Methods and apparatus for synthesizing homogeneous organic molybdenum-containing compounds and their applications, tower reactor

Abstract

This invention relates to the field of organometallic compound production technology, specifically disclosing a method and apparatus for synthesizing a homogeneous organic molybdenum-containing compound, its application, and a tower reactor. The method includes: (1) introducing a molybdenum-containing stream and an organic ligand stream I into a first reaction unit to carry out a first reaction, obtaining a gas phase I and a liquid phase stream I; (2) introducing the liquid phase stream I and the organic ligand stream II from the upper middle and lower parts of the tower reactor, respectively, into the tower reactor in a second reaction unit to carry out a second reaction, obtaining a gas phase II and a liquid phase stream II as the homogeneous organic molybdenum-containing compound. The method of this invention is simple in process, flexible in operation, and has low energy consumption, and can overcome the scale-up effect of complex reaction systems.

Description

Technical Field

[0001] This invention relates to the field of organometallic compound production technology, specifically to a method and apparatus for synthesizing homogeneous molybdenum-containing organic compounds and their applications, as well as a tower reactor. Background Technology

[0002] Since the beginning of the 21st century, global oil resources have become increasingly scarce, conventional oil resources have been decreasing, oil prices have been rising, and oil resources have become increasingly heavy. The utilization of unconventional oil resources has attracted growing attention from various countries. In the future, with the continuous advancement of oil extraction technology and the increasing production of heavy oil, the efficient conversion and utilization of heavy oil will be a focus for major oil companies.

[0003] Heavy oil includes crude oil with an API gravity of less than 20, atmospheric residue, vacuum residue, and unconventional crude oil obtained from secondary oil recovery. These resources are characterized by high levels of sulfur, nitrogen, metals, and asphaltenes, making heavy oil hydrotreating the best way to utilize them efficiently.

[0004] The lightening process of heavy oil mainly includes decarbonization and hydrotreating. These processes redistribute hydrocarbons, altering the hydrocarbon ratio in the residue oil and processing it into higher value-added light products. Decarbonization processes include catalytic cracking, delayed coking, and solvent deasphalting, while hydrotreating processes include hydrocracking, hydrorefining, hydrodesulfurization, and hydroconversion.

[0005] Because slurry-bed hydrocracking has fewer restrictions on feedstock, it is widely used in the hydrocracking process of heavy oil.

[0006] Unlike conventional supported catalysts, slurry-bed residue hydrotreating catalysts are primarily dispersed solid catalysts. Early solid catalysts included granular and powdered forms, with powdered catalysts, which have smaller particle sizes, showing better reaction performance than granular catalysts. Subsequently, water-soluble and oil-soluble catalysts were developed. However, water-soluble catalysts face problems in dispersion and sulfidation during use, significantly affecting their activity. Oil-soluble catalysts, being homogeneous catalysts, can be uniformly dispersed in residue oil and undergo in-situ sulfidation decomposition to generate micron-sized catalyst particles that readily react with the residue oil, thus becoming a focus of research.

[0007] Studies have shown that the main types of homogeneous oil-soluble catalysts are organometallic compounds from Groups IV-VIII. Among them, Mo exhibits higher hydrogenation activity than other transition metals (such as Ni, V, and Co). While commonly used sulfur- and phosphorus-containing oil-soluble organomolybdenum compounds in the lubricating oil field contain metallic molybdenum, their molybdenum-containing compounds generally have high sulfur, nitrogen, and phosphorus content, making them unsuitable as catalyst precursors for the widely used slurry-bed residue oil hydrogenation process. Therefore, it is necessary to develop preparation techniques for homogeneous organic molybdenum-containing compounds suitable for slurry-bed residue oil hydrogenation systems.

[0008] In addition, the synthesis of homogeneous organic molybdenum-containing compounds is hampered by the complexity of the reaction system and the varying reaction conditions required for different raw materials and reaction pathways. This makes large-scale production and intelligent industrial technology difficult to achieve in a solid-liquid mass transfer system, and batch-to-batch product stability is low. Consequently, the widespread application of homogeneous organic molybdenum-containing compounds in large-scale petrochemical plants and high-end lubricant applications is limited.

[0009] In the continuous production process of organic homogeneous molybdenum-containing compounds, it is difficult to achieve efficient utilization of metallic molybdenum and obtain high-quality products because the mass transfer problem between different bulk phases during the reaction process has not been effectively solved.

[0010] Therefore, developing suitable slurry bed residue hydrogenation systems, improving the mass transfer problem between different phases in the reaction process for preparing homogeneous organic molybdenum-containing compounds, addressing the complexity of the preparation process, and enhancing the stability of the products are urgent problems that the petroleum industry needs to solve. Summary of the Invention

[0011] The purpose of this invention is to overcome the problems of mass transfer between different phases during the preparation of homogeneous organic molybdenum-containing compounds, the complexity of the preparation process, and the low stability of homogeneous organic molybdenum-containing compounds.

[0012] To achieve the above objectives, the present invention provides a method for synthesizing a homogeneous organic molybdenum-containing compound, wherein the method is carried out in a system containing a first reaction unit and a second reaction unit, the second reaction unit being provided with a tower reactor; the method includes:

[0013] (1) Introduce the molybdenum-containing stream and the organic ligand stream I into the first reaction unit to carry out the first reaction, and obtain the conversion product I. Separate the conversion product I into gas phase I and liquid phase stream I.

[0014] (2) The liquid phase stream I and the organic ligand stream II are introduced from the upper middle part and the lower part of the tower reactor into the tower reactor in the second reaction unit to carry out the second reaction, respectively, to obtain gas phase II and liquid phase stream II as the organic homogeneous molybdenum-containing compound;

[0015] The weight ratio of organic ligand stream I to organic ligand stream II is 1:0.05-1;

[0016] The pressure of the second reaction is 10 kPa to 1 MPa lower than that of the first reaction;

[0017] The temperature of the second reaction is 5°C to 55°C higher than that of the first reaction.

[0018] A second aspect of the present invention provides a tower reactor, the tower reactor comprising:

[0019] Tower body; wherein a central drive shaft is provided at the central axis of the tower body;

[0020] At least one material inlet; wherein the material inlet includes a liquid phase flow I inlet A4 and an organic ligand flow II inlet A5 respectively disposed in the upper middle and lower parts of the tower body;

[0021] At least one material outlet for drawing material out of the tower body from the tower reactor;

[0022] At least two turntables are provided on the central drive shaft below the direction of the liquid flow inlet A4, and each turntable is arranged parallel to each other along the cross-sectional direction of the tower reactor. Each turntable rotates by the movement of the central drive shaft.

[0023] The third aspect of this invention provides the application of the tower reactor described in the second aspect in the synthesis of homogeneous organic molybdenum-containing compounds.

[0024] The fourth aspect of the present invention provides an apparatus for synthesizing a homogeneous organic molybdenum-containing compound, wherein a first reaction unit and a second reaction unit are arranged sequentially along the liquid phase flow direction, and a tower reactor is arranged in the second reaction unit.

[0025] The first reaction unit is used to carry out a first reaction between the molybdenum-containing stream and the organic ligand stream I to obtain gas phase I and liquid phase stream I;

[0026] The second reaction unit is connected to the first reaction unit so that the organic ligand stream II and the liquid stream I obtained from the first reaction unit can undergo a second reaction in the tower reactor of the second reaction unit to obtain gaseous stream II and liquid stream II as the organic homogeneous molybdenum-containing compound;

[0027] The tower reactor is the tower reactor described in the second aspect.

[0028] The fifth aspect of the present invention provides the application of the apparatus described in the fourth aspect in the hydrogenation reaction of residual oil.

[0029] Compared with the prior art, the present invention has at least the following advantages:

[0030] (1) The dual-reaction-stage synthesis method provided by the present invention can improve the mass transfer problem of different phases in the reaction process of preparing organic homogeneous molybdenum-containing compounds, improve the stability of the product, and have a higher molybdenum yield.

[0031] (2) The method of the present invention is simple, flexible in operation, and has low energy consumption, and can overcome the scale-up effect of complex reaction systems.

[0032] (3) The organic homogeneous molybdenum-containing compounds obtained by the method of the present invention can be uniformly dispersed in the hydrocarbon phase and have excellent hydrogenation activity and selectivity for hydrothermal cracking reaction. Attached Figure Description

[0033] Only key equipment is shown in the figure, while equipment known to those skilled in the art, such as pumps, heaters, and separators, is omitted. This should not be construed as a limitation of the present invention.

[0034] Figure 1 This is a process flow diagram of a preferred embodiment of the present invention for synthesizing a homogeneous organic molybdenum-containing compound;

[0035] Figure 2 This is a schematic diagram of the structure of a tower reactor according to a preferred embodiment of the present invention.

[0036] Explanation of reference numerals in the attached figures

[0037] R1: First reaction unit; R2: Second reaction unit

[0038] D1: Separation Unit

[0039] 1: Molybdenum-containing stream I 2: Organic ligand stream I

[0040] 3: Gas phase I 4: Liquid phase I

[0041] 5: Organic Ligand Flow II 6: Gas Phase II

[0042] 7: Liquid phase stream II 8: Gas

[0043] 9: Liquid phase containing light components 10: Circulating liquid phase stream II

[0044] 2-1: Drive shaft 2-2: Annular baffle

[0045] 2-3: Rotary table; 2-4: Packing section

[0046] A4: Liquid phase flow inlet I; A5: Organic ligand flow inlet II

[0047] A6: Gas Phase II Outlet; A7: Liquid Phase II Outlet

[0048] A10: Circulating Liquid Phase Stream II Inlet Detailed Implementation

[0049] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0050] As previously stated, the first aspect of this invention provides a method for synthesizing a homogeneous organic molybdenum-containing compound, the method being carried out in a system comprising a first reaction unit and a second reaction unit, wherein the second reaction unit is provided with a tower reactor; the method includes:

[0051] (1) Introduce the molybdenum-containing stream and the organic ligand stream I into the first reaction unit to carry out the first reaction, and obtain the conversion product I. Separate the conversion product I into gas phase I and liquid phase stream I.

[0052] (2) The liquid phase stream I and the organic ligand stream II are introduced from the upper middle part and the lower part of the tower reactor into the tower reactor in the second reaction unit to carry out the second reaction, respectively, to obtain gas phase II and liquid phase stream II as the organic homogeneous molybdenum-containing compound;

[0053] The weight ratio of organic ligand stream I to organic ligand stream II is 1:0.05-1;

[0054] The pressure of the second reaction is 10 kPa to 1 MPa lower than that of the first reaction;

[0055] The temperature of the second reaction is 5°C to 55°C higher than that of the first reaction.

[0056] It should be noted that in this invention, the "pressure" or "reaction pressure" refers to relative pressure.

[0057] In this invention, preferably, the weight ratio of the organic ligand stream I to the organic ligand stream II is 1:0.08-0.5.

[0058] In a preferred embodiment, the pressure of the second reaction is 10 kPa to 500 kPa lower than the pressure of the first reaction.

[0059] Preferably, the method further includes: in step (1), the product obtained from the first reaction is subjected to gas-liquid separation to obtain gas phase I and liquid phase stream I.

[0060] Preferably, the method further includes: in step (2), the product obtained from the second reaction is subjected to gas-liquid separation to obtain gas phase II and liquid phase stream II.

[0061] Preferably, in step (1), the conditions of the first reaction are at least: the temperature is 150℃-250℃, the pressure is 30kPa to 2.5MPa, and the average residence time of the liquid phase material in the first reaction unit is 10min to 12h.

[0062] In a preferred embodiment, in step (2), the conditions for the second reaction are at least: the temperature is 180°C to 280°C, the pressure is 0 kPa to 1.5 MPa, and the average residence time of the liquid phase material in the second reaction unit is 15 min to 16 h.

[0063] According to a preferred embodiment, a central drive shaft is provided at the central axis of the tower reactor, and at least two turntables are provided on the central drive shaft below the direction of the liquid phase flow inlet A4. Each of the turntables is arranged parallel to each other along the cross-sectional direction of the tower reactor, and each of the turntables rotates by the movement of the central drive shaft.

[0064] Preferably, at least two annular baffles are provided on the inner wall surface of the tower body below the direction of the liquid flow inlet A4, and each of the annular baffles is arranged parallel to each other along the cross-sectional direction of the tower reactor; and the positions of each of the annular baffles and each of the turntables are such that at least one turntable is provided between any two adjacent annular baffles.

[0065] Preferably, the positions of each of the annular baffles and each of the turntables are such that a turntable is provided between any two adjacent annular baffles. The inventors have discovered that, in this preferred configuration, the shear stress generated within the tower reactor can break the liquid phase material into fine droplets, thereby generating a larger vortex motion. This increases the interphase contact area and mass transfer coefficient during the liquid phase reaction, which can suppress axial backmixing to a certain extent, thereby improving mass transfer efficiency and effectively removing non-polar components generated during the reaction.

[0066] In a preferred embodiment, the inner diameters of each of the annular baffles are the same.

[0067] Preferably, the ratio of the ring width of each of the annular baffles to the inner diameter of the tower reactor is 0.1-0.45:1.

[0068] In a preferred embodiment, the annular baffle is disposed on the inner wall surface of the tower body from below the inlet A4 direction of the liquid phase stream I to above the inlet A5 direction of the organic ligand stream II.

[0069] According to the present invention, preferably, the distance between any two adjacent annular baffles is defined as L1, and the distance between the inlet center position of the liquid phase stream I and the inlet center position of the organic ligand stream II is defined as L2, and the ratio between L1 and L2 satisfies: L1:L2=1:1-15.

[0070] Preferably, the distance between any two adjacent annular baffles is defined as L1, and the distance between the turntable between any two adjacent annular baffles and the annular baffle adjacent to the upper surface of the turntable is defined as L3. The ratio between L1 and L3 satisfies: L1:L3=1:0.2-0.85.

[0071] Preferably, the ratio of the diameter d1 of the turntable to the inner diameter d2 of the annular baffle satisfies: d1:d2=1:0.5-1.

[0072] In a preferred embodiment, in step (1), the weight ratio of the molybdenum-containing stream to the organic ligand stream I is 1:1-12.

[0073] Preferably, the reactors of the first reaction unit and the second reaction unit are each independently provided with circulation pipelines, and the circulation-to-extraction ratios of the reactors of the first reaction unit and the second reaction unit are each independently 0.1-10:1, wherein the circulation-to-extraction ratio = the flow rate of the liquid phase stream returning to the reactor / the flow rate of the liquid phase stream exiting the reactor.

[0074] According to a preferred embodiment, the upper part of the tower reactor is provided with a packing section 2-4.

[0075] It should be noted that this invention does not have specific requirements for the control method of the liquid phase interface of the reactor, and conventional industry methods can be used, such as differential pressure transmitters.

[0076] Preferably, the method further includes: introducing at least a portion of the gas phase I and / or at least a portion of the gas phase II into a separation unit along the flow direction for separation to obtain a gas and a liquid phase containing light components.

[0077] In a preferred embodiment, the method further includes: in step (1), the reactor of the first reaction unit is a jacketed reactor, and the inner cylinder of the jacketed reactor is provided with a molybdenum-containing material inlet, an organic ligand material I inlet, a liquid phase material I outlet, and a gas phase I outlet;

[0078] Optionally, the inner cylinder of the jacketed reactor is also provided with a gas phase flow inlet.

[0079] In a preferred embodiment, the method further includes: providing an organic ligand stream II inlet and an organic ligand stream II outlet on the outer cylinder of the jacketed reactor.

[0080] Preferably, in step (1), the molybdenum-containing stream contains at least one molybdenum-containing raw material selected from molybdenum oxide, molybdenum monocarboxylic acid salts of C1-C6, molybdenum dicarboxylic acid salts of C1-C6, molybdenum tricarboxylic acid salts of C1-C6, dimolybdate, molybdate, secondary molybdate, pentamolybdate, octamolybdate, tetramolybdate, molybdic acid, molybdic anhydride, ammonium dimolybdate, ammonium secondary molybdate, ammonium tetramolybdate, molybdenum dioxide, molybdenum trioxide, and ammonium 12-molybdate phosphate.

[0081] Preferably, the molybdenum-containing raw material is selected from at least one of molybdenum dioxide, molybdenum trioxide, molybdic acid, ammonium dimolybdate, ammonium 12-molybdate phosphate, ammonium paramolybdate, molybdenum salts of C1-C6 monocarboxylic acids, and molybdenum salts of C1-C6 dicarboxylic acids.

[0082] More preferably, the molybdenum-containing raw material is a C1-C6 dicarboxylic acid molybdenum salt, molybdic acid, ammonium paramolybdate, or ammonium tetramolybdate.

[0083] In a preferred embodiment, the organic ligand stream I and the organic ligand stream II are each independently selected from C6-C. 28 Straight-chain oxygen-containing organic acids, C6-C 28 At least one of the branched oxygen-containing organic acids.

[0084] Preferably, the organic ligand stream I and the organic ligand stream II are each independently or identically selected from C6-C. 28 Monocarboxylic acids, C6-C 28 dicarboxylic acids, C6-C 28 It contains at least one of the following: polycarboxylic acids, thiocarboxylic acids, sulfonic acids, and petroleum acids.

[0085] Preferably, organic ligand stream I and organic ligand stream II are each independently selected from at least one of 2-propylheptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, dodecylbenzenesulfonic acid, cycloalkanoic acid, n-nonanoic acid, n-hexanoic acid, isohexanoic acid, and isononanoic acid.

[0086] The following combination Figure 1 A preferred embodiment of the method for synthesizing a homogeneous organic molybdenum-containing compound according to the present invention will be described, specifically:

[0087] This method is carried out in a system containing a first reaction unit R1 and a second reaction unit R2, wherein the second reaction unit is equipped with a tower reactor; the method includes:

[0088] (1) Introduce molybdenum-containing stream 1 and organic ligand stream I 2 into the first reaction unit R1 to carry out the first reaction to obtain conversion product I. Separate the conversion product I into gas phase I 3 and liquid phase stream I 4.

[0089] (2) The liquid phase stream I 4 and the organic ligand stream II 5 are introduced into the second reaction unit R2 from the upper middle part and the lower part of the tower reactor, respectively, to carry out the second reaction and obtain the conversion product II. The conversion product II is subjected to gas-liquid separation to obtain gas phase II 6 and liquid phase stream II 7, which is the organic homogeneous molybdenum-containing compound.

[0090] The method further includes: introducing at least a portion of gas phase I 3 and at least a portion of gas phase II 6 into separation unit D1 for separation to obtain gas 8 and liquid phase 9 containing light components;

[0091] The reactor of the second reaction unit is equipped with a circulation pipeline to return the circulating liquid phase stream II 10 to the tower reactor via the circulating liquid phase stream II inlet A10.

[0092] It should be noted that in the method provided by the present invention, the first reaction unit and / or the second reaction unit can be operated independently in the form of a single system, a series connection of two systems or a parallel connection of two systems, for example, by using a continuous batch reactor with two systems in series, or they can be switched online during operation.

[0093] Preferably, the method of the present invention further includes: introducing molybdenum-containing stream I and organic ligand stream I into the first reaction unit in the presence of dispersed streams;

[0094] The dispersed stream contains a dispersant and / or a co-dispersant;

[0095] Preferably, the dispersant is at least one selected from water, alcohol, and ether;

[0096] The dispersing agent is an acidic dispersant and / or an alkaline dispersant;

[0097] Preferably, the acidic dispersant is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, C1-C6 monocarboxylic acid, C1-C6 dicarboxylic acid, and C1-C6 tricarboxylic acid;

[0098] The alkaline dispersant is selected from at least one of sodium hydroxide, ammonia, and ammonium hydroxide;

[0099] The weight ratio of the dispersant to the molybdenum-containing stream is 0-5:1, and the weight ratio of the dispersing aid to the molybdenum-containing stream is 0-1:1.

[0100] As described above, a second aspect of the present invention provides a tower reactor, the tower reactor comprising:

[0101] Tower body; wherein a central drive shaft is provided at the central axis of the tower body;

[0102] At least one material inlet; wherein the material inlet includes a liquid phase flow I inlet A4 and an organic ligand flow II inlet A5 respectively disposed in the upper middle and lower parts of the tower body;

[0103] At least one material outlet for drawing material out of the tower body from the tower reactor;

[0104] At least two turntables are provided on the central drive shaft below the direction of the liquid flow inlet A4, and each turntable is arranged parallel to each other along the cross-sectional direction of the tower reactor. Each turntable rotates by the movement of the central drive shaft.

[0105] In this invention, the reactor further includes a motor drive transmission shaft disposed at the top of the reactor.

[0106] Preferably, the tower reactor also includes at least two annular baffles.

[0107] Preferably, each of the annular baffles is disposed on the inner wall surface of the tower body below the direction of the liquid flow inlet A4, and each of the annular baffles is parallel to each other along the cross-sectional direction of the tower reactor; and the positions of each of the annular baffles and each of the turntables are such that at least one turntable is disposed between any two adjacent annular baffles.

[0108] Preferably, the positions of each of the annular baffles and each of the turntables are such that a turntable is provided between any two adjacent annular baffles.

[0109] Preferably, the inner diameters of each of the annular baffles are the same.

[0110] Preferably, the ratio of the ring width of each of the annular baffles to the inner diameter of the tower reactor is 0.1-0.45:1.

[0111] In a preferred embodiment, the annular baffle is disposed on the inner wall surface of the tower body from below the inlet A4 direction of the liquid phase stream I to above the inlet A5 direction of the organic ligand stream II.

[0112] Preferably, the distance between any two adjacent annular baffles is defined as L1, and the distance between the center position of the inlet A4 of the liquid phase flow I and the center position of the inlet A5 of the organic ligand flow II is defined as L2. The ratio between L1 and L2 satisfies: L1:L2=1:1-15.

[0113] Preferably, the distance between any two adjacent annular baffles is defined as L1, and the distance between the turntable between any two adjacent annular baffles and the annular baffle adjacent to the upper surface of the turntable is defined as L3. The ratio between L1 and L3 satisfies: L1:L3=1:0.2-0.85.

[0114] According to a preferred embodiment, the ratio of the diameter d1 of the turntable to the inner diameter d2 of the annular baffle satisfies: d1:d2=1:0.5-1.

[0115] In a preferred embodiment, the upper part of the tower reactor is provided with a packing section 2-4.

[0116] The following combination Figure 2 A specific embodiment of the tower reactor described in this invention will be described, specifically: the tower reactor includes:

[0117] Tower body; wherein a central drive shaft 2-1 is provided at the central axis of the tower body;

[0118] Three material inlets; wherein, the material inlets include a liquid phase flow I inlet A4 and an organic ligand flow II inlet A5 respectively located in the upper middle and lower parts of the tower body; the material inlets also include a circulating liquid phase flow II inlet A10;

[0119] Two material outlets are provided for drawing material out of the tower reactor from the tower body; wherein the material outlets include a gas phase II outlet A6 and a liquid phase flow II outlet A7 respectively disposed at the top and bottom of the tower body;

[0120] At least two turntables 2-3 are provided on the central drive shaft 2-1 below the direction of the liquid flow I inlet A4, and each turntable is arranged parallel to each other along the cross-sectional direction of the tower reactor. Each turntable rotates through the movement of the central drive shaft 2-1.

[0121] The tower reactor also includes at least two annular baffles 2-2;

[0122] Each of the annular baffles is arranged on the inner wall surface of the tower body below the direction of the liquid flow I inlet A4, and each of the annular baffles 2-2 is parallel to each other along the cross-sectional direction of the tower reactor; and the arrangement of each of the annular baffles 2-2 and each of the turntables 2-3 is such that a turntable is arranged between any two adjacent annular baffles.

[0123] The inner diameters of all the aforementioned annular baffles are the same;

[0124] The ratio of the ring width of each of the aforementioned annular baffles to the inner diameter of the tower reactor is 0.15-0.4:1;

[0125] The annular baffle is disposed on the inner wall surface of the tower body from below the liquid phase flow I inlet A4 direction to above the organic ligand flow II inlet A5 direction;

[0126] Define the distance between any two adjacent annular baffles as L1, and define the distance between the center position of the liquid phase flow I inlet A4 and the center position of the organic ligand flow II inlet A5 as L2. The ratio between L1 and L2 satisfies: L1:L2=1:3-13;

[0127] Define the distance between any two adjacent annular baffles as L1, and define the distance between the turntable between any two adjacent annular baffles and the annular baffle adjacent to the upper surface of the turntable as L3. The ratio between L1 and L3 satisfies: L1:L3=1:0.3-0.7;

[0128] The ratio of the diameter d1 of the turntable to the inner diameter d2 of the annular baffle satisfies: d1:d2=1:0.55-0.9;

[0129] The upper part of the tower reactor is provided with a packing section 2-4.

[0130] As previously stated, the third aspect of the present invention provides the application of the tower reactor described in the second aspect in the synthesis of homogeneous organic molybdenum-containing compounds.

[0131] As mentioned above, the fourth aspect of the present invention provides an apparatus for synthesizing a homogeneous organic molybdenum-containing compound, wherein a first reaction unit and a second reaction unit are arranged sequentially along the liquid phase flow direction, and the second reaction unit is provided with the tower reactor described in the second aspect.

[0132] The first reaction unit is used to carry out a first reaction on the molybdenum-containing stream and the organic ligand stream I to obtain conversion product I. After gas-liquid separation, gas phase I and liquid phase stream I are obtained.

[0133] The second reaction unit is connected to the first reaction unit so that the organic ligand stream II and the liquid stream I obtained from the first reaction unit can undergo a second reaction in the tower reactor of the second reaction unit to obtain gaseous stream II and liquid stream II as the organic homogeneous molybdenum-containing compound;

[0134] The tower reactor is the tower reactor described in the second aspect.

[0135] In this invention, according to a preferred embodiment, the reactor of the first reaction unit is a jacketed reactor, and the inner cylinder of the jacketed reactor is provided with a molybdenum-containing stream inlet, an organic ligand stream I inlet, a liquid stream I outlet, and a gaseous stream I outlet.

[0136] Optionally, the inner cylinder of the jacketed reactor is also provided with a gas phase flow inlet.

[0137] It should be noted that the present invention does not have specific requirements for the method of controlling the reaction temperature in each reactor, and conventional heating modules in the art can be used.

[0138] Preferably, the apparatus further includes a separation unit, which is connected to the second reaction unit for separating at least a portion of the gas phase I and / or at least a portion of the gas phase II to obtain a gas and a liquid phase containing light components.

[0139] In a preferred embodiment, the separation unit is provided with a gas outlet, a liquid phase outlet containing light components, and a gas phase I inlet and / or a gas phase II inlet.

[0140] As previously stated, the fifth aspect of the present invention provides the application of the apparatus described in the fourth aspect in the hydrogenation reaction of residual oil.

[0141] According to a preferred embodiment, in the hydrogenation reaction of the residue oil, the amount of the organic homogeneous molybdenum-containing compound used is 80-2800 μg / g, calculated as metallic molybdenum.

[0142] Preferably, the conditions for the hydrogenation reaction of the residue oil are at least: the reaction pressure is 10MPa-20MPa, the reaction temperature is 400℃-470℃, and the reaction time is 0.5-8h.

[0143] The inventors discovered that in the residual oil hydrotreating application described in this invention (i.e., under hydrogen protection, the feedstock oil or coal liquid phase is fully contacted and mixed with the organic homogeneous molybdenum-containing compound prepared in this invention before being fed into the hydrotreating reactor), the apparatus provided by this invention facilitates the in-situ sulfidation of the organic homogeneous molybdenum-containing compound into a monolayer stable MoS2 active phase. Furthermore, in the organic phase, the organic homogeneous molybdenum-containing compound exhibits higher dispersion stability than heterogeneous Mo-based catalysts. In this application, the hydrotreating reaction is highly effective, and its coking suppression performance is outstanding.

[0144] The method provided by this invention can improve mass transfer during the reaction process, increase mass transfer efficiency, effectively remove non-polar components generated during the reaction, and improve reaction conversion rate. While overcoming the scale-up effect of complex reaction systems, it also features simple process, flexible operation, and low energy consumption. The reaction apparatus described in this invention is not limited to the synthesis of homogeneous organic molybdenum-containing compounds, but can also be applied to the synthesis of other organometallic compounds.

[0145] The present invention will be described in detail below by way of examples, but this does not mean that the present invention is limited in any way.

[0146] In the following examples, unless otherwise specified, all chemical reagents used are products of Sinopharm Chemical Reagent Co., Ltd.

[0147] Unless otherwise specified, the following examples use Figure 1 The process flow shown is as follows: Figure 2 The process is carried out in the tower reactor shown.

[0148] Molybdenum content determination: Inductively coupled plasma atomic emission spectrometry (ICP-AES) was used.

[0149] For the products obtained in the following examples, namely organic homogeneous molybdenum-containing compounds, the following property parameters of the products were determined: molybdenum content, molybdenum yield, water content, and impurity content, and are listed in Table 1.

[0150] In terms of elements, the yield of metallic molybdenum / % = mass of metallic molybdenum in the organic homogeneous molybdenum-containing compound / mass of metallic molybdenum in the molybdenum-containing raw material * 100%.

[0151] The setup for the tower reactor used below is as follows:

[0152] The tower reactor has a volume of 11 dm³. 3 The length-to-diameter ratio of the tower reactor is 12:1;

[0153] The distance between the top of the tower reactor and the central axis of the inlet A4 of liquid stream I: the distance between the central axis of the inlet A4 of liquid stream I and the central axis of the inlet A5 of organic ligand stream II: the distance between the central axis of the inlet A5 of organic ligand stream II and the bottom of the tower reactor = 2:5:1;

[0154] A central drive shaft is provided at the central axis of the tower reactor, and a turntable is provided on the central drive shaft below the direction of the liquid flow inlet A4. Each of the turntables is arranged parallel to each other along the cross-sectional direction of the tower reactor, and each of the turntables rotates by the movement of the central drive shaft.

[0155] An annular baffle is provided on the inner wall of the tower body below the inlet A4 of the liquid flow I, and each of the annular baffles is arranged parallel to each other along the cross-sectional direction of the tower reactor; and the positions of each of the annular baffles and each of the turntables are such that a turntable is provided between any two adjacent annular baffles.

[0156] The inner diameter of each annular baffle in the reactor is the same, and the ratio of the ring width of each annular baffle to the inner diameter of the tower reactor is 0.35:1.

[0157] Furthermore, the ratio between L1 and L2 is: L1:L2 = 1:6;

[0158] The ratio between L1 and L3 is: L1:L3 = 1:0.6;

[0159] The ratio between d1 and d2 is: d1:d2 = 1:0.9;

[0160] The upper part of the tower reactor is equipped with a packing section.

[0161] Example 1

[0162] This embodiment illustrates the method for synthesizing homogeneous organic molybdenum-containing compounds provided by the present invention. This embodiment is implemented in a system containing a first reaction unit and a second reaction unit. The second reaction unit is equipped with a tower reactor. Specifically:

[0163] (1) Introduce the molybdenum-containing stream and the organic ligand stream I into the first reaction unit to carry out the first reaction to obtain the conversion product I. Separate the conversion product I into gas phase I and liquid phase stream I.

[0164] Wherein, the molybdenum-containing stream is ammonium molybdate, the organic ligand stream I is isononanoic acid, and the first reaction unit is a continuous batch reactor with two systems in series.

[0165] The weight ratio of molybdenum-containing stream to organic ligand stream I was 1:2.63. The conditions for the first reaction were: temperature 230℃, pressure 120kPa, and average residence time of liquid phase material in the first reaction unit was 9h.

[0166] The reactor of the first reaction unit is a jacketed reactor with a gas phase flow inlet on the inner cylinder; the circulation-to-output ratio of the reactor of the first reaction unit is 0.5:1.

[0167] (2) Liquid phase stream I and organic ligand stream II are introduced from the upper middle and lower parts of the tower reactor into the tower reactor in the second reaction unit to carry out the second reaction, to obtain conversion product II. The conversion product II is subjected to gas-liquid separation to obtain gas phase II and liquid phase stream II. Liquid phase stream II is an organic homogeneous molybdenum-containing compound.

[0168] The weight ratio of organic ligand stream I to organic ligand stream II is 1:0.2.

[0169] The conditions for the second reaction are: temperature 255℃, pressure 30kPa, and average residence time of liquid phase material in the second reaction unit is 8h.

[0170] The recycling ratio of the reactor in the second reaction unit is 1:1.

[0171] Furthermore, in steps (1) and (2), all of gas phase I and all of gas phase II are introduced into the separation unit for separation to obtain gas and liquid phase containing light components;

[0172] The separation unit is equipped with a gas outlet, a liquid phase outlet containing light components, and a gas phase I inlet and a gas phase II inlet;

[0173] The reactor of the first reaction unit is a jacketed reactor, and the inner cylinder of the jacketed reactor is provided with a molybdenum-containing stream inlet, an organic ligand stream I inlet, a liquid stream I outlet, and a gaseous stream I outlet.

[0174] The inner cylinder of the jacketed reactor is also provided with a gas phase flow inlet, wherein the gas phase flow is nitrogen.

[0175] The outer cylinder of the jacketed reactor is provided with an organic ligand stream II inlet and an organic ligand stream II outlet;

[0176] The organic homogeneous molybdenum-containing compound obtained in step (2) is named P1.

[0177] Example 2

[0178] This embodiment uses a process similar to that of Embodiment 1, except that the circulation-to-output ratio of the reactor in the first reaction unit and the tower reactor in the second reaction unit is 0.2:1.

[0179] Among them, the organic homogeneous molybdenum-containing compound obtained in step (2) is designated as P2.

[0180] Example 3

[0181] This embodiment uses a process similar to that of Embodiment 2, except that the average residence time of the liquid phase material in the second unit is 12 hours.

[0182] Among them, the organic homogeneous molybdenum-containing compound obtained in step (2) is designated as P3.

[0183] Example 4

[0184] This embodiment uses a process similar to that of Embodiment 1, except that in step (2), the weight ratio of organic ligand stream I to organic ligand stream II is 1:0.8.

[0185] The obtained homogeneous organic molybdenum-containing compound is designated P4.

[0186] Comparative Example 1

[0187] This comparative example was carried out using a process similar to that of Example 1. The difference was that the conditions for the first reaction were: temperature 230°C and pressure 120 kPa, and the conditions for the second reaction were: temperature 170°C and pressure 30 kPa. The organic homogeneous molybdenum-containing compound obtained in step (2) was designated as DP1.

[0188] Comparative Example 2

[0189] This comparative example was carried out using a process similar to that of Example 1. The difference was that the conditions for the first reaction were: temperature 230°C and pressure 120 kPa, and the conditions for the second reaction were: temperature 255°C and pressure 320 kPa. The organic homogeneous molybdenum-containing compound obtained in step (2) was designated as DP2.

[0190] Test Example 1

[0191] This test example illustrates the effectiveness of the organic homogeneous molybdenum-containing compound obtained by the method provided in this invention as a catalyst in the hydrogenation reaction of residual oil.

[0192] This test case applies the products obtained from the aforementioned examples to perform tests, including the following steps:

[0193] S1: In the presence of hydrogen, organic homogeneous molybdenum-containing compounds, sulfur powder, and preheated feedstock oil are added to a high-pressure autoclave hydrogenation reactor in a mass ratio of 0.007:0.002:1 to carry out a residue oil hydrogenation reaction, obtaining hydrogenation reaction products (including gaseous products and liquid products); wherein, the feedstock oil is residue oil, and its properties are shown in Table 2; the conditions for the residue oil hydrogenation reaction are: reaction pressure of 16 MPa, reaction temperature of 430℃, and reaction time of 3 h;

[0194] S2: When the autoclave temperature drops to 60℃, connect the gas sampling system and analyze the content of the gaseous products; take the liquid products for distillation and perform component analysis.

[0195] In each example of application, the amount of the organic homogeneous molybdenum-containing compound used is 1200 μg / g, calculated as metallic molybdenum.

[0196] The content and composition analysis results of the products from the hydrogenation reaction of residual oil are shown in Table 3.

[0197] Table 1

[0198] project P1 P2 P3 P4 DP1 DP2 Molybdenum (oil-soluble) content wt / % 17.93 17.87 18.01 16.95 16.69 15.4 Molybdenum metal yield / % 99.56 99.22 99.99 98.05 97.72 97.2 Water content / wt% trace trace none 0.06 3.03 2.6 Impurity content / wt% 0.023 0.032 0.0014 0.8 7.2 14.4 Blockage during synthesis none none none none none none

[0199] Note: The water content in the trace surface sample is less than one part per thousand; impurities are the remaining part of the product after removing oil-soluble substances and water.

[0200] Table 2

[0201]

[0202]

[0203] Table 3

[0204] project P1 P2 P3 P4 DP1 DP2 Gas / wt% 12.4 12.1 12.2 11.7 10.4 8.8 Gasoline / wt% 20.8 20.0 20.4 19.6 14.9 10.1 Diesel / wt% 22.9 22.5 23.8 21.6 18.3 13.1 Wax oil / wt% 24.5 24.2 25.2 24.1 27.6 21.4 Slag Reduction wt / % 18.8 20.4 17.9 21.4 26.1 41.3 Toluene insoluble matter / wt% 0.7 0.8 0.5 1.5 2.7 5.3

[0205] As can be seen from the above results, the method provided by the present invention has the characteristics of high reaction mass transfer efficiency, high conversion rate, high stability of the prepared organic homogeneous molybdenum-containing compound, high yield of metallic molybdenum, and low impurity content. Moreover, the method is simple, flexible in operation, and has low energy consumption, thus better overcoming the scale-up effect of complex reaction systems, which is conducive to the large-scale application of the production of organic homogeneous molybdenum-containing compounds.

[0206] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for synthesizing a homogeneous organic molybdenum-containing compound, characterized in that, This method is carried out in a system containing a first reaction unit and a second reaction unit, wherein the second reaction unit is equipped with a tower reactor; the method includes: (1) Introduce the molybdenum-containing stream and the organic ligand stream I into the first reaction unit to carry out the first reaction, and obtain gas phase I and liquid phase stream I; (2) The liquid phase stream I and the organic ligand stream II are introduced from the upper middle part and the lower part of the tower reactor into the tower reactor in the second reaction unit to carry out the second reaction, respectively, to obtain gas phase II and liquid phase stream II as the organic homogeneous molybdenum-containing compound; The weight ratio of organic ligand stream I to organic ligand stream II is 1:0.05-1; The pressure of the second reaction is 10 kPa to 1 MPa lower than that of the first reaction; The temperature of the second reaction is 5°C to 55°C higher than that of the first reaction.

2. The method according to claim 1, wherein, In step (1), the conditions for the first reaction are at least: the temperature is 150℃-250℃, the pressure is 30kPa to 2.5MPa, and the average residence time of the liquid phase material in the first reaction unit is 10min to 12h.

3. The method according to claim 1, wherein, In step (2), the conditions for the second reaction must at least be: temperature of 180℃-280℃, pressure of 0kPa to 1.5MPa, and average residence time of liquid phase material in the second reaction unit of 15min-16h.

4. The method according to any one of claims 1-3, wherein, A central drive shaft is provided at the central axis of the tower reactor, and at least two turntables are provided on the central drive shaft below the direction of the liquid phase flow I inlet (A4). Each of the turntables is arranged parallel to each other along the cross-sectional direction of the tower reactor, and each of the turntables rotates by the movement of the central drive shaft.

5. The method according to claim 4, wherein, At least two annular baffles are provided on the inner wall surface of the tower body below the direction of the liquid flow I inlet (A4), and each of the annular baffles is arranged parallel to each other along the cross-sectional direction of the tower reactor; and the positions of each of the annular baffles and each of the turntables are such that at least one turntable is provided between any two adjacent annular baffles.

6. The method according to claim 5, wherein, The inner diameter of each of the aforementioned annular baffles is the same.

7. The method according to claim 5, wherein, The ratio of the ring width of each of the annular baffles to the inner diameter of the tower reactor is 0.1-0.45:

1.

8. The method according to claim 5 or 6, wherein, The annular baffle is disposed on the inner wall surface of the tower body from below the liquid phase flow I inlet (A4) to above the organic ligand flow II inlet (A5).

9. The method according to claim 5 or 6, wherein, Define the distance between any two adjacent annular baffles as L1, and define the distance between the center position of the inlet of the liquid phase stream I and the center position of the inlet of the organic ligand stream II as L2. The ratio between L1 and L2 satisfies: L1:L2=1:1-15.

10. The method according to claim 5 or 6, wherein, Define the distance between any two adjacent annular baffles as L1, and define the distance between the turntable between any two adjacent annular baffles and the annular baffle adjacent to the upper surface of the turntable as L3. The ratio between L1 and L3 satisfies: L1:L3=1:0.2-0.

85.

11. The method according to claim 5 or 6, wherein, The ratio of the diameter d1 of the turntable to the inner diameter d2 of the annular baffle satisfies: d1:d2=1:0.5-1.

12. The method according to any one of claims 1-3, wherein, In step (1), the weight ratio of the molybdenum-containing stream to the organic ligand stream I is 1:1-12.

13. The method according to any one of claims 1-3, wherein, The reactors of the first reaction unit and the second reaction unit are each independently equipped with circulation pipelines, and the circulation-to-extraction ratios of the reactors of the first reaction unit and the second reaction unit are each independently 0.1-10:1, wherein the circulation-to-extraction ratio = the flow rate of the liquid phase stream returning to the reactor / the flow rate of the liquid phase stream exiting the reactor.

14. The method according to any one of claims 1-3, wherein, The upper part of the tower reactor is provided with a packing section (2-4).

15. The method according to any one of claims 1-3, wherein, The method further includes introducing at least a portion of the gas phase I and / or at least a portion of the gas phase II into a separation unit for separation to obtain a gas and a liquid phase containing light components.

16. The method according to any one of claims 1-3, wherein, The method further includes: in step (1), the reactor of the first reaction unit is a jacketed reactor, and the inner cylinder of the jacketed reactor is provided with a molybdenum-containing material inlet, an organic ligand material I inlet, a liquid phase material I outlet, and a gas phase I outlet; Optionally, the inner cylinder of the jacketed reactor is further provided with a gaseous flow inlet, wherein the gaseous flow is nitrogen or hydrogen.

17. The method according to claim 16, wherein, The method further includes: an organic ligand stream II inlet and an organic ligand stream II outlet are provided on the outer cylinder of the jacketed reactor.

18. The method according to any one of claims 1-3, wherein, In step (1), the molybdenum-containing stream contains at least one molybdenum-containing raw material selected from molybdenum oxide, molybdate, molybdic acid and 12-molybdenum phosphate.

19. The method according to claim 18, wherein, The molybdenum oxide is molybdenum dioxide and / or molybdenum trioxide; And / or, the molybdate is selected from at least one of dimolybdate, secondary molybdate, pentamolybdate, octamolybdate, and tetramolybdate.

20. The method according to claim 18, wherein, The molybdate is selected from at least one of ammonium dimolybdate, ammonium paramolybdate, and ammonium tetramolybdate.

21. The method according to claim 18, wherein, The molybdate is selected from at least one of the following: monocarboxylic acid molybdates of C1-C6, dicarboxylic acid molybdates of C1-C6, and tricarboxylic acid molybdates of C1-C6.

22. The method according to any one of claims 1-3, wherein, The molybdenum-containing raw material is selected from at least one of molybdenum dioxide, molybdenum trioxide, molybdic acid, ammonium dimolybdate, ammonium 12-molybdenum phosphate, ammonium paramolybdate, molybdenum salts of C1-C6 monocarboxylic acids, and molybdenum salts of C1-C6 dicarboxylic acids.

23. The method according to any one of claims 1-3, wherein, The molybdenum-containing raw material is selected from at least one of C1-C6 dicarboxylic acid molybdenum salts, molybdic acid, ammonium paramolybdate, and ammonium tetramolybdate.

24. The method according to any one of claims 1-3, wherein, The organic ligand stream I and organic ligand stream II are each independently selected from C6-C. 28 Straight-chain oxygen-containing organic acids, C6-C 28 At least one of the branched oxygen-containing organic acids.

25. The method according to any one of claims 1-3, wherein, The organic ligand stream I and organic ligand stream II are each independently selected from C6-C. 28 Monocarboxylic acids, C6-C 28 It contains at least one of dicarboxylic acids, thiocarboxylic acids, and sulfonic acids.

26. The method according to any one of claims 1-3, wherein, Organic ligand stream I and organic ligand stream II are each independently petroleum acid.

27. The method according to any one of claims 1-3, wherein, The organic ligand stream I and organic ligand stream II are each independently selected from at least one of 2-propylheptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, dodecylbenzenesulfonic acid, cycloalkanoic acid, n-nonanoic acid, n-hexanoic acid, isohexanoic acid, and isononanoic acid.

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