CN110479313B - Hydrogenation catalyst, preparation method and application thereof, and hydrofining method - Google Patents

Hydrogenation catalyst, preparation method and application thereof, and hydrofining method Download PDF

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CN110479313B
CN110479313B CN201810464234.XA CN201810464234A CN110479313B CN 110479313 B CN110479313 B CN 110479313B CN 201810464234 A CN201810464234 A CN 201810464234A CN 110479313 B CN110479313 B CN 110479313B
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catalyst
hydrogenation catalyst
silica
metal component
active metal
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CN110479313A (en
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韩伟
聂红
龙湘云
杨清河
赵新强
邵志才
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—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
    • 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
    • B01J27/051—Molybdenum
    • B01J27/0515—Molybdenum with iron group metals or platinum group metals
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

Abstract

The invention relates to the field of hydrogenation, and discloses a hydrogenation catalyst, a preparation method and application thereof, and a hydrofining method, wherein the catalyst comprises a carrier and an active metal component B loaded on the carrier, part of the active metal component B exists in a trisulfide form, the rest of the active metal component B exists in a trioxide form, the atomic ratio of sulfur to the active metal component B is 2.1-2.9, and the degree of vulcanization of the catalyst is 40-80%. The preparation method of the catalyst comprises the following steps: soaking the carrier by adopting a solution C containing a VIB group metal compound, and drying to obtain a solid A; the solution D containing the organic sulfur source is contacted with the solid A, and then the obtained solid product is dried. The hydrogenation catalyst provided by the invention has excellent hydrogenation reaction activity, and meanwhile, the vulcanization start-up process of the conventional hydrogenation catalyst can be omitted, the start-up time is shortened, and the start-up cost is saved.

Description

Hydrogenation catalyst, preparation method and application thereof, and hydrofining method
Technical Field
The invention relates to the field of hydrogenation, in particular to a hydrogenation catalyst, a preparation method and application thereof, and a hydrofining method.
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, CN1861260A, CN101088619A, CN101088620A, CN1994567A, CN101279296A, CN101491725A, 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, before the catalyst obtained by the above route is filled into a reaction device, passivation treatment is required, potential safety hazards of spontaneous combustion and oxidative inactivation exist in the transportation process, a special pre-vulcanizing device is required, and the construction of the pre-vulcanizing device brings huge capital investment and potential environmental protection pressure and policy risks.
In order to achieve excellent hydrogenation performance of hydrogenation catalysts while avoiding the above-mentioned problems of "in-situ" sulfiding and "ex-situ" sulfiding, more and more attention and research has been paid to the direct preparation route of sulfided hydrogenation catalysts in recent years. Therefore, the technical route still has great use limitation and certain social risk at present.
Disclosure of Invention
The invention aims to overcome the defects of the existing 'in-situ' vulcanization and 'out-of-situ' vulcanization technologies, and provides a novel hydrogenation catalyst, a preparation method of the hydrogenation catalyst, the hydrogenation catalyst prepared by the preparation method, application of the hydrogenation catalyst in hydrofining and a hydrofining method. The hydrogenation catalyst prepared by the preparation method provided by the invention has excellent hydrogenation reaction activity, and meanwhile, the vulcanization start-up process of the conventional hydrogenation catalyst can be omitted, the start-up time is shortened, and the start-up cost is saved.
The invention provides a hydrogenation catalyst in a first aspect, which comprises a carrier and an active metal component B loaded on the carrier, wherein the active metal component B is selected from at least one of VIB group metal elements, part of the active metal component B exists in a trisulfide form, the rest of the active metal component B exists in a trioxide form, the atomic ratio of sulfur to the active metal component B in the catalyst measured by X-ray photoelectron spectroscopy is 2.1-2.9, and the degree of vulcanization of the catalyst is 40-80%
In a second aspect, the present invention provides a method for preparing a hydrogenation catalyst, the method comprising:
(1) soaking the carrier by adopting a solution C containing a VIB group metal compound, and drying to obtain a solid A;
(2) contacting a solution D containing at least one organic sulfur source with a solid A, and then drying the resulting solid product;
the organic sulfur source is a sulfur-containing substance which can be hydrolyzed in the solution D and/or under the contact condition, and the contact temperature is 20-150 ℃ and the contact time is not less than 0.5 hour.
Preferably, the method further comprises introducing a group VIII metal element into the hydrogenation catalyst by means of mode 1) and/or mode 2); the mode 1) includes: adding a group VIII metal compound to the solution C; the mode 2) includes: impregnating the dried substance obtained in the step (2) with a solution E containing a group VIII metal compound.
In a third aspect, the present invention provides a hydrogenation catalyst obtained by the above-mentioned production method.
In a fourth aspect, the present invention provides the use of the above hydrogenation catalyst in hydrorefining.
In a fifth aspect, the present invention provides a hydrofinishing method, comprising: the hydrogenation catalyst provided by the invention is activated to obtain an activated catalyst, and a raw material to be hydrorefined is contacted with the activated catalyst in the presence of hydrogen under the hydrorefining condition.
The inventor of the invention discovers through research that in the process of preparing the hydrogenation catalyst, a solution C containing a VIB group metal compound is adopted to impregnate a carrier, and the carrier is dried to obtain a solid A, and then a solution D containing at least one organic sulfur source is adopted to contact with the solid A under certain conditions (the temperature is 20-150 ℃, and the time is not less than 0.5 hour), so that most of oxidation state active substances can be converted into vulcanization state species, the hydrogenation catalyst with proper vulcanization degree can be obtained through oxygen-sulfur exchange in an aqueous solution, and the vulcanization state catalyst with proper vulcanization degree and higher auxiliary agent modification degree can be obtained through subsequent activation treatment, and the hydrogenation catalyst has stronger activity when being used in hydrogenation reaction. Preferably, the group VIII metal element may be introduced into the catalyst by adding a group VIII metal compound to the solution C and/or impregnating the dried substance obtained in step (2) with a solution E containing a group VIII metal compound, thereby further improving the activity of the catalyst.
The vulcanized hydrogenation catalyst obtained by the existing 'in-situ' vulcanization and 'out-of-situ' vulcanization technologies has the advantages of large acting force of active metal and a carrier, low active metal vulcanization degree and auxiliary agent modification degree, and weak catalyst activity. The sulfidation hydrogenation catalyst prepared by the chemical deposition method disclosed by the prior art has the advantages of small metal loading, namely small metal utilization rate (high production cost), and less action force between the active metal and the carrier and poor catalyst stability.
The method provided by the invention utilizes a conventional impregnation method to prepare an oxidation state catalyst, and then the oxidation state catalyst reacts with a solution D containing at least one organic sulfur source, the metal content is 100 percent, the production cost is lower, part of active metal components B in the obtained hydrogenation catalyst exist in a trioxide form, the rest part of active metal components B exist in a trisulfide form, the atomic ratio of sulfur to the active metal components B is 2.1-2.9, the vulcanization degree of the catalyst is 40-80 percent, the vulcanization degree of the catalyst is moderate and is equivalent to the binding force of a carrier, and the activated hydrogenation catalyst obtained after the catalyst is activated has proper vulcanization degree. When VIII group metal elements are also introduced in the preparation process of the catalyst, the activated hydrogenation catalyst obtained after activation treatment has higher modification degree of the auxiliary agent, and has higher activity when being used for hydrogenation treatment.
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 hydrogenation catalyst in a first aspect, which comprises a carrier and an active metal component B loaded on the carrier, wherein the active metal component B is selected from at least one of VIB group metal elements, part of the active metal component B exists in a trisulfide form, the rest of the active metal component B exists in a trioxide form, the atomic ratio of sulfur to the active metal component B in the catalyst measured by X-ray photoelectron spectroscopy is 2.1-2.9, and the degree of vulcanization of the catalyst is 40-80%
In the hydrogenation catalyst provided by the invention, the active metal component B exists in the form of trioxide and trisulfide, the atomic ratio of sulfur to the active metal component B is 2.1-2.9, the degree of vulcanization of the catalyst is moderate, and the catalyst can have better hydrogenation performance only by simply activating the catalyst before operation.
In the present invention, the ratio of the active metal component B present in the form of trioxide to the active metal component B present in the form of trisulfide can be calculated from the specific numerical value of the atomic ratio of sulfur to the active metal component B.
In the present invention, it is preferable that the active metal component B is a molybdenum and/or tungsten element.
The carrier in the present invention is not particularly limited, and may be any of various carriers commonly used in the art, commercially available or prepared by any method known in the art, and may be a porous oxide carrier, and may be selected from, for example, γ -alumina, silica, alumina-silica, titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-magnesiaOne or more of silica-alumina-zirconia. Particularly preferably, the carrier is gamma-Al with the diameter of 1mm to 5mm2O3And (3) granules.
In the present invention, the presence form of the active metal component B in the hydrogenation catalyst can be determined by X-ray photoelectron spectroscopy (XPS).
In the present invention, without particular reference, X-ray photoelectron spectroscopy (XPS) was carried out on an ESCALab 250 type X-ray photoelectron spectrometer (VG, UK) using a radiation source of Al K α, a resolution of 0.5eV, and an internal standard of binding energy (Eb 285.0eV) of C1s contaminated with carbon.
In the present invention, the atomic ratio of sulfur to the active metal component B is also given by the results of X-ray photoelectron spectroscopy.
In the present invention, the degree of sulfidation of the catalyst is determined by X-ray photoelectron spectroscopy (XPS), wherein the degree of sulfidation is obtained by processing XPS data, as described in Han et al, Journal of Materials Chemistry 2012,22: 25340.
According to a preferred embodiment of the invention, the atomic ratio of sulphur to the reactive metal component B is between 2.5 and 2.8. This preferred embodiment is more advantageous in improving the catalytic performance of the catalyst.
According to a preferred embodiment of the invention, the hydrogenation catalyst has a degree of sulfidation of 60 to 85%, preferably 65 to 72%. The preferable vulcanization degree is more suitable, and the activity and the stability of the catalyst can be better considered. The degree of sulfidation of the hydrogenation catalyst means the proportion of the positive tetravalent active metal component B to the total active metal component B. Although part of the active metal component B is present in the form of trisulfide, S is present in the catalyst2 2-The hydrogenation catalyst therefore contains a positive tetravalent active metal component B in the form of a trisulfide.
According to a preferred embodiment of the present invention, the hydrogenation catalyst has a degree of sulfidation after activation treatment of 65 to 90%, preferably 70 to 90%, more preferably 80 to 89%;
the conditions of the activation treatment include: at a hydrogen space velocity of 1h-1Bars with a hydrogen partial pressure of 4MPaThe treatment was carried out at 250 ℃ for 2 hours and then at 360 ℃ for 4 hours.
The hydrogenation catalyst provided by the invention is activated under a specific activation condition, so that a proper vulcanization degree (higher than the vulcanization degree of a vulcanized hydrogenation catalyst obtained by adopting the existing 'in-situ' vulcanization and 'out-of-situ' vulcanization technologies and lower than the vulcanization degree of a vulcanized hydrogenation catalyst prepared by adopting a chemical deposition method disclosed by the prior art) can be obtained, and the catalyst has higher catalyst activity compared with the vulcanized hydrogenation catalyst provided by the prior art.
The method for testing the sulfidation degree of the catalyst after activation treatment is as described above and is not described herein.
According to a preferred embodiment of the invention, the support is present in an amount of from 60 to 90% by weight, preferably from 70 to 85% by weight, based on the total amount of catalyst, and the active metal component B is present in an amount of from 10 to 40% by weight, preferably from 15 to 30% by weight, calculated as oxide.
The catalyst component contents were measured by X-ray fluorescence spectroscopy RIPP 132-90 (petrochemical analysis (RIPP test), Yangchini, Kangying, Wu Wenhui ed., first 9 months 1990, 371) 379.
The catalyst is a single metal hydrogenation catalyst, and in order to further improve the hydrogenation performance of the catalyst, the catalyst preferably further comprises an active metal component A supported on a carrier, wherein the active metal component A is selected from at least one of the VIII group metal elements.
In the present invention, it is preferable that the active metal component a is a cobalt and/or nickel element.
According to a preferred embodiment of the present invention, after the hydrogenation catalyst is subjected to an activation treatment, the modification degree of the auxiliary agent is 28 to 60%, preferably 35 to 52%, and more preferably 43 to 50%, wherein the modification degree of the auxiliary agent is a ratio of an amount of the active metal component a existing in the form of the class ii active phase a-B-S to a total amount of the active metal component a, as measured by X-ray electron spectroscopy, and the conditions of the activation treatment are as described above and will not be described herein again.
The auxiliary agent of the inventionThe degree of modification refers to the content of the class II active phase A-B-S in the catalyst, namely the ratio of the amount of the active metal component A existing in the form of the class II active phase A-B-S to the total amount of the active metal component A measured by X-ray electron spectroscopy. A represents a VIII group metal element (such as Co and Ni), B represents a VIB group metal element (such as Mo and W), and S is a sulfur element. In the hydrogenation catalyst after activation treatment, the VIII group metal elements exist in different forms, for example, Co is taken as an example, in the vulcanized CoMo catalyst, Co is respectively Co2+Co-Mo-S and Co9S8The Co existing in different forms corresponds to peaks at different positions in the XPS spectrogram, and the Co is calculated by unfolding the peaks2+Co-Mo-S and Co9S8Corresponding peak area by Co-Mo-S corresponding peak area/(Co)2+Corresponding peak area + Co-Mo-S corresponding peak area + Co9S8Corresponding peak area) x 100%, the content of the II-type active phase Co-Mo-S is calculated, and the method is also suitable for NiW catalysts. The specific calculation method can be found in Qielimei article (X-ray photoelectron spectroscopy is used to study the chemical state of active elements in hydrodesulfurization catalyst [ J]And petroleum science and newspaper: petroleum processing, 2011, 27 (4): 638-642).
According to a preferred embodiment of the invention, the support is present in an amount of 54 to 85 wt.%, calculated as oxide, of active metal component a in an amount of 1 to 10 wt.% and active metal component B in an amount of 8 to 45 wt.%, based on the total amount of catalyst; it is further preferred that the content of the carrier is 68 to 84% by weight, the content of the active metal component A is 1.5 to 6% by weight and the content of the active metal component B is 10 to 30% by weight, calculated as oxides, based on the total amount of the catalyst.
It should be noted that, since the active metal components are present in the form of oxides and sulfides, respectively, the metal components are in terms of the content of oxides. Obviously, when the catalyst contains only the above components, the content of each component must satisfy 100%.
In a second aspect, the present invention provides a method for preparing a hydrogenation catalyst, comprising:
(1) soaking the carrier by adopting a solution C containing a VIB group metal compound, and drying to obtain a solid A;
(2) contacting a solution D containing at least one organic sulfur source with a solid A, and then drying the resulting solid product;
the organic sulfur source is a sulfur-containing material capable of being hydrolyzed in the solution D and/or under contact conditions at a temperature of 20 to 150 ℃ for a time of not less than 0.5 hour (preferably 0.5 to 40 hours).
The method provided by the invention comprises the steps of contacting an organic sulfur source with a solid A in a solution under specific conditions (the temperature is 20-150 ℃, and the time is not less than 0.5 hour), and hydrolyzing the organic sulfur source to generate H2S or S2-And further reacts with the solid A to form active species in a sulfurated state in situ. The method is simple to operate, a part of VIB metals in the obtained hydrogenation catalyst exist in a form of trisulfide, and the VIB group metal disulfide with abundant lattice defect sites can be formed by performing subsequent activation treatment on the VIB metals. The inventor of the invention finds out through research that the dynamic conversion process of the trisulfide to the disulfide is very beneficial to the modification of the auxiliary VIII metal atom, namely the formation of rich II active phase A-B-S.
According to a preferred embodiment of the invention, the group VIB metal element is a molybdenum and/or tungsten element. The group VIB metal compound may be at least one selected from molybdenum trioxide, tungsten trioxide, ammonium molybdate, sodium tungstate, ammonium paramolybdate, ammonium metatungstate, ammonium phosphomolybdate and ammonium phosphotungstate.
The selection of the carrier is as described above and will not be described in detail here. When the group VIB metal compound is selected from molybdenum trioxide and/or tungsten trioxide, the solution C may further contain a cosolvent, such as phosphoric acid, and the amount of the cosolvent used may be selected by those skilled in the art according to actual conditions, as long as the molybdenum trioxide and/or tungsten trioxide can be sufficiently dissolved.
The invention has wide selection range of the dosage of the VIB group metal compound and the carrier, and preferably, the dosage of the VIB group metal compound and the carrier is such that the content of the carrier in the prepared catalyst is 60-90 wt%, preferably 70-85 wt%, based on the total amount of the catalyst, and the content of the VIB group metal element is 10-40 wt%, preferably 15-30 wt%, calculated by oxide.
The impregnation in step (1) of the present invention may be a saturated impregnation. The solvent in the solution C may be water, wherein the concentration of the group VIB metal compound may be selected according to the water absorption of the carrier and the amount of the group VIB metal compound to be loaded, which is not described herein again.
The invention does not limit the dried strip in step (1), and the drying conditions widely used in the industry, such as drying at 80-150 deg.C for 1-6 hours in air atmosphere, can be used.
According to the invention, the solid A is not calcined. Whereas the oxidation state catalysts described in the prior art are generally referred to as calcined catalysts.
According to a preferred embodiment of the invention, the pH of the solution D is between 3.5 and 6.5 or between 7.5 and 10.5. In this preferred embodiment of the invention, the solution D is subjected to milder acidic or basic conditions, which in turn promotes the transition of the solid a to the active species in the sulphurized state, while ensuring that the support is not destroyed. When the pH of the solution D is less than 3.5 or more than 10.5, the carrier containing alumina as a main carrier component is dissolved to some extent, which may affect the physical structure of the catalyst and thus the dispersion state of the active species.
According to a preferred embodiment of the invention, the pH of the solution D is between 4.5 and 5.5 or between 8.5 and 9.5. The use of this preferred pH value is more advantageous for the above-mentioned oxygen-sulfur exchange reaction to proceed sufficiently and rapidly.
According to the present invention, the pH of the solution D can be adjusted in various ways, which is not particularly limited in the present invention, for example, by adding an acid and/or a base to adjust the pH of the solution D. The acid 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 acid is at least one selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, and citric acid, and further preferably hydrochloric acid. By adopting the preferred embodiment provided by the invention, the introduced impurity elements can be naturally removed in the later stage of the preparation of the vulcanization type hydrogenation catalyst, and the performance of the catalyst is not influenced.
According to the present invention, preferably, the base is at least one selected from the group consisting of ammonia water, sodium hydroxide, and potassium hydroxide, and more preferably sodium hydroxide.
According to the invention, the solvent of the solution D is preferably water.
According to a preferred embodiment of the present invention, the organic 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),
Figure BDA0001661670860000101
in the formula (1), R1Is H, 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.
According to a preferred embodiment of the present invention, the method for preparing the hydrogenation catalyst comprises:
(1) soaking the carrier by adopting a solution C containing a VIB group metal compound, and drying to obtain a solid A;
(2) contacting a solution D containing at least one organic sulfur source with a solid A, and then drying the resulting solid product;
the organic sulfur source is at least one selected from L-cysteine, thioamide shown in a formula (1), monothioester shown in a formula (2) and dithioester shown in a formula (3),
Figure BDA0001661670860000111
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.
According to the present invention, preferably, the organic sulfur source is a thioamide represented by formula (1), more preferably, the organic sulfur source is thiourea and/or thioacetamide, and most preferably, thioacetamide.
According to a preferred embodiment of the present invention, the concentration of the organic sulfur source in the solution D is 0.05 to 20mol/L, preferably 1 to 15mol/L, and more preferably 4 to 10 mol/L.
According to a preferred embodiment of the present invention, the method further comprises introducing a group VIII metal element into the hydrogenation catalyst by means of the manner 1) and/or the manner 2);
the mode 1) includes: adding a group VIII metal compound to the solution C;
the mode 2) includes: impregnating the dried substance obtained in the step (2) with a solution E containing a group VIII metal compound.
In the mode 1) of the present invention, when the group VIII metal compound is added to the solution C, if the amount of the solvent in the solution C is not enough to dissolve the group VIII metal compound, a person skilled in the art may add a solvent (e.g., water) to the solution C as the case may be.
In the mode 2) of the present invention, the impregnation may be saturation impregnation, and the content of the group VIII metal compound in the solution E (the solvent of the solution E is preferably water) may be determined according to the amount of the group VIII metal element required in the catalyst, and may be appropriately selected by those skilled in the art according to the content of the group VIII metal compound.
According to an embodiment of the present invention, the manner 2) further includes drying the impregnated material. The drying conditions may be the same as those described in step (1).
According to a preferred embodiment of the invention, the group VIII metal element is a cobalt and/or nickel element. The group VIII metal compound may be at least one selected from the group consisting of nitrates, hydroxycarbonates, chlorides, sulfates and acetates of the group VIII metals.
According to a preferred embodiment of the present invention, the amount of the group VIII metal compound, the amount of the group VIB metal compound and the amount of the carrier are such that the catalyst obtained contains 54 to 85 wt% of the carrier, based on the total amount of the catalyst, and the amount of the group VIII metal element is 1 to 10 wt% and the amount of the group VIB metal element is 8 to 45 wt%, calculated as oxides; more preferably, the carrier has a content of 68-84 wt%, calculated as oxide, of group VIII metal elements of 1.5-6 wt% and of group VIB metal elements of 10-30 wt%, based on the total amount of the catalyst.
According to the invention, the contacting is preferably carried out under closed conditions. The operation is carried out under a closed condition, the hydrogen sulfide obtained by hydrolyzing the organic sulfur source can not be released into the air, the air pollution can not be caused, the hydrolysis of the hydrogen sulfide into divalent sulfur ions can be facilitated, and the organic sulfur source can be effectively utilized. The contacting may be carried out in an autoclave or closed reactor capable of withstanding hydrothermal environments, which autoclave or closed reactor can withstand 10 f9Pressure of Pa.
According to the preparation method provided by the invention, the contact temperature is preferably 60-120 ℃ and the contact time is 2-24 hours, and further preferably the contact temperature is 70-100 ℃ and the contact time is 6-18 hours. The adoption of the optimized contact condition can directly influence the oxygen-sulfur exchange degree and speed, further improve the performance of the catalyst, influence the oxygen-sulfur exchange degree and speed due to too low contact temperature, increase the treatment time, influence the physical properties of the carrier due to too high temperature, and further generate adverse effect on the catalyst. The adoption of the contact condition can not only improve the performance of the catalyst, but also shorten the preparation time and improve the efficiency.
In the present invention, the form of obtaining the solid product is not particularly limited, and can be obtained by filtration, for example.
According to the present invention, preferably, the drying conditions of step (2) include: under an inert atmosphere or a reducing atmosphere (preferably an inert atmosphere), at a temperature of 100-250 ℃, preferably 100-130 ℃, for a time of 1-12 hours, preferably 2-6 hours.
According to the preparation method of the present invention, the inert atmosphere may be provided by one or more of nitrogen, argon and helium, preferably nitrogen.
According to the preparation method of the present invention, the reducing atmosphere may be provided by hydrogen and/or hydrogen sulfide and optionally an inert gas.
The reducing atmosphere may contain an inert gas, and when the inert gas is contained in the reducing atmosphere, the volume content of hydrogen and/or hydrogen sulfide is not less than 5%.
Before the catalyst provided by the invention is used, pre-vulcanization is not needed, and only simple activation treatment is needed during start-up to obtain an active metal component with proper vulcanization and obtain a II-type A-B-S active phase with higher catalytic performance.
Therefore, the invention also provides a hydrogenation catalyst prepared by the preparation method. The above-described hydrogenation catalyst of the present invention can be suitably used for various hydrogenation reactions including, but not limited to, hydrorefining, hydrotreating and hydrocracking, and is particularly suitable for the hydrorefining reaction. Therefore, the invention also provides the application of the hydrogenation catalyst in hydrofining. Such hydrofinishing includes, but is not limited to, hydrodesulfurization, hydrodenitrogenation, hydrodearomatization, hydrodecarbonization, hydrodemetallization, and hydrodeoxygenation.
The invention also provides a hydrofining method, which comprises the following steps: the hydrogenation catalyst provided by the invention is activated to obtain an activated catalyst, and a raw material to be hydrorefined is contacted with the activated catalyst in the presence of hydrogen under the hydrorefining condition.
According to the hydrofining method provided by the present invention, preferably, the activating conditions include: under the inert atmosphere or the reducing atmosphere, the temperature is 240-500 ℃, and the time is 1-12 h; further preferably, the catalyst is activated at a temperature of 240-310 ℃ for 0.5-6h and then at a temperature of 320-500 ℃ for 0.5-6h under an inert atmosphere or a reducing atmosphere (preferably a reducing atmosphere). The inventor finds that the activation process is firstly carried out at low temperature (240-.
The inert atmosphere or reducing atmosphere is as described above and will not be described in detail here.
According to a preferred embodiment of the invention, the activated catalyst has a degree of sulfidation of 65 to 90%, preferably 70 to 90%, more preferably 80 to 89%, and/or
The degree of modification with an auxiliary is 28 to 60%, preferably 35 to 52%, and more preferably 43 to 50%. The methods for testing the vulcanization degree and the modification degree of the auxiliary after activation of the catalyst are as described above and will not be described herein.
The catalyst provided by the invention can be used for any raw material needing hydrofining, is particularly suitable for the hydrofining process or the hydrogenation pretreatment process of petroleum distillate oil or coal liquefaction distillate oil, and preferably, the raw material to be hydrofined is the petroleum distillate oil or the coal liquefaction distillate oil. The present invention is illustrated in the examples by way of example of a diesel model compound, but the present invention is not limited thereto.
According to the hydrofinishing process of the present invention, the hydrofinishing conditions may be conventional hydrofinishing conditions. For example: the temperature can be 200-425 ℃, preferably 300-400 ℃; the hydrogen partial pressure may be from 1 to 15 MPa, preferably from 2 to 8 MPa; the volume ratio of the hydrogen to the oil can be 100-5000, and preferably 200-1000; the liquid hourly space velocity can be 0.2-5 hours-1Preferably 0.2 to 3 hours-1。
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 and comparative examples, the contents of the components in the catalyst were measured by X-ray fluorescence spectroscopy analysis RIPP 132-90 (petrochemical analysis (RIPP test method), Yangrodin, Kan English, Wu Wenhui ed, science publishers, first 9 months 1990, 371,379).
The atomic ratio of sulfur to the active metal component B was determined by X-ray photoelectron spectroscopy (XPS).
The degree of sulfidation of the group VIB metal element in the catalyst is determined by X-ray photoelectron spectroscopy (XPS), wherein the degree of sulfidation is obtained by processing XPS data, and the specific processing method can be found in Han et al, Journal of Materails Chemistry 2012,22: 25340. The modifier of the auxiliary agent is obtained by XPS data processing, and the specific processing method can be seen in the chemical state [ J ] of active elements in a hydrodesulfurization catalyst researched by a literature X-ray photoelectron spectroscopy, and the petrology report: petroleum processing, 2011, 27 (4): 638-642.
Among them, X-ray photoelectron spectroscopy (XPS) was performed on an ESCA Lab 250 type X-ray photoelectron spectrometer (VG, england) obtained under the conditions of Al K α as a radiation source, 0.5eV as a resolution, and 285.0eV as a binding energy of C1s contaminated with carbon as an internal standard.
Example 1
(1) 80mL of solution C containing 36.2g of ammonium molybdate was prepared, followed by 100g of γ -Al2O3(diameter 1.5mm, specific surface area 250 m)2Per g, pore volume of about 0.8mL/g, the same applies below) saturated impregnation, and drying at 120 ℃ for 2h to obtain solid A;
(2) preparing 45mL of aqueous solution containing 26.0g of thioacetamide, and adjusting the pH value to 5 by dropwise adding 2.4mol/L of dilute nitric acid in the stirring process to obtain solution D; the solution D was transferred to a 100mL autoclave containing 60g of solid A, which was then placed in a rotary oven and contacted at 85 ℃ for 12 hours, filtered to give a solid product, and dried at 100 ℃ for 3 hours under nitrogen to give catalyst S-1 in the sulfided state. XPS analysis tableIt contains a certain amount of MoS3The species, their composition, degree of sulfidation, atomic ratio of S to Mo are listed in table 1.
(3) 1g of catalyst S-1 in a sulfuration state is placed in a hydrogenation reactor at a hydrogen airspeed of 1h-1Treating the catalyst at 250 ℃ for 2 hours under the condition that the hydrogen partial pressure is 4MPa, and then heating to 360 ℃ for 4 hours to obtain an activated catalyst, wherein the A-S-1 is obtained. The degree of vulcanization is shown in Table 1.
Comparative example 1
Solid a was obtained according to the procedure of step (1) of example 1, and subjected to sulfidation activation using a conventional sulfidation method, specifically: 1g of solid A is filled in a hydrogenation reactor, and CS with the mass fraction of 3 percent is adopted2Cyclohexane solution is taken as a vulcanizing agent, and the vulcanizing conditions comprise: h2The partial pressure is 4MPa, and the space velocity of hydrogen is 1.5h-1The temperature was 360 ℃, the time 4h, and the hydrogen to oil volume ratio 500, giving an activated catalyst, denoted as A-C-1. The degrees of vulcanization of A-C-1 are shown in Table 1.
Comparative example 2
The procedure of example 1 was followed, except that thioacetamide was replaced with an equimolar amount of ammonium sulfide based on elemental sulfur, to obtain sulfided catalysts C-2 and A-C-2, with the sulfided catalyst C-2 containing a certain amount of MoS3The species whose composition, degree of vulcanization, atomic ratio of S to Mo are listed in table 1; the degrees of vulcanization of A-C-2 are shown in Table 1.
Example 2
(1) 80mL of solution C containing 30g of molybdenum trioxide and 8.45g of phosphoric acid was prepared, and then 100g of γ -Al was added2O3Saturated dipping, and drying for 2h at 120 ℃ to obtain solid A;
(2) preparing 60mL of aqueous solution containing 36g of thioacetamide, and adjusting the pH value to 9 by dropwise adding 2.4mol/L ammonia water in the stirring process to obtain solution D; the solution D was transferred to a 100mL autoclave containing 60g of solid A, which was then placed in a rotary oven and contacted at 70 ℃ for 18 hours, filtered to give the solid product, and dried at 100 ℃ for 3 hours under nitrogen to give the catalyst S-2 in the sulfided state. XPS analysis shows that it contains a certain amount of MoS3Species, composition, degree of vulcanization, of S and MoThe atomic ratios are listed in table 1.
(3) 1g of catalyst S-2 in a sulfurized state is placed in a hydrogenation reactor, and the space velocity of hydrogen is 1h-1Treating the catalyst at 250 ℃ for 2 hours under the condition that the hydrogen partial pressure is 4MPa, and then heating to 360 ℃ for 4 hours to obtain an activated catalyst, wherein the A-S-2 is obtained. The degrees of vulcanization are shown in Table 1.
Comparative example 3
80mL of solution C containing 30g of molybdenum trioxide and 8.45g of phosphoric acid was prepared, and then 100g of γ -Al was added2O3Saturated dipping, drying for 2h at 120 ℃ to obtain solid A, carrying out vulcanization activation on the solid A by adopting a traditional vulcanization method, and obtaining an activated catalyst marked as A-C-3 under the same vulcanization condition as the comparative example 1. The degrees of vulcanization of A-C-3 are shown in Table 1.
Example 3
(1) 80mL of solution C containing 43.0g of ammonium metatungstate was prepared, followed by 100g of γ -Al2O3Saturated dipping, and drying for 2h at 120 ℃ to obtain solid A;
(2) preparing 80mL of aqueous solution containing 40g of thioacetamide, and adjusting the pH value to 9.5 by dropwise adding 2.4mol/L of sodium hydroxide in the stirring process to obtain solution D; the solution D was transferred to a 100mL autoclave containing 60g of solid A, which was then placed in a rotary oven and contacted at 90 ℃ for 10 hours, filtered to give the solid product, and dried at 100 ℃ for 3 hours under nitrogen to give the catalyst S-3 in the sulfided state. XPS analysis shows that it contains a certain amount of WS3The species, their composition, degree of sulphurization, atomic ratio of S to W are listed in table 1.
(3) 1g of catalyst S-3 in a sulfuration state is placed in a hydrogenation reactor, and the space velocity of hydrogen is 1h-1Treating the catalyst at 250 ℃ for 2 hours under the condition that the hydrogen partial pressure is 4MPa, and then heating to 360 ℃ for 4 hours to obtain an activated catalyst, wherein the A-S-3 is counted. The degrees of vulcanization are shown in Table 1.
Comparative example 4
Solid A was obtained by the procedure of step (1) of example 3, and sulfided and activated by conventional sulfiding procedures under the same sulfiding conditions as in comparative example 1 to give an activated catalyst, designated A-C-4. The degrees of cure of A-C-4 are shown in Table 1.
Example 4
(1) The same as example 1;
(2) preparing 45mL of aqueous solution containing 30g of thioacetamide, and adjusting the pH value to 4.5 by dropwise adding 2.4mol/L hydrochloric acid in the stirring process to obtain solution D; the solution D was transferred to a 100mL autoclave containing 60g of solid A, which was then placed in a rotary oven and contacted at 100 ℃ for 6 hours, filtered to give the solid product, and dried at 100 ℃ for 3 hours under nitrogen to give the catalyst S-4 in the sulfided state. XPS analysis shows that it contains a certain amount of MoS3The species, their composition, degree of sulfidation, atomic ratio of S to Mo are listed in table 1.
(3) 1g of catalyst S-4 in a sulfuration state is placed in a hydrogenation reactor, and the space velocity of hydrogen is 1h-1Treating the catalyst at 250 ℃ for 2 hours under the condition that the hydrogen partial pressure is 4MPa, and then heating to 360 ℃ for 4 hours to obtain an activated catalyst, wherein the activated catalyst is A-S-4. The degrees of vulcanization are shown in Table 1.
Example 5
The procedure of example 1 was followed except that in step (1), 80mL of solution C containing 43.0g of ammonium metatungstate and 6.45g of phosphoric acid was prepared. Obtaining sulfuration state catalysts S-5 and A-S-5, wherein the sulfuration state catalyst S-5 contains a certain amount of MoS3The species whose composition, degree of vulcanization, atomic ratio of S to Mo are listed in table 1; the degrees of vulcanization of A-S-5 are shown in Table 1.
Example 6
The procedure of example 1 was followed except that, in step (2), the pH was adjusted to 3.5 by dropwise addition of 2.4mol/L hydrochloric acid. Obtaining sulfuration state catalysts S-6 and A-S-6, wherein the sulfuration state catalyst S-6 contains a certain amount of MoS3The species whose composition, degree of vulcanization, atomic ratio of S to Mo are listed in table 1; the degrees of vulcanization of A-S-6 are shown in Table 1.
Example 7
The procedure of example 1 was followed except that, in step (1), the pH was adjusted to 10.5 by dropwise addition of 2.4mol/L aqueous ammonia. Obtaining sulfuration state catalysts S-7 and A-S-7, wherein the sulfuration state catalyst S-7 contains a certain amount of MoS3The species whose composition, degree of vulcanization, atomic ratio of S to Mo are listed in table 1; vulcanization of A-S-7The degrees are shown in Table 1.
Example 8
The procedure of example 1 was followed except that, in step (2), solution D was transferred to a 100mL autoclave containing 60g of solid A, and the autoclave was then placed in a rotary oven and contacted at 60 ℃ for 12 hours. Obtaining sulfuration state catalysts S-8 and A-S-8, wherein the sulfuration state catalyst S-8 contains a certain amount of MoS3The species whose composition, degree of vulcanization, atomic ratio of S to Mo are listed in table 1; the degrees of vulcanization of A-S-8 are shown in Table 1.
Example 9
The procedure of example 1 was followed except that, in step (2), solution D was transferred to a 100mL autoclave containing 60g of solid A, and the autoclave was then placed in a rotary oven and contacted at 140 ℃ for 12 hours. Obtaining sulfuration state catalysts S-9 and A-S-9, wherein the sulfuration state catalyst S-9 contains a certain amount of MoS3The species whose composition, degree of vulcanization, atomic ratio of S to Mo are listed in table 1; the degrees of vulcanization of A-S-9 are shown in Table 1.
Example 10
The procedure of example 1 was followed except that, in step (2), the pH was adjusted to 2 by dropwise addition of 2.4mol/L hydrochloric acid. Obtaining sulfuration state catalysts S-10 and A-S-10, wherein the sulfuration state catalyst S-10 contains a certain amount of MoS3The species whose composition, degree of vulcanization, atomic ratio of S to Mo are listed in table 1; the degrees of vulcanization of A-S-10 are shown in Table 1.
Example 11
The procedure of example 1 was followed except that, in step (2), the pH was adjusted to 11.5 by dropwise addition of 2.4mol/L aqueous ammonia. Obtaining sulfuration state catalysts S-11 and A-S-11, wherein the sulfuration state catalyst S-11 contains a certain amount of MoS3The species whose composition, degree of vulcanization, atomic ratio of S to Mo are listed in table 1; the degrees of vulcanization of A-S-11 are shown in Table 1.
Example 12
The procedure of example 1 was followed except that 80mL of solution C containing 36.2g of ammonium molybdate and 26g of nickel nitrate was prepared in step (1). Obtaining the sulfuration state catalysts S-12 and A-S-12, wherein the sulfuration state catalyst S-12 contains a certain amount of MoS3Species, composition, degree of cure,The atomic ratio of S to Mo is listed in Table 1; the degrees of vulcanization and the degree of coagent modification for A-S-12 are listed in Table 1.
Example 13
According to the method of the embodiment 1, except that the method further comprises the steps of preparing 48mL of solution E containing 26g of nickel nitrate, carrying out saturated impregnation on the sulfidized catalyst S-1 obtained in the step (2) by using the solution E, and drying at 120 ℃ for 2h to obtain the sulfidized catalyst S-13; A-S-13 was obtained by activating the sulfided catalyst S-13 according to the method of step (3) of example 1, the sulfided catalyst S-13 containing a certain amount of MoS3The species whose composition, degree of vulcanization, atomic ratio of S to Mo are listed in table 1; the degrees of vulcanization and the degree of coagent modification for A-S-13 are listed in Table 1.
TABLE 1
Figure BDA0001661670860000201
Figure BDA0001661670860000211
Test example 1
The catalysts provided in the above examples and comparative examples were subjected to hydrodesulfurization activity evaluation.
Evaluation of hydrodesulfurization activity: raw materials are respectively an n-heptane solution with the mass content of Dibenzothiophene (DBT) of 1 percent and an n-heptane solution with the mass content of 4, 6-dimethyldibenzothiophene (4,6-DMDBT) of 0.45 percent; the reaction conditions are as follows: 4.0MPa, 345 ℃, 400 of hydrogen-oil volume ratio and 2.0h of liquid hourly space velocity-1. After the reaction is stabilized for 3 hours, samples are taken every 4 hours, and the sulfur content in the raw material of the hydrodesulfurization reaction and the obtained product is determined by gas chromatography for three times, and the average value is taken. The DBT and 4,6-DMDBT hydrodesulfurization reactions were treated as first order reactions, the catalyst hydrodesulfurization activity was expressed as the hydrodesulfurization activity relative to reference D (comparative example 1), and the relative hydrodesulfurization activity of the catalyst was calculated according to equation (1):
Figure BDA0001661670860000212
wherein k (S) represents the hydrodesulfurization activity of the catalyst and k (D)S) Represents the hydrodesulphurisation activity of reference agent D (comparative example 1).
In the formula, SSpThe sulfur content in the reaction product of the catalyst is mass percent; sSfThe sulfur content in the reaction raw material using the catalyst is mass percent; sDpThe sulfur content in the reaction product using the reference agent D is mass percent; sDfThe results of evaluating hydrodesulfurization of the catalysts prepared in examples and comparative examples are shown in Table 2, in order to obtain the sulfur content by mass in the reaction material using reference D.
TABLE 2
Figure BDA0001661670860000221
Figure BDA0001661670860000231
It can be shown from the results in tables 1 and 2 that, compared with the hydrogenation catalyst prepared by the conventional method, the hydrogenation catalyst prepared by the method provided by the invention has the advantages that part of the active metal component B exists in the form of trisulfide, the rest of the active metal component B exists in the form of trioxide, the atomic ratio of sulfur to the active metal component B is 2.1-2.9, the degree of vulcanization is moderate, the bonding force of the sulfur to the carrier is equivalent, after simple activation treatment, the degree of vulcanization of the catalyst is high, when the active metal component A is contained, the modification degree of the auxiliary agent is high, the utilization rate of the active metal is fully improved, and more importantly, the catalyst provided by the invention has obviously better hydrodesulfurization 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 vulcanization processes.
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 (39)

1. A hydrogenation catalyst, the catalyst includes the carrier and active metal component B loaded on the carrier, the active metal component B is selected from at least one kind in VIB group metal element, characterized by that, some active metal component B exists in the form of trisulfide, the remaining part active metal component B exists in the form of trioxide, in the said catalyst measured by X-ray photoelectron spectroscopy, the atomic ratio of sulfur and active metal component B is 2.5-2.8, the sulfurization degree of the catalyst is 65-72%.
2. The hydrogenation catalyst of claim 1,
the active metal component B is molybdenum and/or tungsten;
the support is selected from one or more of gamma-alumina, silica, alumina-silica, titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia.
3. The hydrogenation catalyst of claim 1,
the hydrogenation catalyst has a vulcanization degree of 65-90% after activation treatment; the conditions of the activation treatment include: at a hydrogen space velocity of 1h-1Treating at 250 deg.C for 2 hr under hydrogen partial pressure of 4MPa, and heating to 360 deg.C for 4 hr.
4. The hydrogenation catalyst according to claim 3,
the hydrogenation catalyst has a vulcanization degree of 70-90% after activation treatment.
5. The hydrogenation catalyst according to claim 3,
the hydrogenation catalyst has a vulcanization degree of 80-89% after activation treatment.
6. A hydrogenation catalyst according to any one of claims 1 to 5, wherein the support is present in an amount of from 60 to 90% by weight, calculated as oxide, based on the total amount of catalyst, and the active metal component B is present in an amount of from 10 to 40% by weight.
7. A hydrogenation catalyst according to any one of claims 1 to 5, wherein the support is present in an amount of from 70 to 85% by weight, calculated as oxide, based on the total amount of catalyst, and the active metal component B is present in an amount of from 15 to 30% by weight.
8. A hydrogenation catalyst according to any one of claims 1 to 5, wherein the catalyst further comprises an active metal component A selected from at least one of the group VIII metal elements, supported on a carrier; and/or
After the hydrogenation catalyst is activated, the modification degree of the auxiliary agent is 28-60%, wherein the modification degree of the auxiliary agent refers to the ratio of the amount of an active metal component A existing in a II-type active phase A-B-S form to the total amount of the active metal component A measured by an X-ray electron energy spectrum; the conditions of the activation treatment include: at a hydrogen space velocity of 1h-1Treating at 250 deg.C for 2 hr under hydrogen partial pressure of 4MPa, and heating to 360 deg.C for 4 hr.
9. The hydrogenation catalyst according to claim 8, wherein the hydrogenation catalyst has an assistant modification degree of 35-52% after activation treatment.
10. The hydrogenation catalyst according to claim 8, wherein the hydrogenation catalyst has an assistant modification degree of 43 to 50% after activation treatment.
11. The hydrogenation catalyst according to claim 8, wherein the active metal component A is a cobalt and/or nickel element.
12. A hydrogenation catalyst according to claim 8, wherein the support is present in an amount of from 54 to 85% by weight, based on the total amount of the catalyst, of active metal component A in an amount of from 1 to 10% by weight and active metal component B in an amount of from 8 to 45% by weight, calculated as oxide.
13. A hydrogenation catalyst according to claim 8, wherein the support is present in an amount of 68 to 84 wt%, calculated as oxide, of active metal component A in an amount of 1.5 to 6 wt% and active metal component B in an amount of 10 to 30 wt%, based on the total amount of the catalyst.
14. A method of preparing a hydrogenation catalyst as claimed in any one of claims 1 to 13, wherein the method comprises:
(1) soaking the carrier by adopting a solution C containing a VIB group metal compound, and drying to obtain a solid A;
(2) contacting a solution D containing at least one organic sulfur source with a solid A, and then drying the resulting solid product;
the organic sulfur source is a sulfur-containing substance which can be hydrolyzed in the solution D and/or under the contact condition, the contact temperature is 60-120 ℃, and the contact time is 2-24 hours;
the pH of the solution D is 3.5-6.5 or 7.5-10.5.
15. The production method according to claim 14,
the pH of the solution D is 4.5-5.5 or 8.5-9.5.
16. The production method according to claim 14, wherein the organic 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),
Figure FDA0003391490190000031
Figure FDA0003391490190000041
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.
17. The production method according to claim 16, wherein the organic sulfur source is a thioamide represented by formula (1).
18. The process according to claim 14, wherein the organic sulfur source is thiourea and/or thioacetamide.
19. The preparation method according to claim 14, wherein the molar ratio of the organic sulfur source to the group VIB metal compound is 2-6:1, wherein the organic sulfur source is calculated by sulfur element, and the group VIB metal compound is calculated by group VIB metal element.
20. The method of claim 19, wherein the molar ratio of the organosulfur source to the group VIB metal compound is from 3 to 6: 1.
21. The production method according to claim 14,
the concentration of the organic sulfur source in the solution D is 0.05-20 mol/L.
22. The production method according to claim 14,
the concentration of the organic sulfur source in the solution D is 1-15 mol/L.
23. The production method according to claim 14,
the concentration of the organic sulfur source in the solution D is 4-10 mol/L.
24. The production method according to any one of claims 14 to 23, wherein the group VIB metal element is a molybdenum and/or tungsten element, and the group VIB metal compound is at least one selected from molybdenum trioxide, tungsten trioxide, ammonium molybdate, sodium tungstate, ammonium metatolybdate, ammonium metatungstate, ammonium phosphomolybdate and ammonium phosphotungstate;
the support is selected from one or more of gamma-alumina, silica, alumina-silica, titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia.
25. The production method according to any one of claims 14 to 23,
the dosage of the VIB group metal compound and the carrier is such that the content of the carrier in the prepared catalyst is 60-90 wt% based on the total amount of the catalyst, and the content of the VIB group metal element is 10-40 wt% calculated by oxide.
26. The production method according to any one of claims 14 to 23,
the amount of the VIB group metal compound and the carrier is such that the content of the carrier in the prepared catalyst is 70-85 wt% based on the total amount of the catalyst, and the content of the VIB group metal element is 15-30 wt% calculated by oxide.
27. The production method according to any one of claims 14 to 23,
the method further comprises introducing a group VIII metal element into the hydrogenation catalyst by means of mode 1) and/or mode 2);
the mode 1) includes: adding a group VIII metal compound to the solution C;
the mode 2) includes: impregnating the dried substance obtained in the step (2) with a solution E containing a group VIII metal compound.
28. The production method according to claim 27, wherein,
the VIII group metal element is cobalt and/or nickel element, and the VIII group metal compound is at least one selected from nitrate, basic carbonate, chloride, sulfate and acetate of VIII group metal.
29. The production method according to claim 27, wherein,
the amount of the VIII group metal compound, the VIB group metal compound and the carrier is such that in the prepared catalyst, based on the total amount of the catalyst, the content of the carrier is 54-85 wt%, the content of the VIII group metal element is 1-10 wt% and the content of the VIB group metal element is 8-45 wt% calculated by oxides.
30. The production method according to claim 27, wherein,
the amount of the VIII group metal compound, the VIB group metal compound and the carrier is such that the prepared catalyst contains 68-84 wt% of the carrier based on the total amount of the catalyst, the VIII group metal element content is 1.5-6 wt% and the VIB group metal element content is 10-30 wt% in terms of oxides.
31. The method of any one of claims 14-23, wherein the contacting is at a temperature of 70-100 ℃ for a period of 6-18 hours.
32. The production method according to any one of claims 14 to 23,
the contacting is performed under closed conditions.
33. The production method according to any one of claims 14 to 23,
the drying conditions in the step (2) comprise: under an inert atmosphere or a reducing atmosphere, the temperature is 100-250 ℃, and the time is 1-12 hours.
34. The production method according to any one of claims 14 to 23,
the drying conditions in the step (2) comprise: under inert atmosphere or reducing atmosphere at 100-130 deg.c for 2-6 hr.
35. A hydrogenation catalyst produced by the production method according to any one of claims 14 to 34.
36. Use of a hydrogenation catalyst as claimed in any one of claims 1 to 13 and 35 in hydrofinishing.
37. A process for hydrofinishing, which process comprises: activating a hydrogenation catalyst according to any one of claims 1-13 and 35 to obtain an activated catalyst, and contacting a feed to be hydrorefined with the activated catalyst under hydrorefining conditions in the presence of hydrogen.
38. The method of claim 37, wherein the activating conditions comprise: activating for 1-12h at the temperature of 240-500 ℃ in an inert atmosphere or a reducing atmosphere.
39. The method of claim 37, wherein,
the conditions for the activation include: activating for 0.5-6h at the temperature of 240-310 ℃ and then activating for 0.5-6h at the temperature of 320-500 ℃ in an inert atmosphere or a reducing atmosphere.
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CN115305116B (en) * 2021-05-08 2023-10-10 中国石油化工股份有限公司 Method for co-producing naphtha and diesel oil by hydrogenating water-containing oil product
CN116060040A (en) * 2021-10-30 2023-05-05 中国石油化工股份有限公司 Sulfuration type hydrogenation catalyst, preparation method and application thereof

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3804750A (en) * 1972-12-22 1974-04-16 Atlantic Richfield Co Shale oil treatment
CN1994567A (en) * 2006-12-20 2007-07-11 中国科学院山西煤炭化学研究所 Hydrogenation catalyst precuring method
CN101279296A (en) * 2007-04-04 2008-10-08 中国石油化工股份有限公司 Sulfuration type catalyst and preparation thereof
CN101491765A (en) * 2008-01-23 2009-07-29 中国石油化工股份有限公司 Preparation method of vulcanization type hydrogenation catalyst
CN102039147A (en) * 2009-10-21 2011-05-04 中国石油化工股份有限公司 Preparation method of vulcanized catalyst
CN102989492A (en) * 2011-09-15 2013-03-27 中国石油天然气股份有限公司 Supported composite sulfur phosphide hydrotreatment catalyst, preparation and applications thereof
CN103769125A (en) * 2012-10-24 2014-05-07 中国石油化工股份有限公司 Preparation method of hydro-treatment catalyst
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
CN104707629A (en) * 2015-04-08 2015-06-17 兰州理工大学 Preparation method of hydrogenating catalyst for load type transition metal sulfide
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
CN106925343A (en) * 2015-12-29 2017-07-07 中国石油天然气股份有限公司 A kind of denitrification activity heavy distillate hydrotreating catalyst high and preparation method thereof
CN107971034A (en) * 2016-10-21 2018-05-01 中国石油化工股份有限公司 A kind of sulfurized hydrogenation catalyst and its preparation method and application

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3804750A (en) * 1972-12-22 1974-04-16 Atlantic Richfield Co Shale oil treatment
CN1994567A (en) * 2006-12-20 2007-07-11 中国科学院山西煤炭化学研究所 Hydrogenation catalyst precuring method
CN101279296A (en) * 2007-04-04 2008-10-08 中国石油化工股份有限公司 Sulfuration type catalyst and preparation thereof
CN101491765A (en) * 2008-01-23 2009-07-29 中国石油化工股份有限公司 Preparation method of vulcanization type hydrogenation catalyst
CN102039147A (en) * 2009-10-21 2011-05-04 中国石油化工股份有限公司 Preparation method of vulcanized catalyst
CN102989492A (en) * 2011-09-15 2013-03-27 中国石油天然气股份有限公司 Supported composite sulfur phosphide hydrotreatment catalyst, preparation and applications thereof
CN103769125A (en) * 2012-10-24 2014-05-07 中国石油化工股份有限公司 Preparation method of hydro-treatment catalyst
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
CN104707629A (en) * 2015-04-08 2015-06-17 兰州理工大学 Preparation method of hydrogenating catalyst for load type transition metal sulfide
CN106925343A (en) * 2015-12-29 2017-07-07 中国石油天然气股份有限公司 A kind of denitrification activity heavy distillate hydrotreating catalyst high and preparation method thereof
CN107971034A (en) * 2016-10-21 2018-05-01 中国石油化工股份有限公司 A kind of sulfurized hydrogenation catalyst and its preparation method and application

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"MoS3/Al2O3复合材料的合成及其用于";高杨等;《石油学报（石油加工）》;20180131;第34卷(第1期);第56-63页 *
"煤焦油加氢脱硫催化剂的制备及其催化性能研究";曹彦伟;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20170215(第2期);B014-1418 *
《Preparation and Characterization of SBA-15 Supported Cobal-Molybdenum Sulfide Catalysts for HDS Reaction: An All Sulfide Route to Hydrodesulfurization Catalysts》;Z.-D. Huang·W et al.;《Catal Lett 》;20080528;第124卷;第24-33页 *

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