A heavy oil hydro-decarbon residue catalyst, its preparation method and application

Abstract

The application discloses a heavy oil hydrodecarbon residue catalyst, a preparation method and application thereof. The catalyst comprises a carrier and an active component, the active component comprises Mo and Mg, the content of Mo is 5.0%-15.0% based on the catalyst weight, the content of Mg is 0.2%-1.5%, and the mass ratio of Mo to S is above 1.5. The heavy oil hydrodecarbon residue catalyst is used for processing low-sulfur heavy residue oil materials such as tail oil obtained by processing ebullated bed residual oil, and has good hydrodecarbon residue activity and good activity stability.

Description

Technical Field

[0001] This invention belongs to the field of hydrogenation technology, and specifically relates to a hydrogenation decarbonization catalyst, its preparation method, and its application. Background Technology

[0002] Currently, the active phase of hydrogenation catalysts used in the petrochemical industry is a nano-scale cluster with Mo(W)S2 as the main body and Ni or Co modified on the outer layer. A key characteristic of these catalysts is their high requirement for the sulfur content of the raw materials and the reaction atmosphere. When the sulfur content in the raw materials is low, the hydrogen sulfide in the reaction system is insufficient to maintain the stable structure of the active phase, which will be reduced by hydrogen, resulting in a decrease in reaction activity.

[0003] To adapt to low-sulfur feedstocks, researchers have proposed various methods to maintain the stability of sulfur in the active phase.

[0004] CN1488729A discloses a two-stage hydrotreating process for dearomatics removal from distillate oil. This method employs a two-stage hydrotreating process, with both reactors using non-precious metal catalysts. A switching pipeline is installed between the inlet and outlet of the two reactors. When the catalyst activity in the second reactor decreases, a switching operation is performed: the original second reactor becomes the first reactor, and the original first reactor becomes the second reactor. This method solves the problem of easy catalyst deactivation in the second stage of the two-stage hydrotreating process for distillate oil using non-precious metal catalysts, and extends the catalyst operating cycle.

[0005] CN102465014B discloses a hydrocracking method for processing low-sulfur feedstock. The method includes: hydrotreating a high-sulfur feedstock, performing gas-liquid separation on the reaction effluent to obtain a sulfur-containing, hydrogen-rich gas; hydrocracking a low-sulfur feedstock oil, performing gas-liquid separation on the reaction effluent to obtain a sulfur-lean, hydrogen-rich gas; mixing the sulfur-containing, hydrogen-rich gas with the sulfur-lean, hydrogen-rich gas, selectively removing hydrogen sulfide, and then recycling it back to the reactor inlet. This method effectively combines the two hydrogen-rich gas streams from the hydrotreating and hydrocracking processes, fully utilizing the sulfur-containing, hydrogen-rich gas from the hydrotreating process to replenish sulfur in the low-sulfur feedstock hydrocracking unit, effectively solving the catalyst sulfur loss problem during long-term operation of the low-sulfur hydrocracking unit.

[0006] CN105749933B discloses a method for preparing a hydrogenation catalyst. The hydrogenation catalyst comprises a support and an active metal component supported on the support. The active metal component is distributed in a double layer along the radial direction of the support. The core layer of active metal component is NiO and WO3, and the shell layer of active metal component is MoO3, NiO, and / or CoO. The method includes the following steps: immersing a hydrothermally treated support in an acidic solution containing molybdenum compounds, nickel compounds, and / or cobalt compounds, and then drying it to obtain a support; immersing the support in an alkaline solution containing nickel compounds and tungsten compounds, and then drying and calcining it to obtain the catalyst. This catalyst utilizes the layered distribution of the active metal component on the support to improve the catalyst's hydrodesulfurization, decarbonization, and denitrification activity; however, it still suffers from poor stability when processing low-sulfur feedstocks. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides a heavy oil hydrodecarbonization catalyst, its preparation method, and its application. When used in the hydrodecarbonization reaction of heavy residue oil under low-sulfur conditions, the catalyst of this invention not only exhibits good hydrodecarbonization activity but also good activity stability, especially in processing fluidized bed hydrotreated tail oil.

[0008] The first aspect of the present invention provides a heavy oil hydrotreating decarbonization catalyst, comprising a support and an active component, wherein the active component comprises Mo and Mg, and based on the weight of the catalyst, the content of Mo is 5.0%-15.0%, the content of Mg is 0.2%-1.5%, preferably 0.5%-1.5%, and the mass ratio of Mo to S is 1.5 or more.

[0009] Furthermore, the hydrodecarbonization catalyst includes a support, an active component, and an S element, wherein the active component is Mo and Mg.

[0010] In existing technologies, the sulfur content in sulfide-state hydrodecarbonization catalysts is generally above 10 wt%. However, the active components of this invention use a combination of Mo and Mg, and control the sulfur content in the catalyst at a low level. This is beneficial to improving the hydrodecarbonization capability of the catalyst and preventing the loss of sulfur in the active phase under low sulfur reaction conditions.

[0011] Furthermore, in the hydrodecarbonization catalyst, the mass ratio of Mo to S is preferably 1.5-3.0, more preferably 1.6-2.4. In contrast, the mass ratio of Mo to S in the prior art is generally less than 1.5, typically between 1 and 1.3. The inventors have discovered that using the catalyst of this invention, especially when the mass ratio of Mo to S is above 1.5, can improve the catalyst's hydrodecarbonization capacity and prevent the loss of sulfur in the active phase under low-sulfur reaction conditions.

[0012] Furthermore, based on the weight of the catalyst, the support content is 78%-92%, and the contents of Mo, S, and Mg are 8%-22%.

[0013] Furthermore, XPS testing revealed that the catalyst contains Mo with valences of +2, 0, and +4, wherein +2-valent Mo accounts for 50%-75% of the total Mo atoms, 0-valent Mo accounts for 10%-32% of the total Mo atoms, and +4-valent Mo accounts for 1%-25% of the total Mo atoms; preferably, +2-valent Mo accounts for 55%-70% of the total Mo atoms, 0-valent Mo accounts for 15%-29% of the total Mo atoms, and +4-valent Mo accounts for 4%-20% of the total Mo atoms. The inventors of this invention have discovered that by controlling the proportions of different valence states of Mo in the metallic active phase, especially by ensuring that +2-valent and 0-valent Mo exist in the catalyst at specific ratios, it is more beneficial for Mo to combine with Mg and S to form the metallic active phase, and it is also more beneficial to prevent the loss of sulfur in the active phase under low-sulfur reaction conditions.

[0014] Furthermore, the sum of +4 valence Mo, +2 valence Mo, and 0 valence Mo accounts for more than 90% of the total Mo atoms, preferably 90%-99%. The catalyst provided by this invention may also contain +5 or +6 valence Mo in addition to +2 valence Mo, 0 valence Mo, and +4 valence Mo.

[0015] Furthermore, the present invention does not particularly limit the carrier, and it can be any carrier conventionally used in the art, a commercially available product, or prepared by any method in the prior art. For example, the carrier can be an inorganic refractory oxide. Preferably, the carrier is one or more of alumina, silicon oxide, and amorphous aluminum silicate. Considering both cost and effect, alumina is preferred as the carrier. The carrier may contain one or more of modifying elements such as phosphorus, silicon, boron, fluorine, and sodium. The amount of the modifying element added is conventional, preferably 0.2%-1.0% of the carrier mass. The carrier has the following properties: specific surface area of ​​200-350 m². 2 / g, preferably 220-300m 2 / g, pore volume 0.5-1.2cm 3 / g, preferably 0.7-1.1cm 3 / g.

[0016] A second aspect of the present invention provides a method for preparing the above-mentioned catalyst, comprising:

[0017] (1) Hexacarbonyl molybdenum and organomagnesia compounds were introduced into the support by impregnation to obtain catalyst precursor I;

[0018] (2) In the presence of an inert gas, the dispersant is contacted with the catalyst precursor I to obtain catalyst precursor II;

[0019] (3) Using at least one of steps (3-1) or (3-2), wherein,

[0020] Step (3-1) includes sulfiding the catalyst precursor II, wherein the sulfidation results in a Mo to S mass ratio of 1.5 or more, preferably 1.5-3.0, and more preferably 1.6-2.4, based on the total weight of the catalyst in the prepared hydrodecarbonization catalyst.

[0021] Step (3-2) involves impregnating catalyst precursor II with an impregnation solution containing polysulfide compounds, followed by drying.

[0022] Further, in step (1), there is no particular limitation on the impregnation method; it can be equal-volume impregnation or excessive impregnation. In this invention, the hexacarbonylmolybdenum and organomagnesium compounds can be introduced into the carrier simultaneously through co-impregnation or separately through stepwise impregnation; there is no particular limitation on the order of introduction. According to this invention, it is preferred that the hexacarbonylmolybdenum and organomagnesium compounds are introduced through co-impregnation.

[0023] Further, step (1) preferably includes: impregnating the carrier with an impregnation solution containing molybdenum hexacarbonyl and an organomagnesium compound, and then drying it; preferably, the impregnation is an equal-volume impregnation method or an excess impregnation method. The drying conditions can be selected over a wide range, as long as the solvent is removed without causing the molybdenum hexacarbonyl and organomagnesium compounds to evaporate.

[0024] Further, in step (1), the drying method is vacuum drying, wherein the drying temperature is 60-120℃, preferably 80-100℃, the vacuum degree during drying is 0.1-2.0 torr, preferably 0.2-1.0 torr, and the drying time is 1-10 hours, preferably 2-8 hours.

[0025] Further, in step (1), the solvent in the impregnation solution is one or more of ethanol, benzene, toluene, xylene, ethylbenzene, and tetrahydronaphthalene, more preferably at least one of toluene, xylene, ethylbenzene, and tetrahydronaphthalene, and optionally ethanol. Preferably, the organomagmonium compound is selected from one or more of magnesium citrate, magnesium glycine, magnesium gluconate, magnesium salicylate, and magnesium laurate.

[0026] Further, in the impregnation solution of step (1), the concentration of molybdenum hexacarbonyl is 0.2-3.5 mol / L, preferably 0.4-2.0 mol / L, and the concentration of organomagnesium compound is 0.05-0.8 mol / L, preferably 0.1-0.6 mol / L.

[0027] Further, in step (1), the support is a conventional catalyst support for hydrodecarbonization of residual oil, which can be selected from one or more of alumina, silica, and amorphous silica-alumina. The properties of the support are as follows: specific surface area of ​​200-350 m² / g. 2 / g, preferably 220-300m 2 / g, pore volume 0.5-1.2cm 3 / g, preferably 0.7-1.1cm 3 / g. The carrier may be doped with one or more modifying elements such as phosphorus, silicon, boron, fluorine, and sodium. The amount of the modifying element added is conventional, preferably 0.2%-1.0% of the carrier mass.

[0028] Furthermore, the amounts of the support, molybdenum hexacarbonyl, and organomagnesium compound are such that, based on the total weight of the catalyst, the prepared hydrodecarbonization catalyst contains 5.0%-15.0% Mo and 0.2%-1.5%, preferably 0.5%-1.5%. Those skilled in the art can appropriately select the amount and concentration of the impregnation solution based on the above disclosure.

[0029] Furthermore, in step (2), the inert gas is one or more of nitrogen, argon, helium and neon.

[0030] Furthermore, in step (2), contacting the dispersant with the catalyst precursor I yields a stable organic molybdenum dimer, which is more conducive to the subsequent formation of a highly dispersed active phase. There are no particular limitations on the method of contacting the dispersant with the catalyst precursor I; it can be done continuously or intermittently. The dispersant can be introduced in gaseous or liquid form; this invention does not impose any particular limitation on this.

[0031] Furthermore, in step (2), the type of dispersant is selected from a wide range, as long as it can contact the catalyst precursor I to obtain a stable organic molybdenum dimer. Preferably, the dispersant is selected from at least one of acetic acid, acetic anhydride, citric acid, dimethyl malonate, malonic acid, and succinic acid; more preferably, the dispersant is acetic acid and / or acetic anhydride.

[0032] Further, in a preferred case, in step (2), the amount of dispersant used is 1 to 10 g relative to 1 g of the catalyst precursor I, preferably 2 to 5 g.

[0033] Further, preferably, the contact conditions in step (2) include: a pressure of 0–1 MPa, preferably 0.1–0.5 MPa, a temperature of 80–180°C, preferably 100–150°C, and a time of 8–36 hours, preferably 12–24 hours. Wherein, the pressure is gauge pressure.

[0034] Further, preferably, the method further includes removing the remaining dispersant after the contact described in step (2) by evaporation drying, preferably by vacuum drying under reduced pressure. The drying conditions are selected within a wide range, aiming to remove the solvent without causing significant loss of the loaded organomolybdenum species and organomagnesium compounds from the carrier surface. Preferably, the evaporation drying conditions include: a drying temperature of 80–150°C, preferably 100–120°C; a drying vacuum of 0.1–2 torr, preferably 0.2–1 torr; and a drying time of 1–8 hours, preferably 2–6 hours.

[0035] Furthermore, the contact described in step (2) can be carried out in a reactor, such as an autoclave, preferably under closed conditions.

[0036] Further, the dispersant and the catalyst precursor I are placed in a reaction vessel, sealed, and inert gas is introduced to the contact pressure. The mixture is then heated to the contact temperature and kept at a constant temperature. The method also includes cooling the catalyst precursor obtained in step (2) and then subjecting it to vacuum drying under reduced pressure.

[0037] Furthermore, there are no particular limitations on the sulfidation process described in step (3-1), and conventional methods in the art can be used. Known sulfidation methods can be employed, and preferably, the sulfidation includes dry sulfidation and / or wet sulfidation. The dry sulfidation and wet sulfidation methods described in this invention have their conventional interpretations in the art. There are no particular limitations on the conditions for dry sulfidation and wet sulfidation, as long as the mass ratio of Mo to S in the hydrogenation catalyst is 1.5 or higher (preferably 1.5 to 3.0, more preferably 1.6 to 2.4).

[0038] Furthermore, it is preferable to treat catalyst precursor II using step (3-2), which is more conducive to obtaining a catalyst with better hydrogenation processing capability.

[0039] The specific implementation method of the impregnation in step (3-2) can be as described above, and will not be repeated here. Preferably, the impregnation in step (3-2) is an equal-volume impregnation.

[0040] Further, in step (3), the solvent in the impregnation solution containing polysulfide compounds is at least one of C5-C10 alkanes and / or cycloalkanes and aromatics, preferably one or more of cyclohexane, n-heptane, n-octane, tetrahydronaphthalene, decahydronaphthalene, toluene, and xylene.

[0041] Further, the polysulfide compound refers to a compound containing at least 2 moles of sulfur per mole, for example, 2-3 moles. The polysulfide compound is preferably one or more of di-tert-butyl polysulfide (preferably 2-3 moles of sulfur), tert-nonyl polysulfide (preferably 2-3 moles of sulfur), tert-dodecyl polysulfide (preferably 2-3 moles of sulfur), and dihexanedisulfide.

[0042] Furthermore, the di-tert-butyl polysulfides include, but are not limited to, di-tert-butyl disulfide and di-tert-butyl trisulfide.

[0043] Furthermore, the tert-nonyl polysulfides include, but are not limited to, tert-nonyl dimersulfides and tert-nonyl trimersulfides.

[0044] Furthermore, the tert-dodecyl polysulfides include, but are not limited to, tert-dodecyl trimersulfides and tert-dodecyl dimersulfides.

[0045] Furthermore, the dihexanedisulfide includes, but is not limited to, n-dihexanedisulfide and tert-dihexanedisulfide.

[0046] Furthermore, in the impregnation solution containing polysulfide compounds, the mass concentration of polysulfide compounds is 2%-20%, preferably 3%-15%.

[0047] Further, preferably, the amount of the impregnation solution containing polysulfide compounds and the catalyst precursor II is such that the mass ratio of Mo to S in the prepared hydrogenation catalyst is 1.5 or more, preferably 1.5 to 3.0, and more preferably 1.6 to 2.4.

[0048] Further, in step (3-2), preferably, the method further includes drying after the impregnation. Preferably, the drying is vacuum drying under reduced pressure. More preferably, the drying conditions include: a drying temperature of 60-120°C, preferably 80-100°C; a vacuum degree of 0.1-2.0 torr, preferably 0.2-1.0 torr; and a drying time of 1-6 hours, preferably 2-4 hours.

[0049] Furthermore, the material obtained from drying in step (3-2) can be used directly as a product, and can be treated with hydrogen before use. Alternatively, the material obtained from drying in step (3-2) can be treated with hydrogen and then used directly. It is understood that the methods before and after hydrogen treatment and the resulting products are all within the scope of protection of this invention.

[0050] Furthermore, preferably, step (3-2) further includes hydrogen treatment of the dried material.

[0051] Further, preferably, in step (3-2), the hydrogen treatment is carried out in a hydrogen atmosphere provided by a hydrogen-containing gas.

[0052] Further, preferably, the hydrogen-containing gas contains hydrogen and an inert gas. The range of types of inert gas selected is as described above, and will not be repeated here.

[0053] Further, preferably, the hydrogen content in the hydrogen-containing gas is not less than 50% v, preferably 50-100% v, and more preferably 100% v.

[0054] Further, preferably, the hydrogen gas is passed through in a single pass during the hydrogen treatment process. More preferably, the amount of hydrogen used is 0.1 to 1 NL relative to 1 g of the dried material, preferably 0.2 to 0.8 NL.

[0055] Furthermore, the hydrogen treatment is carried out under closed conditions, for example, in a reaction vessel.

[0056] Further, preferably, the conditions for hydrogen treatment include: a hydrogen treatment temperature of 180–300°C, preferably 200–260°C, and a treatment time of 2–10 hours, preferably 3–6 hours.

[0057] Furthermore, after hydrogen treatment in step (3-2), the process may also include cooling, inert gas replacement, and other processes.

[0058] The third aspect of this invention provides the application of the above-mentioned catalyst in the hydrodecarbonization reaction of low-sulfur heavy feedstock.

[0059] Further, the low-sulfur heavy feedstock is at least one selected from fluidized bed hydrotreated tail oil, coal tar, and Fischer-Tropsch synthesis oil, more preferably fluidized bed hydrotreated tail oil. The density of the low-sulfur heavy feedstock is 0.95–1.05 g / cm³. 3 The sulfur content is below 8000 ppm, which can be 1500-7000 ppm; the nitrogen content is below 5000 ppm, which can be 500-5000 ppm; and the residual carbon content is 8%-25%.

[0060] Furthermore, the hydrotreating and decarbonization reaction conditions are as follows: reaction temperature 300-450℃, reaction pressure 12-25MPa, hydrogen-to-oil volume ratio 500-2000:1, and liquid hourly space velocity 0.1-0.5h⁻¹. -1 .

[0061] Compared with the prior art, the present invention has the following advantages:

[0062] 1. In conventional hydrogenation catalysts, the active metals are usually Mo and Ni(Co), with the active phase being mainly MoS2 (+4 valence Mo) and Ni(Co) distributed around MoS2. The inventors of this invention discovered that by controlling the proportion of Mo in different valence states within the active metal phase, especially ensuring that +2 valence Mo and 0 valence Mo exist in a specific proportion within the catalyst, Mo can combine with Mg and S to form a metallic active phase. This results in a tighter bond between Mo and sulfur, preventing the loss of sulfur from the active phase under low-sulfur reaction conditions. Furthermore, by adjusting the electron distribution on the main crystal plane of the active metal phase using Mg, the orbital energy levels of the main crystal plane are increased, significantly enhancing the transfer ability of activated hydrogen on the surface of the active phase. This is more conducive to the saturation of aromatics and provides excellent hydrogenation dearomatization and decarbonization capabilities when processing low-sulfur feedstocks.

[0063] 2. In the preparation method of the catalyst of the present invention, low-valence organic molybdenum and organic magnesium sources are used to introduce magnesium and molybdenum species into the catalyst, achieving uniform mixing of molybdenum and magnesium on the catalyst surface. The molybdenum source is then treated with a dispersant, preferably acetic acid and / or acetic anhydride, to obtain a molybdenum tetraacetate monomer. In this monomer, molybdenum atoms are linked by Mo-Mo chemical bonds. Compared with conventional molybdenum oxide species, the molybdenum interatomic distance in the molybdenum tetraacetate monomer is smaller, and the coordination number is lower, which is beneficial for the formation of low-valence molybdenum sulfide species during the sulfidation process. Finally, a polysulfide is used as a sulfur source to treat the molybdenum tetraacetate monomer. Due to the limited sulfur content, the low valence of molybdenum, and the electron-donating effect of magnesium, the valence of molybdenum in the prepared catalyst is mainly 0 and +2.

[0064] 3. The method provided by this invention is particularly suitable for hydrotreating fluidized bed hydrotreating tail oil. Unlike straight-run residue, fluidized bed hydrotreating tail oil is residue after fluidized bed hydrotreating. Although it has lower sulfur, nitrogen, and aromatic hydrocarbon content, the nitrogen atoms in the remaining nitrogen compounds are often protected by numerous condensed aromatic rings, making them more difficult to approach and remove from the catalyst's active site, further increasing the difficulty of hydroremoval. When the hydrotreating method of this invention is used to treat fluidized bed hydrotreating tail oil, it ensures the full utilization of hydroremoval carbon and nitrogen removal activity under low-sulfur conditions, and also improves the stability of the hydrotreating process. Detailed Implementation

[0065] The present invention will be further described below with reference to embodiments, but it should be understood that the scope of protection of the present invention is not limited to the embodiments. In the present invention, unless otherwise expressly stated, percentages and contents are all expressed by mass.

[0066] In this invention, the contents of Mo, Mg, and S in the hydrodecarbonization catalyst can be determined by ICP using an OPTIMA 7000DV atomic emission spectrometer manufactured by PE Corporation. 0.1 g of the sample is dissolved in a mixed solution with a volume ratio of 3HCl:1HNO3:0.5HF. The mixed solution is then diluted with deionized water to a specific volume, ensuring the content of the analyte element in the solution is between 1 and 10 ppm, before measurement.

[0067] In this invention, the XPS operating conditions are as follows: light source: Mg Kα, energy step: 0.05 eV, scan range: 200-250 eV (molybdenum), 280-300 eV (carbon). When analyzing the valence state of molybdenum, molybdenum species with a 3d5 / 2 orbital binding energy of 227-228 eV are considered to have a valence of 0; those with a valence between 228-229 eV are considered to have a valence of +2; those with a valence between 229-231 eV are considered to have a valence of +4; and those with a valence greater than 231 eV are considered to have a valence of +5 or +6.

[0068] The carriers used in the following embodiments and comparative examples of this invention were prepared by the following methods:

[0069] Weigh 1000.0g of alumina dry adhesive powder, add 15.0g of acetic acid and 30.0g of butylene terephthalol, mix well, then add 1000.0g of an aqueous solution containing 2.0% nitric acid. After rolling for 10.0min, extrude the mixture using a 2.0mm diameter clover-shaped perforated plate. Dry at 120℃ for 4.0h, then calcine at 600℃ for 4.0h. The calcined and shaped carrier, sieved to a length of 4-6mm, is designated S-0. The carrier properties are as follows: specific surface area of ​​290m². 2 / g, pore volume is 0.96cm 3 / g.

[0070] Example 1

[0071] Take 20.0g of molybdenum hexacarbonyl and 10.0g of magnesium citrate, mix them with 120g of toluene and 30.0g of ethanol to prepare solution MQ-1.

[0072] Take 100.0g of S-0, impregnate it with MQ-1, and then dry it under reduced pressure at a temperature of 100℃ and a vacuum of 0.5 torr for 6.0 hours. The resulting catalyst precursor is denoted as P-1.

[0073] P-1 was placed in a high-pressure reactor, along with 250.0 g of acetic acid. After sealing, nitrogen gas at 0.5 MPa was introduced, and the mixture was heated to 100°C and kept at that temperature for 24 hours. After cooling, the catalyst was dried under reduced pressure at a temperature of 120°C and a vacuum of 0.2 torr for 4.0 hours. The resulting catalyst precursor was denoted as Y-1.

[0074] 10g of di-tert-butyl trimersulfide was mixed with 80.0g of toluene to prepare solution SQ-1. Y-1 was impregnated with SQ-1, and then the catalyst was dried under reduced pressure at a temperature of 90℃ and a vacuum degree of 0.3 torr for 4.0 hours. The resulting catalyst precursor was denoted as SY-1.

[0075] Take 50.0g of SY-1 and put it into a reaction vessel. Under closed conditions, introduce 30.0NL of hydrogen gas and control the reaction temperature at 200℃. React for 4.0 hours. After cooling, replace with nitrogen gas. The resulting catalyst is denoted as Cat-1.

[0076] Example 2

[0077] Take 30.0g of molybdenum hexacarbonyl and 10.0g of magnesium glycine, and prepare a solution MQ-2 with 120g of xylene and 30.0g of ethanol.

[0078] Take 100.0g of S-0, impregnate it with MQ-2, and then dry it under reduced pressure at a temperature of 120℃ and a vacuum of 0.2 torr for 5.0 hours. The resulting catalyst precursor is denoted as P-2.

[0079] P-2 was placed in a high-pressure reactor, along with 270.0 g of acetic acid. After sealing, nitrogen gas at 0.3 MPa was introduced, and the reactor was heated to 120°C and kept at that temperature for 24 hours. After cooling, the catalyst was dried under reduced pressure at a temperature of 110°C and a vacuum of 0.2 torr for 4.0 hours. The resulting catalyst precursor was denoted as Y-2.

[0080] 10g of tert-nonyl trimerium sulfide and 80.0g of tetrahydronaphthalene were mixed to prepare solution SQ-2. Y-2 was impregnated with SQ-2, and then the catalyst was dried under reduced pressure at a temperature of 100℃ and a vacuum of 0.2 torr for 4.0 hours. The resulting catalyst precursor was denoted as SY-2.

[0081] Take 50.0g of SY-2 and put it into a reaction vessel. Under closed conditions, introduce 35.0NL of hydrogen gas and control the reaction temperature at 220℃. React for 4.0 hours. After cooling, replace with nitrogen gas. The resulting catalyst is denoted as Cat-2.

[0082] Example 3

[0083] Take 40.0g of molybdenum hexacarbonyl and 20.0g of magnesium salicylate, and prepare solution MQ-3 with 120g of benzene and 30.0g of ethanol.

[0084] Take 100.0g of S-0, impregnate it with MQ-3, and then dry it under reduced pressure at a temperature of 120℃ and a vacuum of 0.2 torr for 6.0 hours. The resulting catalyst precursor is denoted as P-3.

[0085] P-3 was placed in a high-pressure reactor, along with 260.0 g of acetic acid. After sealing, nitrogen gas at 0.2 MPa was introduced, and the mixture was heated to 110°C and kept at that temperature for 30 hours. After cooling, the catalyst was dried under reduced pressure at a temperature of 120°C and a vacuum of 0.2 torr for 6.0 hours. The resulting catalyst precursor was denoted as Y-3.

[0086] 10g of tert-dodecyl trimersulfide and 80.0g of decahydronaphthalene were mixed to prepare solution SQ-3. Y-3 was impregnated with SQ-3, and then the catalyst was dried under reduced pressure at a temperature of 110℃ and a vacuum of 0.2 torr for 6.0 hours. The resulting catalyst precursor was designated SY-3.

[0087] Take 50.0g of SY-3 and put it into a reaction vessel. Under closed conditions, introduce 25.0NL of hydrogen gas and control the reaction temperature at 240℃. React for 3.0 hours. After cooling, replace with nitrogen gas. The resulting catalyst is denoted as Cat-3.

[0088] Example 4

[0089] Take 50.0g of molybdenum hexacarbonyl and 25.0g of magnesium laurate, and prepare solution MQ-4 with 120g of tetrahydronaphthalene and 30.0g of ethanol.

[0090] Take 100.0g of S-0, impregnate it with MQ-4, and then dry it under reduced pressure at a temperature of 110℃ and a vacuum of 0.2 torr for 4.0 hours. The resulting catalyst precursor is denoted as P-4.

[0091] P-4 was placed in a high-pressure reactor, along with 300.0 g of acetic acid. After sealing, nitrogen gas at 0.4 MPa was introduced, and the mixture was heated to 120°C and kept at that temperature for 32 hours. After cooling, the catalyst was dried under reduced pressure at a temperature of 120°C and a vacuum of 0.2 torr for 5.0 hours. The resulting catalyst precursor was denoted as Y-4.

[0092] 10g of tert-dihexane disulfide and 80.0g of tetrahydronaphthalene were mixed to prepare solution SQ-4. Y-4 was impregnated with SQ-4, and then the catalyst was dried under reduced pressure at a temperature of 120℃ and a vacuum of 0.2 torr for 6.0 hours. The resulting catalyst precursor was denoted as SY-4.

[0093] 50.0g of SY-4 was placed in a reactor. Under sealed conditions, 20.0NL of hydrogen gas was introduced and the reaction temperature was controlled at 230℃. The reaction was carried out for 6.0 hours. After cooling, the reaction was purged with nitrogen gas. The resulting catalyst was denoted as Cat-4.

[0094] Comparative Example 1

[0095] Take 20.0g of ammonium molybdate and 10.0g of magnesium nitrate, and prepare 120mL of aqueous solution, which is denoted as DQ-1.

[0096] The catalyst obtained by impregnating 100.0g of S-0 with DQ-1, evaporating at 120℃ for 5.0 hours, and then burning at 500℃ for 5.0 hours is designated as DCT-1.

[0097] Prepare a sulfiding solution by mixing 1000.0g of cyclohexane with 50.0g of DMDS, and label it DSQ-1.

[0098] 10.0 g of DCT-1 was placed in a reaction tube, and hydrogen and DSQ-1 were introduced for sulfidation. The sulfidation temperature was 340℃, the sulfidation time was 8.0 hours, the hydrogen pressure was 5.0 MPa, the hydrogen flow rate was 150 ml / L, and the DSQ-1 flow rate was 20.0 ml / h. The sulfidated catalyst was designated DCT-S1.

[0099] Comparative Example 2

[0100] Take 20.0g of ammonium molybdate and 12.0g of nickel nitrate hexahydrate, and prepare 100mL of aqueous solution, which is denoted as DQ-2.

[0101] The catalyst obtained by impregnating 100.0g of S-0 with DQ-2, evaporating at 120℃ for 5.0 hours, and calcining at 500℃ for 5.0 hours is designated as DCT-2.

[0102] Prepare a sulfidation solution by mixing 1000.0g of cyclohexane with 50.0g of DMDS, and label it DSQ-2.

[0103] 10.0 g of DCT-2 was placed in a reaction tube, and hydrogen and DSQ-2 were introduced for sulfidation. The sulfidation temperature was 340℃, the sulfidation time was 8.0 hours, the hydrogen pressure was 5.0 MPa, the hydrogen flow rate was 150 ml / L, and the DSQ-2 flow rate was 20.0 ml / h. The sulfidated catalyst was designated DCT-S2.

[0104] Comparative Example 3

[0105] The preparation methods of catalyst precursor P-2 and sulfur-containing solution SQ-2 are the same as in Example 2.

[0106] P-2 was impregnated with SQ-2, and then the catalyst was dried under reduced pressure at a temperature of 100°C, a vacuum of 0.2 torr, and a drying time of 4.0 hours. The resulting catalyst precursor was designated DSP-3.

[0107] 50.0g of DSP-3 was placed in a reactor. Under sealed conditions, 35.0NL of hydrogen gas was introduced and the reaction temperature was controlled at 220℃. The reaction was carried out for 4.0 hours. After cooling, the reaction was replaced with nitrogen gas. The resulting catalyst was designated as DCT-3.

[0108] Table 1 shows the elemental analysis of the catalysts obtained in each example.

[0109] Catalyst number Mo / wt% Mg / wt% S / wt% Mo:S mass ratio Cat-1 6.3 1.0 3.4 1.9 Cat-2 9.2 1.1 4.7 1.9 Cat-3 11.5 1.3 5.6 2.0 Cat-4 14.0 1.1 6.7 2.1 DCT-S1 9.0 1.1 7.6 1.2 DCT-S2 8.9 - 6.0 1.4 DCT-3 9.1 1.0 5.8 1.6

[0110] Table 2 shows the valence state analysis results of Mo in the catalysts obtained in each example.

[0111] Catalyst number 0% Mo percentage +2 valent Mo percentage / % +4 valent Mo percentage / % Cat-1 21.6 67.4 6.6 Cat-2 19.7 62.3 8.0 Cat-3 22.2 63.4 11.8 Cat-4 25.0 68.9 5.3 DCT-S1 ＜1 2.6 76.4 DCT-S2 ＜1 1.9 75.5 DCT-3 2.2 36.4 53.5

[0112] Examples 5-8

[0113] Hydrogenated oil from fluidized bed residue was selected as feedstock, and a fixed-bed process was used to evaluate the hydrogenation of the catalysts obtained in Examples 1-4. The properties of the hydrogenated oil from the fluidized bed unit are shown in Table 3.

[0114] Table 3 Properties of oils produced by hydrotreating fluidized bed residue oil

[0115] project numerical values project numerical values <![CDATA[Density / g·cm -3 > 0.971 Nitrogen content, μg / g 3261 Vanadium + Nickel content, μg / g 53.61 H / C atomic ratio 1.42 Sulfur content, μg / g 3994 Kang's carbon residue, % 15.2

[0116] A hydroprotective agent (FZC-100B) and a hydrodemetallization catalyst (FZC-204A) were loaded before the aforementioned catalyst, with a loading volume ratio of 1:2:4 for the protective agent, the hydrodemetallization catalyst, and the catalyst obtained in the examples. The operating conditions were: reaction temperature 380℃, reaction pressure 20.0 MPa, hydrogen-to-oil volume ratio 1800:1, and liquid hourly space velocity (LHSV) 0.2 h⁻¹. -1 After 1500 hours of reaction evaluation, the residual carbon value and nitrogen content of the hydrotreated oil fraction at a temperature not lower than 300℃ were analyzed, and the results are shown in Table 4.

[0117] Comparative Examples 4-6

[0118] The hydrogenated oil from the fluidized bed residue (see Table 3) was selected as the feedstock, and a fixed-bed process was used to evaluate the activity of the catalysts obtained in Comparative Examples 1-3. A hydrotreating protectant (FZC-100B) and a hydrodemetallization catalyst (FZC-204A) were loaded before the above catalysts, with a loading volume ratio of 1:2:4 for the protectant, hydrodemetallization catalyst, and the catalysts obtained in the comparative examples. The operating conditions were: reaction temperature 380℃, reaction pressure 20.0 MPa, hydrogen-to-oil volume ratio 1800:1, and liquid hourly space velocity (LISH) 0.2 h⁻¹. -1 After 1500 hours of reaction evaluation, the residual carbon value and nitrogen content of the hydrotreated oil fraction at temperatures not lower than 300℃ were analyzed, and the results are shown in Table 4.

[0119] Table 4 Properties of Oils Generated by Fixed-Bed Hydrogenation

[0120]

[0121]

[0122] As can be seen from the evaluation results in Table 4, the catalyst of the present invention has good hydrodenitrification and hydrodecarbonization activity and good stability when hydrotreating low-sulfur fluidized bed residue oil to produce oil.

Claims

1. A heavy oil hydrodecarbon residue catalyst, wherein, The catalyst comprises a carrier and an active component, the active component comprises Mo and Mg, the content of Mo is 5.0%-15.0% based on the weight of the catalyst, the content of Mg is 0.2%-1.5% based on the weight of the catalyst, the mass ratio of Mo to S is 1.5 or more, and in the catalyst, Mo comprises +2 valence Mo, 0 valence Mo and +4 valence Mo, wherein the +2 valence Mo accounts for 50%-75% of the total Mo in terms of atoms, the 0 valence Mo accounts for 10%-32% of the total Mo in terms of atoms, and the +4 valence Mo accounts for 1%-25% of the total Mo in terms of atoms.

2. The catalyst according to claim 1, characterized in that, In the catalyst, the content of Mg is 0.5%-1.5% based on the weight of the catalyst.

3. The catalyst of claim 1, wherein The mass ratio of Mo to S is 1.5-3.

0.

4. The catalyst of claim 3, wherein The mass ratio of Mo to S is 1.6-2.

4.

5. The catalyst of claim 1, wherein The +2 valence Mo accounts for 55%-70% of the total Mo in terms of atoms, the 0 valence Mo accounts for 15%-29% of the total Mo in terms of atoms, and the +4 valence Mo accounts for 4%-20% of the total Mo in terms of atoms.

6. The catalyst of claim 1, wherein The total of +4 valence Mo, +2 valence Mo and 0 valence Mo accounts for 90% or more of the total Mo in terms of atoms.

7. The catalyst of claim 6, wherein The total of +4 valence Mo, +2 valence Mo and 0 valence Mo accounts for 90%-99% of the total Mo in terms of atoms.

8. The catalyst of claim 1, wherein The carrier is one or more of alumina, silica and amorphous silica-alumina.

9. The catalyst of claim 8, wherein The carrier contains one or more of modified elements phosphorus, silicon, boron, fluorine and sodium.

10. The catalyst of claim 9, wherein The addition amount of the modified element is 0.2%-1.0% of the mass of the carrier.

11. The catalyst of claim 1, wherein The support has the following properties: specific surface area of 200-350 m 2 / g, pore volume of 0.5-1.2 cm 3 / g.

12. The catalyst of claim 11, wherein, The support has the following properties: specific surface area of 220-300 m 2 / g, pore volume of 0.7-1.1 cm 3 / g.

13. The catalyst of claim 1, wherein The content of the carrier is 78%-92% based on the weight of the catalyst, and the contents of Mo, S and Mg are 8%-22%.

14. A preparation method of the catalyst according to any one of claims 1-13, comprising: (1) introducing molybdenum hexacarbonyl and an organic magnesium compound into the carrier by impregnation to obtain catalyst precursor I; (2) contacting a dispersant with the catalyst precursor I in the presence of an inert gas to obtain catalyst precursor II; (3) using at least one of step (3-1) or step (3-2), wherein, step (3-1) comprises sulfidizing the catalyst precursor II; step (3-2) comprises impregnating the catalyst precursor II with an impregnation solution containing a polysulfide compound and then drying.

15. The method of claim 14, wherein, In step (1), the carrier is impregnated with an impregnation solution containing molybdenum hexacarbonyl and an organic magnesium compound, and then dried.

16. The method of claim 15, wherein, In step (1), the impregnation is an equal-volume impregnation method or an excess-impregnation method.

17. The method of claim 15, wherein, In step (1), the solvent in the impregnation solution is one or more of ethanol, benzene, toluene, xylene, ethylbenzene and tetrahydronaphthalene.

18. The method of claim 17, wherein, In step (1), the solvent in the impregnation solution is at least one of toluene, xylene, ethylbenzene and tetrahydronaphthalene, and optionally ethanol.

19. The method of claim 15, wherein, The organic magnesium compound is selected from one or more of magnesium citrate, magnesium glycinate, magnesium gluconate, magnesium salicylate and magnesium laurate.

20. The method of claim 15, wherein, In the impregnation solution, the concentration of molybdenum hexacarbonyl is 0.2-3.5 mol / L, and the concentration of the organic magnesium compound is 0.05-0.8 mol / L.

21. The method of claim 20, wherein, The concentration of the hexacarbonylmolybdenum in the impregnating solution is 0.4-2.0 mol / L, and the concentration of the organic magnesium compound is 0.1-0.6 mol / L.

22. The method of claim 15, wherein, In step (1), the drying method is vacuum drying under reduced pressure, wherein the drying temperature is 60-120℃, the vacuum degree during drying is 0.1-2.0 torr, and the drying time is 1-10 hours.

23. The method of claim 22, wherein, In step (1), the drying temperature is 80-100℃, the vacuum degree during drying is 0.2-1.0 torr, and the drying time is 2-8 hours.

24. The method of claim 14, wherein, In step (2), the dispersant is at least one selected from acetic acid, acetic anhydride, citric acid, dimethyl malonate, malonic acid and succinic acid. In step (2), the amount of the dispersant used is 1-10 g per 1 g of the catalyst precursor I. In step (2), the contacting condition includes a pressure of 0-1.0 MPa, a treatment temperature of 80-180℃, and a treatment time of 8-36 hours, wherein the pressure is a gauge pressure.

25. The method of claim 24, wherein, In step (2), the dispersant is acetic acid and / or acetic anhydride. In step (2), the amount of the dispersant used is 2-5 g per 1 g of the catalyst precursor I. In step (2), the contacting condition includes a pressure of 0.1-0.5 MPa, a treatment temperature of 100-150℃, and a treatment time of 12-24 hours.

26. The method of claim 14, wherein, After the contacting in step (2), the remaining dispersant is removed by evaporation drying.

27. The method of claim 26, wherein, After the contacting in step (2), the remaining dispersant is removed by vacuum drying under reduced pressure.

28. The method of claim 26, wherein, The evaporation drying condition includes a drying temperature of 80-150℃, a vacuum degree during drying of 0.1-2.0 torr, and a drying time of 1-8 hours.

29. The method of claim 28, wherein, The evaporation drying condition includes a drying temperature of 100-120℃, a vacuum degree during drying of 0.2-1.0 torr, and a drying time of 2-6 hours.

30. The method of claim 14, wherein, In step (3-2), the solvent in the impregnating solution containing the polysulfide compound is at least one selected from aromatic hydrocarbons, C5-C10 alkanes and C5-C10 cycloalkanes.

31. The method of claim 30, wherein, In step (3-2), the solvent is one or more selected from cyclohexane, n-heptane, n-octane, tetrahydronaphthalene, decahydronaphthalene, toluene and xylene.

32. The method of claim 14, wherein, In step (3-2), the mass concentration of the polysulfide compound in the impregnating solution containing the polysulfide compound is 2%-20%.

33. The method of claim 32, wherein, In step (3-2), the mass concentration of the polysulfide compound in the impregnating solution containing the polysulfide compound is 3%-15%.

34. The method of claim 14, wherein, In step (3-2), the impregnating method is equal-volume impregnation.

35. The method of claim 14, wherein, After the impregnation in step (3-2), drying is performed, and the drying method is vacuum drying under reduced pressure, wherein the drying temperature is 60-120℃, the vacuum degree during drying is 0.1-2.0 torr, and the drying time is 1-6 hours.

36. The method of claim 35, wherein, In step (3-2), the drying method is vacuum drying under reduced pressure, wherein the drying temperature is 80-100℃, the vacuum degree during drying is 0.2-1.0 torr, and the drying time is 2-4 hours.

37. The method of claim 14, wherein, The dried material obtained in step (3-2) is subjected to hydrogen treatment, the hydrogen is once-through, and the hydrogen amount is 0.1-1 NL per 1 g of the dried material; the hydrogen treatment is carried out in a closed condition.

38. The method of claim 37, wherein, The hydrogen treatment temperature is 180-300 ℃, and the treatment time is 2.0-10.0 hours.

39. The method of claim 38, wherein, The hydrogen treatment temperature is 200-260 ℃, and the treatment time is 3.0-6.0 hours.

40. The method of claim 37, wherein, The hydrogen amount is 0.2-0.8 NL per 1 g of the dried material.

41. Use of the catalyst according to any one of claims 1-13 in a hydro-decarbon residue reaction of a low-sulfur heavy feedstock, the mass content of sulfur in the low-sulfur heavy feedstock being 8000 ppm or less.

42. The use of claim 41, wherein, The low-sulfur heavy feedstock is at least one of ebullated-bed hydroprocessing tail oil, coal tar, and Fischer-Tropsch synthesis oil.

43. The use of claim 42, wherein, The low-sulfur heavy feedstock is ebullated-bed hydroprocessing tail oil.

44. The use according to claim 42 or 43, wherein The low-sulfur heavy feedstock has a density of 0.95-1.05 g / cm 3 , a mass content of nitrogen of 5000 ppm or less, and a mass content of residual carbon of 8-25%.

45. The use according to claim 44, wherein the compound is ###00011### 44 45 The hydro-decarbon residue removal reaction conditions are as follows: reaction temperature is 300-450℃, reaction pressure is 12-25 MPa, hydrogen / oil volume ratio is 500-2000:1, liquid hourly space velocity is 0.1-0.5 h -1 .

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