in the step (1) at 20-120 ℃ for 0.5-48 hours to obtain an aged product; (3) impregnating a catalyst support with the aged product; (4) roasting the solid material impregnated in the step (3) in an inert or reducing atmosphere; the method further comprises the step of introducing a group VIII metal element in step (1) and/or step (3). The method provided by the invention omits a vulcanization process, and the prepared catalyst active component is highly dispersed and fully vulcanized, so that the hydrogenation performance of the catalyst is obviously improved finally.
Description
Technical Field
The invention relates to the field of hydrofining, in particular to a preparation method of a vulcanized hydrogenation catalyst, the vulcanized hydrogenation catalyst prepared by the method and application of the vulcanized hydrogenation catalyst in hydrodesulfurization and/or hydrodenitrogenation.
Background
The hydrogenation technology is the most important means for producing clean oil products, wherein the high-efficiency hydrogenation catalyst is the core technology of the hydrogenation technology. Uses VIB group metal W or Mo as main active component, VIII group metal Ni or Co as auxiliary active component and gamma-A12O3Or modified gamma-A12O3The supported catalyst as a carrier is a hydrogenation catalyst which is widely used in industry at present.
The traditional preparation technology mainly adopts an impregnation method to introduce an oxidized precursor of an active component into a carrier pore passage, and then the hydrogenation catalyst is obtained through aging, drying and roasting. Wherein the Co, Ni, Mo and W active components are present in the form of oxides. However, in actual use, the active components of the hydrogenation catalyst exist in the form of sulfides of Co, Ni, Mo and W, so that the hydrogenation catalyst is subjected to sulfidation activation, namely presulfiding, before use. The presulfurization process in the traditional preparation technology adopts an in-situ sulfuration technology, namely, firstly, an oxidation state catalyst is loaded into a hydrogenation reactor, and then hydrogen and a vulcanizing agent are introduced into the reactor for sulfuration in the process of continuously raising the temperature, although the technology is still the most widely applied technology at present, the technology still has a series of problems: 1) the vulcanization time is too long, and the start-up is delayed; 2) the device is easy to corrode and age in the vulcanization process; 3) the vulcanizing agent is inflammable and toxic, and is easy to cause environmental pollution; 4) higher cost, etc. In view of the problems of the "in-plant" vulcanization technology, CN1861258A, CN 1861260A, CN 101088619A, CN 101088620A, CN 1994567A, CN 101279296A, CN 101491725A, US6365542 developed a series of "out-of-plant" vulcanization technologies, which mainly include two routes: the first technical route is to introduce a vulcanizing agent (elemental sulfur, vegetable oil, organic sulfide, organic polysulfide, sulfone, sulfoxide, etc.) into the voids of the hydrogenation catalyst in an oxidized state by sublimation, melting or impregnation, and then to vulcanize the catalyst by heat treatment in the presence of an inert gas; the second technical route is to complete the presulfiding of the catalyst in the oxidation state in the presence of hydrogen and hydrogen sulfide or readily decomposable organic sulfiding agents on a dedicated presulfiding unit. However, no matter the in-situ vulcanization or the out-of-situ vulcanization is adopted, the catalyst is required to be firstly subjected to an oxidation state and then pre-vulcanized, so that the preparation process of the catalyst is complex, and meanwhile, certain environmental protection and safety risks are brought by the use and transportation of a large amount of vulcanizing agents.
In view of the problems of the two sulfidation methods, researchers began to turn their attention to direct synthesis of presulfided hydrogenation catalysts or search for a preparation route.
For example, CN102039147A discloses a preparation method of a sulfided catalyst, which uses alkyl ammonium molybdenum (tungstate) sulfide salt containing metal Mo or W, inorganic salt of Ni or Co, and organic assistant as impregnation liquid, and impregnates a required catalyst carrier, and then dries the catalyst carrier to directly obtain the sulfided catalyst. The method has the advantages of simple preparation process, no need of inert gas protection in the preparation process, easy formation of II-type active phase with high catalytic activity, and high catalyst service performance, but finally has high preparation cost and low application possibility because the thio-molybdenum (tungstate) which is difficult to synthesize and has very high price is also adopted as an active precursor.
CN104707629A discloses a preparation method of a supported transition metal sulfide hydrogenation catalyst, which adopts tetrathiomolybdate and soluble nickel and cobalt salts to prepare a Ni (Co) MoS hydrofining catalyst with high sulfidity by a three-step method of liquid-phase impregnation adsorption-precipitation-high-temperature reduction. Compared with the method, the method avoids the use of a template agent, an alkaline solution and an organic solvent. However, in the preparation method, under the condition of a certain solution volume, the loading amount of the active metal is uncontrollable in the liquid-phase impregnation and adsorption process, and the relative atomic ratio of the auxiliary active component Ni (Co) to the main active component Mo is difficult to adjust; in addition, in the adsorption equilibrium and precipitation, active metal components which cannot be loaded on the carrier still exist in the solution, so that the metal utilization rate is low, and the raw material loss is caused.
CN105521799A discloses a vulcanization type hydrogenation catalyst and a preparation method thereof, wherein the method adopts liquid phase reaction to generate MoS3Then the catalyst is absorbed on a deposition carrier, and finally the hydrogenation catalyst with high sulfuration degree, high dispersivity and high activity can be obtained after the treatment of reducing gas or inert gas. However, this approach requires consideration to avoid MoS2Oxidation, thereby increasing operational complexity.
In conclusion, the activity of the sulfided hydrogenation catalyst provided by the prior art is improved to some extent, but the improvement degree is limited, and the preparation method of the sulfided hydrogenation catalyst has the defects of more complex preparation route, poorer controllability and higher cost, so that the industrial application of the methods is limited to a certain extent.
Disclosure of Invention
Aiming at the defects of lower activity, more complex preparation process, poorer controllability and higher cost of the vulcanized hydrogenation catalyst in the prior art, the invention provides a preparation method of a novel vulcanized hydrogenation catalyst, the vulcanized hydrogenation catalyst prepared by the method and the application of the vulcanized hydrogenation catalyst in hydrodesulfurization and/or hydrodenitrogenation.
In order to achieve the above object, one aspect of the present invention provides a method for preparing a sulfided hydrogenation catalyst, the method comprising the steps of:
(1) preparing a solution A containing VIB group metal salt, a sulfur source and an optional water-soluble organic dispersant, wherein the sulfur source is a sulfur-containing substance which can be hydrolyzed at 50-100 ℃ under an acidic condition, and the pH value of the solution A is 1-8;
(2) aging the solution A in the step (1) at 20-120 ℃ for 0.5-48 hours to obtain an aged product;
(3) impregnating a catalyst support with the aged product;
(4) roasting the solid material impregnated in the step (3) in an inert or reducing atmosphere;
the method further comprises the step of introducing a group VIII metal element in step (1) and/or step (3).
According to a preferred embodiment of the present invention, in the step (4), the roasting conditions include: roasting at 310 ℃ for 0.5-5 hours at 240 ℃ and then at 400 ℃ for 0.5-6 hours at 320 ℃.
The second aspect of the present invention provides a sulfided hydrogenation catalyst prepared by the above-described preparation method.
The invention also provides the application of the vulcanized hydrogenation catalyst in hydrodesulfurization and/or hydrodenitrogenation.
The inventor of the invention discovers through research that in the process of preparing the vulcanized hydrogenation catalyst, a solution A containing VIB group metal salt, a sulfur source and optionally a water-soluble organic dispersant with a certain pH value is prepared, then the solution A is aged, then a carrier is impregnated, and a VIII group metal element is introduced in a specific step, so that the activity of the vulcanized hydrogenation catalyst can be effectively improved. The reason is probably because the invention makes use of VIB group metal salt and sulfur source to fully generate O-S exchange reaction under the condition of specific pH, so that the oxidation state VIB group metal salt is converted into the vulcanization state VIB group metal salt, the aging treatment further promotes the O-S exchange, VIII group metal salt is introduced in the step (1) and/or the step (3), so that the vulcanization state VIB group metal salt and VIII group metal salt generate certain charge attraction, then the catalyst carrier is impregnated, and finally the catalyst carrier is roasted (heat treatment) in inert or reducing atmosphere to obtain the vulcanization type hydrogenation catalyst. The method is more beneficial to exerting the auxiliary effect of VIII group metals, and is more beneficial to modifying the corner position of VIB group metals by the auxiliary (VIII group metals) to form more II-type Co (Ni) -Mo (W) -S active centers.
The advantages of the invention can be summarized as follows: compared with the similar catalyst prepared by the traditional impregnation method, the method of the inventionThe hydrogenation catalyst prepared by the method has more excellent hydrogenation performance, and the reason is probably that the hydrogenation catalyst prepared by the method has excellent sulfidation degree of active components, promotes the formation of more II active centers, ensures that active metals can fully exert catalytic activity, and simultaneously avoids low-activity Mo (W) S in the conventional catalyst2-O-Al2O3The existence of species ensures higher intrinsic activity of the active components. Preferably, the precursor species in a sulfurized state is calcined by adopting a proper temperature control procedure, so that additive atoms (VIII group metal) can be more embedded into the edge site structure of the disulfide active phase platelet of the VIB group metal, and more II-type active centers with better additive effect are formed. In addition, compared with the prior art, the method has the advantages of simple technical operation, easy repetition, high utilization rate of active metal, low preparation cost of the catalyst, no need of pre-vulcanization of the prepared catalyst, saving of start-up time and environmental friendliness.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a vulcanized hydrogenation catalyst, which comprises the following steps:
(1) preparing a solution A containing VIB group metal salt, a sulfur source and an optional water-soluble organic dispersant, wherein the sulfur source is a sulfur-containing substance which can be hydrolyzed at 50-100 ℃ under an acidic condition, and the pH value of the solution A is 1-8;
(2) aging the solution A in the step (1) at 20-120 ℃ for 0.5-48 hours to obtain an aged product;
(3) impregnating a catalyst support with the aged product;
(4) roasting the solid material impregnated in the step (3) in an inert or reducing atmosphere;
the method further comprises the step of introducing a group VIII metal element in step (1) and/or step (3).
In the invention, the solution A is adjusted to a proper pH value in the step (1), then aging treatment is carried out under the conditions of the step (2), so that sufficient O-S exchange is carried out on the VIB group metal salt and a sulfur source (obtaining VIB group metal salt in a sulfuration state), further sufficient O-S exchange is carried out, VIII group metal elements are introduced in the step (1) and/or the step (3), and then a carrier is impregnated. On one hand, the method can ensure that certain charge attraction is generated between the vulcanized VIB group metal salt and VIII group metal salt, and is more beneficial to modifying the corner position of the VIB group metal by the aid (VIII group metal) to form more II-type Co (Ni) -Mo (W) -S active centers. In the prior art, a solution containing VIB group metal salt, a sulfur source and optionally a water-soluble organic dispersant is directly contacted with a carrier, and VIII group metal is loaded after roasting. The performance of the catalyst prepared by the method provided by the invention is obviously superior to that of the catalyst prepared by the prior art.
According to a preferred embodiment of the invention, the pH of the solution A is between 3 and 7. The preferable pH value is more beneficial to charge attraction between the VIB group metal salt and the VIII group metal salt in the vulcanized state, and is more beneficial to modifying the corner position of the VIB group metal by the aid (VIII group metal) to form more II-type Co (Ni) -Mo (W) -S active centers, so that the hydrodesulfurization/denitrification performance of the catalyst is further improved.
According to the invention, the pH of solution A can be adjusted in various ways, for example by adding acidic and/or basic substances.
The acidic substance may be an organic acid or an inorganic acid, and the present invention is not particularly limited thereto. According to the present invention, preferably, the acidic substance is at least one selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, and acetic acid, and more preferably hydrochloric acid. By adopting the preferred embodiment, the introduced impurity elements are naturally removed in the drying or roasting process in the later stage of the catalyst preparation, and the performance of the catalyst is not influenced.
According to the present invention, preferably, the alkaline substance is at least one selected from the group consisting of ammonia water, sodium hydroxide, and potassium hydroxide, and more preferably sodium hydroxide.
In the invention, the adding amount of the sulfur source is based on the condition of fully vulcanizing the VIB group metal and the VIII group metal, and preferably, the molar ratio of the sulfur source to the VIB group metal is 3-6 in terms of sulfur: 1. this preferred embodiment is more conducive to the synergistic effect of the group VIII and group VIB metals and more conducive to the formation of the active phase.
In the present invention, the sulfur source may be various sulfur-containing substances that can be hydrolyzed under acidic conditions at 50 to 100 ℃. Preferably, the sulfur source is at least one selected from the group consisting of L-cysteine, a thioamide represented by formula (1), a monothioester represented by formula (2), and a dithioester represented by formula (3),
in the formula (1), R1Is NH2-、CH3-、CH3CH2-、CH3NH-or (CH)3)2N-，R2And R3Each independently is H or C1-C4 alkyl; in the formula (2), R4Is H or C1-C4 alkyl, R5Is C1-C4 alkyl; in the formula (3), R6Is H or C1-C4 alkyl, R7Is a C1-C4 alkyl group, said C1-C4 alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl. R2And R3May be the same or different. More preferably, the sulfur source is a thioamide represented by formula (1), still more preferably, the sulfur source is thiourea and/or thioacetamide, and most preferably, the sulfur source is thioacetamide.
According to a preferred embodiment of the present invention, the solution a contains a water-soluble organic dispersant. The selection range of the adding amount of the water-soluble organic dispersant is wide, and the volume content of the water-soluble organic dispersant in the solution A is preferably 5-50%, and more preferably 10-30%.
According to the method provided by the invention, the water-soluble organic dispersant is preferably water-soluble organic solvents with various boiling points of 15-90 ℃, more preferably, the water-soluble organic dispersant is selected from at least one of methanol, ethanol, acetone, ethylene glycol and glycerol, and more preferably at least one of ethanol, acetone, ethylene glycol and glycerol.
In the present invention, the solvent forming the solution a is preferably water.
The specific process of preparing the solution a containing the group VIB metal salt, the sulfur source and optionally the water-soluble organic dispersant is not particularly limited in the present invention, and in order to facilitate the dispersion of the components, it is preferable to prepare the solution containing the group VIB metal salt and the sulfur source first and then add the dispersant (if the solution a contains the dispersant, then add it, otherwise, add it is not). Preferably, the solution a is formulated under stirring conditions to provide more complete and uniform contact between the group VIB metal salt and the sulfur source and dispersant. The stirring speed may be 10-500 rpm.
According to the invention, the group VIB metal is preferably molybdenum and/or tungsten. The group VIB metal salt may be at least one of sodium molybdate, ammonium paramolybdate, sodium tungstate, ammonium tungstate, and ammonium metatungstate.
According to the invention, the concentration of the group VIB metal salt in solution A is preferably between 0.05 and 10 mol/L.
According to the present invention, preferably, in the step (2), the solution A is aged at 25 to 100 ℃ for 4 to 30 hours.
It is to be noted that when the pH of the solution a is low (strong acidity), it is preferable that the aging treatment of step (2) is performed at a slightly low temperature, and when the pH of the solution a is high (weak acidity), it is preferable that the aging treatment of step (2) is performed at a slightly high temperature. The preferable pH value of the solution A and the aging treatment condition in the step (2) ensure that the O-S exchange is more sufficient, are more favorable for improving the sulfurization degree of active metal and are more favorable for improving the hydrodesulfurization/denitrification performance of the prepared catalyst.
The aging treatment according to the invention can be carried out under closed conditions (for example, in an autoclave) or under open conditions (for example, in a beaker), for which there is no particular requirement.
In the present invention, as long as the group VIII metal element is introduced in step (1) and/or step (3), the specific mode of introducing the group VIII metal element in the present invention is not particularly limited. Preferably, the method for introducing the group VIII metal element in step (1) comprises: in step (1), a solution a is prepared containing a group VIB metal salt, a group VIII metal salt, a sulfur source, and optionally a water-soluble organic dispersant. The specific process for preparing the solution a is not particularly limited, for example, a solution containing a group VIB metal salt, a group VIII metal salt and a sulfur source is prepared, and then a dispersant is added (if the solution a contains a dispersant, the dispersant is added, and vice versa). Preferably, the solution A is prepared under stirring conditions so as to ensure that the VIB group metal salt, the VIII group metal salt, the sulfur source and the dispersant are contacted more fully and uniformly. The stirring speed may be 10-500 rpm. Preferably, the method for introducing the group VIII metal element in step (3) includes: in step (3), the aged product is contacted with a group VIII metal salt, followed by impregnation of the catalyst support. The specific embodiment and conditions of contacting the aged product with the group VIII metal salt are not particularly limited in the present invention, and those skilled in the art can appropriately select the specific embodiment according to the requirements of the water absorption of the catalyst carrier and the loading amounts of the group VIB metal and the group VIII metal (the volume of the solution obtained by contacting the aged product with the group VIII metal salt is determined by the water absorption of the catalyst carrier (can be adjusted by adding water or removing water by evaporation), and the concentrations of the group VIB metal-containing compound and the group VIII metal salt are determined by the loading amounts of the group VIB metal and the group VIII metal).
According to the present invention, the group VIII metal may be cobalt and/or nickel, and the group VIII metal salt may be a soluble salt of cobalt and/or nickel, for example, at least one of a nitrate, a carbonate, a basic carbonate, and an acetate of cobalt and/or nickel.
The amount of the group VIII metal salt added is determined according to the content of the group VIII metal element required for the catalyst, and in general, the molar ratio of the group VIII metal to the group VIB metal, each calculated on the metal element, may be from 0.2 to 1.5, preferably from 0.3 to 0.8.
According to the invention, the catalyst support may be a porous refractory inorganic oxide support, for example γ -Al2O3、SiO2、TiO2、SBA-15、ZrO2、TiO2-γ-Al2O3And SiO2-γ-Al2O3One or more of (a). It is further preferred that the diameter of the catalyst support is between 2 and 5 mm. Particularly preferably, the catalyst carrier is gamma-Al with the diameter of 2mm to 5mm2O3Particles, SiO 2mm to 5mm in diameter2-γ-Al2O3Particles or TiO with a diameter of 2mm to 5mm2-γ-Al2O3And (3) granules.
According to the method provided by the invention, the method can further comprise drying the solid material impregnated in the step (3) and then roasting. Preferably, the drying is performed in air or an inert atmosphere, and the drying conditions may include: the temperature is 10-80 deg.C (preferably 20-50 deg.C).
According to the present invention, the inert atmosphere may be provided by one or more of nitrogen, argon and helium, and the reducing atmosphere may be provided by hydrogen and/or hydrogen sulfide and optionally an inert gas; the present invention is not particularly limited in this regard. Preferably, the roasting in the step (4) is performed in a hydrogen-containing atmosphere, and further preferably, the volume content of hydrogen in the hydrogen-containing atmosphere is not less than 0.5%.
According to a preferred embodiment of the present invention, in the step (4), the roasting conditions include: roasting at 310 ℃ of 240-5 ℃ for 0.5-5 hours, then heating to 400 ℃ of 320-6 ℃ for 0.5-6 hours, preferably, roasting at 290 ℃ of 270-4 ℃ for 1-4 hours, then heating to 400 ℃ of 350-4 ℃ for 1-4 hours.
The temperature rising rate of the roasting process is not particularly limited in the present invention, and according to a specific embodiment of the present invention, the roasting process may be raised to 310 ℃ at a temperature rising rate of 0.5-10 ℃/min, and then stayed for 0.5-5 hours, and then raised to 400 ℃ at a temperature rising rate of 0.5-20 ℃/min, and stayed for 0.5-6 hours, preferably, raised to 290 ℃ at a temperature rising rate of 3-8 ℃/min, and stayed for 1-4 hours, and then raised to 400 ℃ at a temperature rising rate of 350 ℃ at a temperature rising rate of 5-15 ℃/min, and stayed for 1-4 hours.
The selection range of the usage amounts of the group VIB metal salt, the group VIII metal and the catalyst carrier is wide, and can be conventional in the field, preferably, the usage amounts of the group VIB metal salt, the group VIII metal salt and the catalyst carrier are such that the carrier content in the prepared catalyst is 60-90 wt%, the group VIB metal content is 5-35 wt% and the group VIII metal content is 1-11 wt% in terms of oxides, and further preferably, the usage amounts of the group VIB metal salt, the group VIII metal salt and the catalyst carrier are such that the carrier content in the prepared catalyst is 73-84 wt%, the group VIB metal content is 10-25 wt% and the group VIII metal content is 2-6 wt% in terms of oxides.
The sulfurized hydrogenation catalyst prepared by the method has excellent hydrodesulfurization and denitrification activity, so the invention also provides the sulfurized hydrogenation catalyst prepared by the method and the application of the sulfurized hydrogenation catalyst in hydrodesulfurization and/or hydrodenitrification.
The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is intended to help the reader to clearly understand the spirit of the present invention, but not to limit the scope of the present invention.
In the following examples, the contents of the components in the catalyst were measured by X-ray fluorescence spectroscopy (XRF) using a ZSX-100e X-ray fluorescence spectrometer at a current of 50mA and a voltage of 50kV using an Rh target.
The degree of dispersion and degree of sulfidation of the host Mo (or W) in the catalyst were determined by X-ray photoelectron spectroscopy (XPS), wherein the degree of dispersion is expressed by the surface metal atomic ratio (Mo (W)/Al) given by the XPS analysis results, and the degree of sulfidation is obtained by processing XPS data, as described in Han et Al, Journal of materials Chemistry 2012,22:25340, wherein the X-ray photoelectron spectroscopy (XPS) was performed on an ESCA Lab 250X-ray photoelectron spectrometer (VG, uk), using Al K α as a radiation source, a resolution of 0.5eV, and a binding energy of C1s (Eb 285.0eV) with carbon contamination as an internal standard.
Example 1
(1) Preparing 40mL of solution containing 2.4mol/L sodium molybdate and 8.0mol/L thioacetamide, dropwise adding (at the speed of 1mL/min)4.5mL of absolute ethyl alcohol in the process of continuously stirring, and then dropwise adding 2.4mol/L hydrochloric acid in the process of stirring to adjust the pH value to 6 to obtain solution A;
(2) aging the solution A obtained in the step (1) at 60 ℃ for 24 hours to obtain an aged product;
(3) adding 9.0g of nickel acetate into the aged product in the step (2), adding water to a constant volume or heating and concentrating to 48mL, and impregnating 60.0g of gamma-Al with the diameter of 1-5mm with the solution2O3Particles (liquid absorption rate 0.8mL/g), immersion time is 1 hour;
(4) drying the solid product impregnated in the step (3) for 3 hours at 50 ℃ in a nitrogen atmosphere, and then carrying out drying in H2In the atmosphere, raising the temperature to 300 ℃ at the temperature raising rate of 5 ℃/min and keeping the temperature for 1h, raising the temperature to 360 ℃ at the temperature raising rate of 20 ℃/min and keeping the temperature for 1h, and roasting to obtain the sulfide type hydrogenation catalyst S-1.
The results of the analysis of the metal content, the dispersity and the degree of sulfidation in the catalyst are shown in Table 1.
Comparative example 1
According to the method of example 1, except that 2.4mol/L aqueous ammonia was added dropwise to adjust the pH to 10, solution A was obtained, and sulfided hydrogenation catalyst D-1 was obtained.
The results of the analysis of the metal content, the dispersity and the degree of sulfidation in the catalyst are shown in Table 1.
Comparative example 2
The procedure of example 1 was followed, except that the aging step of step (2) was not included, and nickel acetate was directly added to the solution A, to obtain a sulfided hydrogenation catalyst D-2.
The results of the analysis of the metal content, the dispersity and the degree of sulfidation in the catalyst are shown in Table 1.
Example 2
(1) Preparing 40mL of solution containing 2.4mol/L sodium molybdate, 0.9mol/L nickel acetate and 9.0mol/L thioacetamide, dropwise adding 3mL of acetone (at the speed of 1mL/min) in the process of continuously stirring, and then dropwise adding 2.4mol/L hydrochloric acid in the process of stirring to adjust the pH value to 6 to obtain solution A;
(2) aging the solution A obtained in the step (1) at 60 ℃ for 24 hours, adding water to a constant volume or heating and concentrating to 48mL to obtain an aged product;
(3) impregnating 60.0g of gamma-Al with the diameter of 1-5mm with the aged product obtained in the step (2)2O3Particles (liquid absorption rate 0.8mL/g), immersion time is 2 hours;
(4) drying the solid product impregnated in the step (3) for 3 hours at 50 ℃ in a nitrogen atmosphere, and then carrying out drying in H2In the atmosphere, raising the temperature to 300 ℃ at the temperature raising rate of 5 ℃/min and keeping the temperature for 1h, raising the temperature to 360 ℃ at the temperature raising rate of 20 ℃/min and keeping the temperature for 1h, and roasting to obtain the sulfide type hydrogenation catalyst S-2.
The results of the analysis of the metal content, the dispersity and the degree of sulfidation in the catalyst are shown in Table 1.
Example 3
(1) Preparing 40mL of solution containing 2.4mol/L sodium molybdate, 0.9mol/L cobalt acetate and 8.0mol/L thioacetamide, dropwise adding 3mL of acetone (at the speed of 1mL/min) in the process of continuously stirring, and then dropwise adding 2.4mol/L hydrochloric acid in the process of stirring to adjust the pH value to 7 to obtain solution A;
(2) aging the solution A obtained in the step (1) at 95 ℃ for 6 hours, adding water to a constant volume or heating and concentrating to 48mL to obtain an aged product;
(3) impregnating 60.0g of gamma-Al with the diameter of 1-5mm with the aged product obtained in the step (2)2O3Particles (liquid absorption rate 0.8mL/g), immersion time is 1 hour;
(4) drying the solid product impregnated in the step (3) for 3 hours at 50 ℃ in a nitrogen atmosphere, and then carrying out drying in H2Raising the temperature to 290 ℃ at a heating rate of 5 ℃/min in the atmosphere and keeping the temperatureAnd keeping the temperature for 3 hours, raising the temperature to 360 ℃ at the temperature rise rate of 10 ℃/minute, and keeping the temperature rise program for 4 hours for roasting to obtain the sulfide type hydrogenation catalyst S-3.
The results of the analysis of the metal content, the dispersity and the degree of sulfidation in the catalyst are shown in Table 1.
Example 4
(1) Preparing 40mL of solution containing 2.1mol/L ammonium metatungstate (calculated by tungsten element), 1.1mol/L nickel acetate and 10.0mol/L thioacetamide, dripping 3mL of glycerol (with the speed of 1mL/min) in the process of continuously stirring, and then dripping 2.4mol/L hydrochloric acid in the process of stirring to adjust the pH value to 3 to obtain solution A;
(2) aging the solution A obtained in the step (1) at 25 ℃ for 30 hours, adding water to a constant volume or heating and concentrating to 48mL to obtain an aged product;
(3) impregnating 60.0g of gamma-Al with the diameter of 1-5mm with the aged product obtained in the step (2)2O3Particles (liquid absorption rate 0.8mL/g), immersion time is 1 hour;
(4) drying the solid product impregnated in the step (3) for 3 hours at 50 ℃ in a nitrogen atmosphere, and then carrying out drying in H2In the atmosphere, the temperature is increased to 290 ℃ at the temperature increasing rate of 5 ℃/min and kept for 3h, and then the temperature is increased to 360 ℃ at the temperature increasing rate of 10 ℃/min and kept for 4h for roasting, so as to obtain the sulfide type hydrogenation catalyst S-4.
The results of the analysis of the metal content, the dispersity and the degree of sulfidation in the catalyst are shown in Table 1.
Example 5
(1) Preparing 40mL of solution containing 1.8mol/L ammonium metatungstate (calculated by tungsten element), 0.42mol/L ammonium paramolybdate (calculated by molybdenum element), 1.0mol/L nickel acetate and 8.0mol/L thioacetamide, dripping (at the speed of 1mL/min)4.5mL of glycol in the process of continuously stirring, and then dripping 2.4mol/L hydrochloric acid in the process of stirring to adjust the pH value to 6 to obtain solution A;
(2) aging the solution A obtained in the step (1) at 25 ℃ for 20 hours, adding water to a constant volume or heating and concentrating to 48mL to obtain an aged product;
(3) impregnating 60.0g of gamma-Al with the diameter of 1-5mm with the aged product obtained in the step (2)2O3Particles (liquid absorption rate 0.8mL/g), immersion time is 2 hours;
(4) drying the solid product impregnated in the step (3) for 3 hours at 50 ℃ in a nitrogen atmosphere, and then carrying out drying in H2/Ar(H2The volume content of the catalyst is 5 percent), heating to 290 ℃ at a heating rate of 5 ℃/min and keeping for 2h, then heating to 400 ℃ at a heating rate of 5 ℃/min and keeping for 2h, and roasting to obtain the sulfide type hydrogenation catalyst S-5.
The results of the analysis of the metal content, the dispersity and the degree of sulfidation in the catalyst are shown in Table 1.
Example 6
(1) Preparing 40mL of solution containing 1.8mol/L ammonium metatungstate (calculated by tungsten element), 0.42mol/L ammonium paramolybdate (calculated by molybdenum element), 0.76mol/L nickel acetate, 0.24mol/L cobalt acetate and 8.0mol/L thiopropionamide, dropwise adding (at the speed of 1mL/min)3.5mL of acetone in the process of continuously stirring, and then dropwise adding 2.4mol/L hydrochloric acid in the process of stirring to adjust the pH value to 5 to obtain solution A;
(2) aging the solution A obtained in the step (1) at 45 ℃ for 24 hours, adding water to a constant volume or heating and concentrating to 48mL to obtain an aged product;
(3) impregnating 60.0g of gamma-Al with the diameter of 1-5mm with the aged product obtained in the step (2)2O3Particles (liquid absorption rate 0.8mL/g), immersion time is 2 hours;
(4) drying the solid product impregnated in the step (3) for 3 hours at 50 ℃ in a nitrogen atmosphere, and then carrying out drying in H2S/H2(H2The volume fraction of S is 10 percent), raising the temperature to 290 ℃ at a heating rate of 5 ℃/min and keeping the temperature for 2h, raising the temperature to 400 ℃ at a heating rate of 5 ℃/min and keeping the temperature for 2h, and roasting to obtain the sulfide type hydrogenation catalyst S-6.
The results of the analysis of the metal content, the dispersity and the degree of sulfidation in the catalyst are shown in Table 1.
Example 7
A sulfided hydrogenation catalyst S-7 was obtained by following the procedure of example 1, except that anhydrous ethanol was replaced with an equal amount of water.
The results of the analysis of the metal content, the dispersity and the degree of sulfidation in the catalyst are shown in Table 1.
Example 8
The procedure of example 2 was followed except that, in step (1), 2.4mol/L hydrochloric acid was added dropwise to adjust the pH to 8 to obtain a solution A and obtain a sulfided hydrogenation catalyst S-8.
The results of the analysis of the metal content, the dispersity and the degree of sulfidation in the catalyst are shown in Table 1.
Example 9
The procedure of example 2 was followed, except that the calcination in step (4) was not carried out by a temperature-raising procedure, but was carried out at 360 ℃ for 4 hours, to obtain a sulfided hydrogenation catalyst S-9.
The results of the analysis of the metal content, the dispersity and the degree of sulfidation in the catalyst are shown in Table 1.
Comparative example 3
Preparing NiMo/gamma-Al by normal temperature isovolumetric immersion method2O3A catalyst. The method specifically comprises the following steps: weighing 12.5g of ammonium molybdate tetrahydrate and 6.7g of nickel nitrate, preparing about 80mL of impregnation liquid, dropwise adding a small amount of hydrochloric acid to a pH value of about 4.5, and dropwise adding the solution to 100g of gamma-Al which is in a vacuum state and has the diameter of 1-5mm2O3The carrier (liquid absorption rate is 0.8mL/g), then the carrier is placed at room temperature until the carrier is naturally dried, then the carrier is placed in a drying oven to be dried for 10h at 120 ℃, and the carrier is roasted for 4h at 500 ℃ to obtain NiMo/gamma-Al2O3Then 1g of NiMo/gamma-Al is taken2O3Loading into a micro hydrogenation reactor for in-situ vulcanization, wherein the vulcanization conditions are as follows: 4.0MPa, 300 ℃, 4h, a hydrogen-oil volume ratio of 300, an oil inlet flow of the vulcanized oil of 8mL/h, and obtaining the catalyst D-3 after the vulcanization.
The results of the analysis of the metal content, the dispersity and the degree of sulfidation in the catalyst are shown in Table 1.
Comparative example 4
Preparation of CoMo/gamma-Al by normal-temperature isometric immersion method2O3A catalyst. The method specifically comprises the following steps: weighing 12.5g of ammonium molybdate tetrahydrate and 6.7g of cobalt nitrate, preparing about 80mL of impregnation liquid, dropwise adding a small amount of hydrochloric acid to a pH value of about 4.5 during the preparation, and dropwise adding the solution to 100g of gamma-Al which is in a vacuum state and has the diameter of 1-5mm2O3Placing the carrier (with liquid absorption rate of 0.8mL/g) in a room temperature until the carrier is naturally dried, then placing the carrier in an oven to dry at 120 ℃ for 10h, and roasting at 500 ℃ for 4h to obtain the CoMo/Al2O3Then CoMo/gamma-Al was sulfided as described in comparative example 32O3Sulfurizing to obtain catalyst D-4.
The results of the analysis of the metal content, the dispersity and the degree of sulfidation in the catalyst are shown in Table 1.
Comparative example 5
Preparing NiW/gamma-Al by normal temperature isovolumetric immersion method2O3A catalyst. The method specifically comprises the following steps: weighing 48.0g of sodium tungstate and 7.0g of nickel nitrate to prepare about 80mL of impregnation liquid, and dropwise adding the impregnation liquid to 100g of gamma-Al which is in a vacuum state and has the diameter of 1-5mm2O3Placing the carrier (liquid absorption rate is 0.8mL/g) in a room temperature until the carrier is naturally dried, then placing the carrier in an oven to dry at 120 ℃ for 10h, and roasting at 500 ℃ for 4h to obtain NiW/Al2O3Then NiW/gamma-Al was vulcanized as described in comparative example 32O3Sulfurizing to obtain catalyst D-5.
Comparative example 6
Preparing NiMoW/gamma-Al by adopting normal-temperature isometric impregnation method2O3A catalyst. The method specifically comprises the following steps: 27.3g of ammonium metatungstate was weighed (in WO)3Calculated), 4.1g of paramolybdic acid (in MoO)3Calculated) and 20.1g of nickel nitrate to prepare about 80mL of impregnation liquid, and dripping the impregnation liquid into 100g of gamma-Al with the diameter of 1-5mm in a vacuum state2O3Placing the carrier (liquid absorption rate is 0.8mL/g) in a room temperature until the carrier is naturally dried, then placing the carrier in an oven to dry at 120 ℃ for 10h, and roasting at 500 ℃ for 4h to obtain NiMoW/Al2O3NiMoW/gamma-Al was then vulcanized as described in comparative example 32O3Sulfurizing to obtain catalyst D-6.
The results of the analysis of the metal content, the dispersity and the degree of sulfidation in the catalyst are shown in Table 1.
Comparative example 7
Preparing CoMoNiW/gamma-Al by adopting normal-temperature isometric impregnation method2O3A catalyst. The method specifically comprises the following steps: 27.3g of ammonium metatungstate was weighed (in WO)3Calculated), 4.1g of paramolybdic acid (in MoO)3Calculated) 15.5g of nickel nitrate and 4.6g of cobalt nitrate to prepare about 80mL of impregnation solution, and dropwise adding the solution to 100g of gamma-Al which is in a vacuum state and has the diameter of 1-5mm2O3Placing the carrier (the liquid absorption rate is 0.8mL/g) in a room temperature until the carrier is naturally dried, then placing the carrier in an oven to dry for 10h at 120 ℃, and roasting for 4h at 500 ℃ to obtain the CoMoNiW/Al2O3CoMoNiW/gamma-Al was then vulcanized as described in comparative example 32O3Sulfurizing to obtain catalyst D-7.
The results of the analysis of the metal content, the dispersity and the degree of sulfidation in the catalyst are shown in Table 1.
TABLE 1 analysis results of the metal content, dispersity and sulfidity of the catalyst
Test examples
In the present test example, desulfurization and denitrification activities of the hydrogenation catalyst provided by the present invention and the hydrogenation catalyst provided by the comparative example were evaluated in accordance with the following methods, and the results are shown.
Hydrodesulfurization: the desulfurization activity of the catalyst was evaluated on a WFSP3050 continuous high-pressure reactor manufactured by Xiaguan apparatus company of Tianjin, using a cyclohexane solution containing 1% by mass of 4, 6-dimethyldibenzothiophene (4, 6-DMDBT). The catalyst does not need to be presulfided before reaction. The reaction conditions are as follows: 4.0MPa, 340 ℃, the volume ratio of hydrogen to oil is 300, and the oil inlet flow is 8 mL/h. After the reaction was stabilized for 3 hours, the reaction was sampled for 4 hours, the sample was analyzed by an HS-500 type high frequency infrared sulfur and nitrogen analyzer, and the activity was expressed by the desulfurization rate of 4,6-DMDBT (average of 10 samples), and the results are shown in Table 2.
And (3) hydrodenitrogenation: the denitrification activity of the catalyst was evaluated on a WFSP3050 continuous high-pressure reactor manufactured by Warit instruments of Tianjin, using an n-heptane solution containing 1% by mass of quinoline (Q) as a raw material. The catalyst does not need to be presulfided before reaction. The reaction conditions are as follows: 4.0MPa, 340 ℃, the volume ratio of hydrogen to oil is 400, and the oil inlet flow is 8 mL/h. After 3 hours of reaction stability, samples were taken for 4 hours of reaction, and the samples were analyzed by an HS-500 type high frequency infrared sulfur and nitrogen analyzer, and the activity was expressed by the denitrification rate of Q (average of 10 samples), and the results are shown in Table 2.
The reaction desulfurization (nitrogen) rate X is calculated as follows:
TABLE 2 evaluation results of hydrodesulfurization and denitrogenation activities of the catalysts
The results in tables 1 and 2 show that compared with hydrogenation catalysts prepared by conventional methods, the sulfided hydrogenation catalysts prepared by the present invention have significantly better active component dispersion degree, and the active components are substantially completely sulfided, which is much higher than the sulfided degree of active metals on conventional catalysts, and the utilization rate of active metals is substantially improved. More importantly, the catalyst provided by the invention has obviously better hydrodesulfurization and denitrification activity although the compositions of the two types of catalysts are similar. The above results are sufficient to show that the preparation provided by the present invention has advantages that are not comparable to conventional impregnation methods.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (20)
1. A method for preparing a sulfided hydrogenation catalyst, the method comprising the steps of:
(1) preparing a solution A containing VIB group metal salt, a sulfur source and an optional water-soluble organic dispersant, wherein the sulfur source is a sulfur-containing substance which can be hydrolyzed at 50-100 ℃ under an acidic condition, and the pH value of the solution A is 6-7;
(2) aging the solution A in the step (1) at 20-120 ℃ for 0.5-48 hours to obtain an aged product;
(3) impregnating a catalyst support with the aged product;
(4) roasting the solid material impregnated in the step (3) in an inert or reducing atmosphere; the roasting conditions comprise: roasting at 310 ℃ of 240 ℃ for 0.5-5 hours, then heating to 400 ℃ of 320 ℃ for 0.5-6 hours;
the method further comprises the step of introducing a group VIII metal element in step (1) and/or step (3).
2. The preparation method according to claim 1, wherein the molar ratio of the sulfur source to the group VIB metal element is 3-6: 1.
3. the production method according to claim 1, wherein the sulfur source is at least one selected from the group consisting of L-cysteine, a thioamide represented by formula (1), a monothioester represented by formula (2), and a dithioester represented by formula (3),
in the formula (1), R1Is NH2-、CH3-、CH3CH2-、CH3NH-or (CH)3)2N-，R2And R3Each independently is H or C1-C4 alkyl;
in the formula (2), R4Is H or C1-C4 alkyl, R5Is C1-C4 alkyl;
in the formula (3), R6Is H or C1-C4 alkyl, R7Is C1-C4 alkyl.
4. The production method according to claim 3, wherein the sulfur source is a thioamide represented by formula (1).
5. The production method according to claim 3, wherein the sulfur source is thiourea and/or thioacetamide.
6. The production method according to claim 3, wherein the sulfur source is thioacetamide.
7. The production method according to claim 1, wherein the volume content of the water-soluble organic dispersant in the solution a is 5 to 50%.
8. The production method according to claim 1,
the water-soluble organic dispersant is at least one selected from methanol, ethanol, acetone, ethylene glycol and glycerol.
9. The process according to claim 1, wherein the group VIB metal is molybdenum and/or tungsten.
10. The process according to claim 1, wherein the concentration of the group VIB metal salt in the solution A is between 0.05 and 10 mol/L.
11. The production method according to claim 1, wherein in the step (2), the solution A is aged at 25 to 100 ℃ for 4 to 30 hours.
12. The production method according to any one of claims 1 to 11,
the method for introducing the VIII group metal element in the step (1) comprises the following steps: in step (1), preparing a solution A containing a group VIB metal salt, a group VIII metal salt, a sulfur source and optionally a water-soluble organic dispersant;
the method for introducing the VIII group metal element in the step (3) comprises the following steps: in step (3), the aged product is contacted with a group VIII metal salt, followed by impregnation of the catalyst support.
13. The preparation method according to claim 12, wherein the group VIII metal salt is added in a molar ratio of 0.2 to 1.5 of the group VIB metal calculated on the metal element.
14. The method according to claim 12, wherein the group VIII metal salt is added in a molar ratio of 0.3 to 0.8, calculated as the metal element, to the group VIB metal.
15. The method of claim 12 wherein the group VIII metal salt is at least one of a nitrate, carbonate, hydroxycarbonate, and acetate salt of cobalt and/or nickel.
16. The process according to any one of claims 1 to 11, wherein the group VIB metal salt, the group VIII metal and the catalyst support are used in amounts such that the catalyst is obtained with a support content of 60 to 90 wt.%, based on the oxides, of 5 to 35 wt.% and a group VIII metal content of 1 to 11 wt.%.
17. The production method according to any one of claims 1 to 11, wherein the catalyst support is a porous heat-resistant inorganic oxide support.
18. The production method according to any one of claims 1 to 11, wherein the catalyst support is γ -Al2O3、SiO2、TiO2、SBA-15、ZrO2And SiO2-γ-Al2O3One or more of (a).
19. A sulfided hydrogenation catalyst made by the method of any of claims 1-18.
20. Use of the sulphided hydrogenation catalyst of claim 19 in hydrodesulphurisation and/or hydrodenitrogenation.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088618A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Prepn process of hydrogenation catalyst composition |
| CN101590414A (en) * | 2008-05-30 | 2009-12-02 | 中国石油天然气股份有限公司 | A kind of method of preparing hyrorefining catalyst by in situ decomposition method |
| WO2012085357A1 (en) * | 2010-12-22 | 2012-06-28 | IFP Energies Nouvelles | Method for the hydrodesulphurisation of gasoline fractions using a catalyst based on heteropolyanions trapped in a mesostructured silica support |
| CN103801333A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of sulfur-loaded hydrogenation catalyst |
| CN105214728A (en) * | 2015-10-14 | 2016-01-06 | 中国石油大学(华东) | A kind of preparation method of non-loading type nickel molybdenum match hydrogenation catalyst |
| CN105289636A (en) * | 2015-11-03 | 2016-02-03 | 广东工业大学 | Nanometer Ni-Mo/graphene oxide catalyst and preparation method thereof |
| CN105521799A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Vulcanized hydrogenation catalyst, and preparation method and application thereof |
| CN106492844A (en) * | 2016-11-24 | 2017-03-15 | 青岛大学 | A kind of preparation method and application of amorphous nano molybdenum disulfide catalyst |
-
2017
- 2017-09-29 CN CN201710912634.8A patent/CN109569664B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088618A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Prepn process of hydrogenation catalyst composition |
| CN101590414A (en) * | 2008-05-30 | 2009-12-02 | 中国石油天然气股份有限公司 | A kind of method of preparing hyrorefining catalyst by in situ decomposition method |
| WO2012085357A1 (en) * | 2010-12-22 | 2012-06-28 | IFP Energies Nouvelles | Method for the hydrodesulphurisation of gasoline fractions using a catalyst based on heteropolyanions trapped in a mesostructured silica support |
| CN103801333A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of sulfur-loaded hydrogenation catalyst |
| CN105521799A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Vulcanized hydrogenation catalyst, and preparation method and application thereof |
| CN105214728A (en) * | 2015-10-14 | 2016-01-06 | 中国石油大学(华东) | A kind of preparation method of non-loading type nickel molybdenum match hydrogenation catalyst |
| CN105289636A (en) * | 2015-11-03 | 2016-02-03 | 广东工业大学 | Nanometer Ni-Mo/graphene oxide catalyst and preparation method thereof |
| CN106492844A (en) * | 2016-11-24 | 2017-03-15 | 青岛大学 | A kind of preparation method and application of amorphous nano molybdenum disulfide catalyst |
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