A method and apparatus for synthesizing homogeneous organic molybdenum-containing compounds and their applications

Abstract

This invention relates to the technical field of organometallic compound production, and discloses a method and apparatus for synthesizing a homogeneous organic molybdenum-containing compound and its application. The method is implemented in a system containing a first reaction unit and a second reaction unit. The first reaction unit comprises at least two batch reactors connected in series. The batch reactors are cylindrical structures containing an inner cylinder and an outer cylinder. The inner cylinder and the outer cylinder are kept in communication so that the material in the inner cylinder can overflow into the outer cylinder. The method includes: introducing a molybdenum-containing material and an organic ligand material into reaction unit 1 for a first reaction to obtain gas phase I and liquid phase I; introducing the organic ligand material and the liquid phase I into the second reaction unit for a second reaction to obtain gas phase II and the homogeneous organic molybdenum-containing compound. The method provided by this invention features high reaction mass transfer efficiency and high conversion rate.

Description

Technical Field

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

[0002] Since the beginning of the 21st century, global oil resources have become increasingly scarce, conventional oil resources have been continuously 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. Among these, the efficient conversion and utilization of heavy oil has become a key focus for major oil companies.

[0003] Heavy oil is characterized by high sulfur, nitrogen, metal, and asphaltenes content, making it difficult to process using conventional catalytic converters. The lightening process of heavy oil mainly involves decarbonization and hydrotreating, which redistributes hydrocarbons, thereby altering the hydrocarbon ratio in the residue oil and processing it into higher value-added light products. Among these processes, slurry-bed hydrocracking can process highly demanding feedstocks, thus demonstrating promising development prospects.

[0004] Unlike conventional supported catalysts, the catalysts used in slurry bed residue hydrotreating are primarily dispersed catalysts. Early solid catalysts included granular and powdered forms, followed by the development of water-soluble and oil-soluble catalysts. However, water-soluble catalysts face challenges in dispersion and sulfidation during use, significantly impacting their activity. Oil-soluble catalysts, being homogeneous, 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.

[0005] Therefore, the dispersion performance of the catalyst in residual oil determines its reaction performance. Studies have shown that homogeneous oil-soluble catalysts are mainly organometallic compounds from Group IV-VIII, among which Mo exhibits higher hydrogenation activity than other transition metals (such as Ni, V, Co, etc.).

[0006] However, oil-soluble molybdenum compounds commonly used in the lubricating oil industry are unsuitable as catalyst precursors for slurry bed residue oil hydrotreating processes, which have a large usage volume, due to their high sulfur, nitrogen, and phosphorus content.

[0007] Furthermore, the complex reaction systems in the synthesis of homogeneous organic molybdenum-containing compounds make large-scale production and intelligent industrial technology difficult to achieve. The stability of batch production is also easily affected. Therefore, developing a preparation technology for homogeneous organic molybdenum-containing compounds suitable for slurry-bed residue hydrotreating systems and capable of large-scale production is an urgent problem to be solved. Summary of the Invention

[0008] The purpose of this invention is to overcome the problems in the prior art, such as the easy occurrence of side reactions during the synthesis of homogeneous molybdenum-containing organic compounds, as well as the low reaction selectivity, low production efficiency, and inability to produce continuously.

[0009] To achieve the above objectives, the present invention provides a method for synthesizing a homogeneous organic molybdenum-containing compound. This method is carried out in a system comprising a first reaction unit and a second reaction unit. The first reaction unit includes at least two batch reactors connected in series. The batch reactors are sleeve structures containing an inner cylinder and an outer cylinder. The inner cylinder and the outer cylinder are kept in communication so that the material in the inner cylinder can overflow into the outer cylinder. The method includes:

[0010] (1) The molybdenum-containing stream is introduced from the upstream batch reactor and flows through each batch reactor connected in series in sequence, and is drawn out from the downstream batch reactor. Each batch reactor is provided with an organic ligand stream inlet so that the molybdenum-containing stream or the liquid stream from the adjacent upstream batch reactor can contact the organic ligand stream introduced from the organic ligand stream inlet to carry out the first reaction in the first reaction unit, and the liquid stream I is obtained from the outlet of the downstream batch reactor.

[0011] (2) The organic ligand stream and the liquid stream I from step (1) are introduced into the second reaction unit to carry out a second reaction, to obtain gas phase II and liquid stream II as the organic homogeneous molybdenum-containing compound;

[0012] The pressure of the second reaction is 10 kPa to 1 MPa lower than that of the first reaction;

[0013] The temperature of the second reaction is 5°C to 55°C higher than that of the first reaction.

[0014] A second aspect of the present invention provides an apparatus for synthesizing a homogeneous organic molybdenum-containing compound, the apparatus comprising a first reaction unit and a second reaction unit that are kept in communication.

[0015] The first reaction unit is provided with at least two batch reactors connected in series; the batch reactor is a sleeve structure containing an inner cylinder and an outer cylinder; the inner cylinder and the outer cylinder are kept in communication so that the material in the inner cylinder can enter the outer cylinder by overflow;

[0016] The second reaction unit is provided with a material inlet, and the second reaction unit is connected to the first reaction unit through a pipeline, so that the material introduced by the material inlet can undergo a second reaction with the material flow from the first reaction unit in the second reaction unit.

[0017] The third aspect of the present invention provides the application of the apparatus described in the second aspect in the hydrogenation reaction of residual oil.

[0018] Compared with the prior art, the present invention has at least the following advantages:

[0019] (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.

[0020] (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;

[0021] (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

[0022] 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.

[0023] Figure 1 This is a process flow diagram of a preferred embodiment of the present invention for synthesizing a homogeneous organic molybdenum-containing compound;

[0024] Figure 2 This is a schematic diagram of the structure of the first reaction unit shown in a preferred embodiment of the present invention.

[0025] Explanation of reference numerals in the attached figures

[0026] R1: First reaction unit; R2: Second reaction unit

[0027] D1: Separation Unit 1: Molybdenum-containing stream

[0028] 2: Organic ligand stream 3: Gas phase I

[0029] 4: Liquid phase I 5: Gas phase II

[0030] 6: Gas; 7: Liquid phase containing light components

[0031] 8: Liquid phase flow II 9: Inner cylinder

[0032] 10: Outer cylinder 11: Transmission device

[0033] a: Import I b: Import II

[0034] c: Import III

[0035] R1-1: First batch reactor; R1-2: Second batch reactor

[0036] R1-3: The third batch reactor; 1-1: SL-type static mixer.

[0037] 1-4, 1-7: Static Mixer Detailed Implementation

[0038] 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.

[0039] As previously stated, the first aspect of this invention provides a method for synthesizing a homogeneous organic molybdenum-containing compound. This method is carried out in a system comprising a first reaction unit and a second reaction unit. The first reaction unit includes at least two batch reactors connected in series. The batch reactors are sleeve structures containing an inner cylinder and an outer cylinder. The inner cylinder and the outer cylinder are kept in communication so that the material in the inner cylinder can overflow into the outer cylinder. The method includes:

[0040] (1) The molybdenum-containing stream is introduced from the upstream batch reactor and flows through each batch reactor connected in series in sequence, and is drawn out from the downstream batch reactor. Each batch reactor is provided with an organic ligand stream inlet so that the molybdenum-containing stream or the liquid stream from the adjacent upstream batch reactor can contact the organic ligand stream introduced from the organic ligand stream inlet to carry out the first reaction in the first reaction unit, and the liquid stream I is obtained from the outlet of the downstream batch reactor.

[0041] (2) The organic ligand stream and the liquid stream I from step (1) are introduced into the second reaction unit to carry out a second reaction, to obtain gas phase II and liquid stream II as the organic homogeneous molybdenum-containing compound;

[0042] The pressure of the second reaction is 10 kPa to 1 MPa lower than that of the first reaction;

[0043] The temperature of the second reaction is 5°C to 55°C higher than that of the first reaction.

[0044] It should be noted that in this invention, the "pressure" or "reaction pressure" refers to relative pressure.

[0045] Preferably, in each of the aforementioned batch reactors, the organic ligand stream introduced from the organic ligand stream inlet enters the inner cylinder and / or outer cylinder.

[0046] In a preferred embodiment, in step (1), in the upstream batch reactor, the organic ligand stream introduced from the organic ligand stream inlet enters the inner and outer cylinders, and the weight ratio of the organic ligand streams entering the inner and outer cylinders is 0.5-8:1.

[0047] According to a preferred embodiment, in step (1), except for the upstream batch reactor, all organic ligand streams introduced from the organic ligand stream inlet enter the outer cylinder.

[0048] Preferably, in each batch reactor, except for the upstream batch reactor, the weight ratio of the liquid phase stream from the adjacent upstream batch reactor to the organic ligand stream introduced from the organic ligand stream inlet is independently 1:0.05-0.5.

[0049] More preferably, except for the upstream batch reactor, the organic ligand streams introduced from each of the organic ligand stream inlets have the same weight.

[0050] Preferably, in the first reaction unit, at least one of the batch reactors is provided with a liquid phase circulating stream, and the circulation-to-extraction ratio of the liquid phase circulating stream in the batch reactor is 0.1-6:1, 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.

[0051] In a preferred embodiment, in step (1), the weight ratio of the molybdenum-containing stream to the organic ligand stream in the upstream batch reactor is 1:1-10. It should be noted that the amount of organic ligand stream in the upstream batch reactor includes the total amount of organic ligand stream entering the inner and outer cylinders of the upstream batch reactor.

[0052] In a preferred embodiment, in step (2), the weight ratio of the liquid phase stream I to the organic ligand stream is 1:0.04-0.5. It should be noted that the organic ligand stream is the organic ligand stream introduced into the second reaction unit in step (2), and does not include the organic ligand stream introduced into the first reaction unit in step (1).

[0053] According to a preferred embodiment, the method of the present invention further includes: obtaining gas phase I from the top of the batch reactor, and introducing at least a portion of gas phase I and / or at least a portion of gas phase II into a separation unit for separation to obtain gas and a liquid phase containing light components.

[0054] According to a preferred embodiment, the method of the present invention further includes: recycling at least a portion of the liquid phase containing the light component as part of the organic ligand stream back to the first reaction unit.

[0055] In a preferred embodiment, in step (1), the reaction conditions in each of the batch reactors are each independently satisfied at least as follows: the temperature is 150°C to 250°C, the pressure is 30 kPa to 2.5 MPa, and the average residence time of the liquid phase material is 10 min to 12 h.

[0056] More preferably, in step (1), the reaction conditions in each of the batch reactors are the same.

[0057] Preferably, in step (2), the conditions of the second reaction are at least: the temperature is 180℃-280℃, the pressure is 0kPa to 1.5MPa, and the average residence time of the liquid phase material in the second reaction unit is 15min to 16h.

[0058] According to a preferred embodiment, 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.

[0059] Preferably, in step (1), 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 monobasic acids of C1-C6, and molybdenum salts of dibasic acids of C1-C6.

[0060] More preferably, in step (1), the molybdenum-containing raw material is a C1-C6 dicarboxylic acid molybdenum salt, molybdic acid, ammonium paramolybdate, or ammonium tetramolybdate.

[0061] According to a preferred embodiment, the organic ligand stream is selected from C6-C. 28 Straight-chain oxygen-containing organic acids, C6-C 28 At least one of the branched oxygen-containing organic acids.

[0062] Preferably, the organic ligand stream is 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.

[0063] More preferably, the organic ligand stream is 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.

[0064] Preferably, in the first reaction unit, the organic ligand stream introduced from each of the organic ligand stream inlets is the same as or different from the organic ligand stream introduced into the second reaction unit in step (2).

[0065] More preferably, in the first reaction unit, the organic ligand stream introduced from each of the organic ligand stream inlets is the same as the organic ligand stream introduced into the second reaction unit in step (2).

[0066] 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.

[0067] According to a preferred embodiment, the method of the present invention further includes: mixing at least a portion of the organic ligand stream with the molybdenum-containing stream via an SL-type static mixer, and then introducing the mixture into a first reaction unit for a first reaction.

[0068] According to a preferred embodiment, the method of the present invention includes:

[0069] (1) Introduce the molybdenum-containing stream and the organic ligand stream into reaction unit 1 to carry out the first reaction to obtain gas phase I and liquid phase stream I;

[0070] The process involves mixing the molybdenum-containing stream and the first portion of the organic ligand stream in an SL-type static mixer before introducing them into the inner cylinder of the first batch reactor. The second portion of the organic ligand stream also enters the inner cylinder of the first batch reactor, while the third portion enters the outer cylinder of the first batch reactor for a first-stage reaction. A gas phase I-1 is obtained from the upper part of the first batch reactor, and a liquid phase stream I-1 is obtained from the lower part. The weight ratio of the first portion of the organic ligand stream to the second portion of the organic ligand stream is 0-5:1.

[0071] The liquid phase stream I-1 is introduced into the second batch reactor to undergo a secondary reaction with the fourth organic ligand stream to obtain gas phase I-2 and liquid phase stream I-2;

[0072] Similarly, the liquid phase stream In-1 obtained from the (n-1)th batch reactor is introduced into the adjacent downstream nth batch reactor to carry out the nth-stage reaction with the (n+2)th part of the organic ligand stream until the reaction in the last batch reactor is completed, and the liquid phase stream I is obtained. The gas phase drawn out from the top of each batch reactor is collected to obtain the gas phase I.

[0073] (2) The organic ligand stream and the liquid stream I from step (1) are introduced into the second reaction unit to carry out a second reaction, to obtain gas phase II and liquid stream II as the organic homogeneous molybdenum-containing compound;

[0074] All of the gas phase I and all of the gas phase II are introduced into the separation unit for separation to obtain a gas and a liquid phase containing light components.

[0075] The following combination Figure 1 and Figure 2 A preferred embodiment of the method for synthesizing a homogeneous organic molybdenum-containing compound according to the present invention will be described, specifically:

[0076] (1) Introduce molybdenum-containing stream 1 and organic ligand stream 2 into reaction unit 1R1 to carry out the first reaction to obtain gas phase I and liquid phase stream I;

[0077] The process involves mixing the molybdenum-containing stream 1 and the first portion of the organic ligand stream in a static mixer 1-1 (SL type) and then introducing the mixture into the inner cylinder 9 of the first batch reactor R1-1 via inlet Ia. The second portion of the organic ligand stream enters the inner cylinder 9 of the first batch reactor R1-1 via inlet IIb, and the third portion of the organic ligand stream enters the outer cylinder 10 of the first batch reactor R1-1 via inlet IIIc for a first-stage reaction. A gas phase I-1 is obtained from the upper part of the first batch reactor, and a liquid phase stream I-1 is obtained from the lower part. The inner cylinder is equipped with a stirrer and a transmission device 11 connected to the stirrer.

[0078] The liquid phase stream I-1 is introduced into the inner cylinder of the second batch reactor R1-2 via a pump and static mixer 1-4, and then overflows into the outer cylinder of the batch reactor to carry out a secondary reaction with the fourth organic ligand stream to obtain gas phase I-2 and liquid phase stream I-2.

[0079] The liquid stream I-2 obtained from the second batch reactor R1-2 is introduced into the adjacent downstream third batch reactor R1-3 via a pump and static mixer 1-7 to undergo a three-stage reaction with the fifth organic ligand stream to obtain liquid stream I4. Gas phases I-1, I-2, and I-3 are collected to obtain gas phase I3.

[0080] Each batch reactor is equipped with a circulating flow system;

[0081] (2) The organic ligand stream and the liquid stream I from step (1) are introduced into the second reaction unit R2 to carry out a second reaction, resulting in gas phase II and liquid stream II8 as the organic homogeneous molybdenum-containing compound;

[0082] All of the gas phase I3 and all of the gas phase II5 are introduced into the separation unit D1 for separation to obtain gas 6 and liquid phase 7 containing light components.

[0083] 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;

[0084] The dispersed stream contains a dispersant and / or a co-dispersant;

[0085] Preferably, the dispersant is at least one selected from water, alcohol, and ether;

[0086] The dispersing agent is an acidic dispersant and / or an alkaline dispersant;

[0087] 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;

[0088] The alkaline dispersant is selected from at least one of sodium hydroxide, ammonia, and ammonium hydroxide;

[0089] 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.

[0090] As mentioned above, a second aspect of the present invention provides an apparatus for synthesizing a homogeneous organic molybdenum-containing compound, the apparatus comprising a first reaction unit and a second reaction unit that are kept in communication.

[0091] The first reaction unit is provided with at least two batch reactors connected in series; the batch reactor is a sleeve structure containing an inner cylinder and an outer cylinder; the inner cylinder and the outer cylinder are kept in communication so that the material in the inner cylinder can enter the outer cylinder by overflow;

[0092] The second reaction unit is provided with a material inlet, and the second reaction unit is connected to the first reaction unit through a pipeline, so that the material introduced by the material inlet can undergo a second reaction with the material flow from the first reaction unit in the second reaction unit.

[0093] Preferably, the device further includes a separation unit that is in communication with the second reaction unit and is used to separate at least a portion of the material in the second reaction unit.

[0094] Preferably, the separation unit is also connected to the first reaction unit via a pipeline for separating at least a portion of the materials in the first reaction unit.

[0095] 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.

[0096] According to a preferred embodiment, the apparatus further includes: at least one material inlet and at least one gaseous material outlet provided at the upper part of the batch reactor, at least one liquid material outlet provided at the lower part of the batch reactor, and at least one material inlet provided at the middle part of the batch reactor.

[0097] Optionally, the reactor is further provided with a gaseous stream inlet, wherein the gaseous stream is nitrogen or hydrogen.

[0098] According to a preferred embodiment, the device further includes a heating module disposed outside the batch reactor.

[0099] Preferably, in the batch reactor, the sleeve is provided with a stirrer and a transmission device connected to the stirrer.

[0100] As previously stated, a third aspect of the present invention provides the application of the apparatus described in the second aspect in a residue hydrotreating reaction.

[0101] 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.

[0102] Preferably, the conditions for the hydrogenation reaction of the residue oil are at least: pressure of 10MPa-20MPa, reaction temperature of 400℃-470℃, and reaction time of 0.5-8h.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] In the following examples, unless otherwise specified, all chemical reagents used are products of Sinopharm Chemical Reagent Co., Ltd.

[0107] Unless otherwise specified, the following examples use Figure 1 The process flow shown is followed.

[0108] Molybdenum content determination: Inductively coupled plasma atomic emission spectrometry (ICP-AES) was used.

[0109] 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.

[0110] 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%.

[0111] The following setup for the batch reactor is as follows:

[0112] The volume of the outer cylinder of the batch reactor is 2.5 dm³. 3 The inner cylinder has a volume of 7.5m³. 3 The length-to-diameter ratio of the inner cylinder and the outer cylinder is 2:1;

[0113] The upper part of the batch reactor is provided with three material inlets and at least one gaseous material outlet, the lower part of the batch reactor is provided with one liquid material outlet, and the middle part of the batch reactor is provided with one material inlet; the batch reactor is also provided with a gaseous material inlet, wherein the gaseous material is nitrogen.

[0114] The external heating module is installed on the reactor.

[0115] Example 1

[0116] 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 first reaction unit comprises two batch reactors connected in series. Each batch reactor has a sleeve structure containing an inner cylinder and an outer cylinder. The inner cylinder and the outer cylinder are kept in communication so that the material in the inner cylinder can overflow into the outer cylinder. Specifically...

[0117] (1) Introduce the molybdenum-containing stream (ammonium molybdate) and the organic ligand (isononanoic acid) into reaction unit 1 to carry out the first reaction, and obtain gas phase I and liquid phase stream I;

[0118] The process involves mixing the molybdenum-containing stream and the first portion of the organic ligand stream in an SL-type static mixer, then introducing the mixture into the inner cylinder of the first batch reactor through inlet I. The second portion of the organic ligand stream enters the inner cylinder of the first batch reactor through inlet II, and the third portion of the organic ligand stream enters the outer cylinder of the first batch reactor through inlet III, for a first-stage reaction. A gas phase I-1 is obtained from the upper part of the first batch reactor, and a liquid phase stream I-1 is obtained from the lower part. The inner cylinder of the batch reactor is equipped with a stirrer and a transmission device connected to the stirrer.

[0119] The liquid phase stream I-1 is introduced into the inner cylinder of the second batch reactor via a pump and a static mixer, and then overflows into the outer cylinder of the batch reactor to undergo a secondary reaction with the fourth organic ligand stream to obtain liquid phase stream I-2 (i.e., liquid phase stream I) and gas phase I-2.

[0120] Gas phase I-1 and gas phase I-2 are collected to obtain gas phase I;

[0121] (2) The organic ligand stream and the liquid stream I from step (1) are introduced into the second reaction unit to carry out a second reaction, to obtain gas phase II and liquid stream II as the organic homogeneous molybdenum-containing compound;

[0122] All of the gas phase I and all of the gas phase II are introduced into the separation unit for separation to obtain a gas and a liquid phase containing light components.

[0123] In step (1), in the upstream batch reactor, the organic ligand stream introduced from the organic ligand stream inlet enters the inner cylinder and the outer cylinder, and the weight ratio of the organic ligand stream entering the inner cylinder and the outer cylinder is 4:1.

[0124] In the organic ligand stream entering the inner cylinder, the weight ratio of the first organic ligand stream to the second organic ligand stream is 1:1.

[0125] In the second batch reactor, the weight ratio of the liquid stream from the adjacent upstream batch reactor to the organic ligand stream introduced from the organic ligand stream inlet is 1:0.1.

[0126] Each batch reactor is equipped with a liquid phase circulating stream, and the circulation-to-extraction ratio of the liquid phase circulating stream in each batch reactor is 0.5:1.

[0127] The molybdenum-containing stream and the organic ligand stream in the upstream batch reactor are used in a weight ratio of 1:2.2.

[0128] The reaction conditions in each batch reactor in the first reaction were: temperature 230℃, pressure 120kPa, and average residence time of liquid phase material 9h.

[0129] In step (2), the weight ratio of the liquid phase stream I to the organic ligand stream is 1:0.15;

[0130] 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.

[0131] 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;

[0132] The organic homogeneous molybdenum-containing compound obtained in step (2) is named P1.

[0133] Example 2

[0134] This embodiment uses a process similar to that of Embodiment 1. The difference is that in step (1), the weight ratio of the organic ligand stream entering the inner cylinder and the outer cylinder is 3:1, and the average residence time of the liquid phase material in each batch reactor in the first reaction is 12h.

[0135] Among them, the organic homogeneous molybdenum-containing compound obtained in step (2) is designated as P2.

[0136] Example 3

[0137] This embodiment uses a process similar to that of Embodiment 1, except that each batch reactor is equipped with a liquid phase circulating stream, and the circulation-to-extraction ratio of the liquid phase circulating stream in the batch reactor is 0.1:1.

[0138] Among them, the organic homogeneous molybdenum-containing compound obtained in step (2) is designated as P3.

[0139] Comparative Example 1

[0140] This comparative example uses a process similar to that of Example 1. The difference is that the reaction conditions in each of the batch reactors in the first reaction are: temperature 230°C and pressure 120 kPa, while the conditions for the second reaction are: temperature 170°C and pressure 30 kPa.

[0141] The organic homogeneous molybdenum-containing compound obtained in step (2) is designated as DP1.

[0142] Comparative Example 2

[0143] This comparative example uses a process similar to that of Example 1. The difference is that the reaction conditions in each of the batch reactors in the first reaction are: temperature 230°C and pressure 120 kPa, while the conditions for the second reaction are: temperature 255°C and pressure 320 kPa.

[0144] Among them, the organic homogeneous molybdenum-containing compound obtained in step (2) is designated as DP2.

[0145] Comparative Example 3

[0146] This comparative example uses a similar process to Example 1, except that...

[0147] The first reaction is carried out using a single batch reactor without an inner cylinder. Specifically, in step (1), the molybdenum-containing stream and the organic ligand stream are introduced into the outer cylinder of the upstream batch reactor at a weight ratio of 1:2.2 to carry out the first-stage reaction, resulting in gas phase I and liquid phase stream I.

[0148] The organic homogeneous molybdenum-containing compound obtained in step (2) is designated as DP3.

[0149] Test Example 1

[0150] 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.

[0151] This test case applies the products obtained from the aforementioned examples to perform tests, including the following steps:

[0152] S1: In the presence of hydrogen, an organic homogeneous molybdenum-containing compound, 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: pressure of 16 MPa, reaction temperature of 430℃, and reaction time of 3 h;

[0153] 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.

[0154] In each example of application, the amount of the organic homogeneous molybdenum-containing compound used is 1200 μg / g, calculated as metallic molybdenum.

[0155] The content and composition analysis results of the products from the hydrogenation reaction of residual oil are shown in Table 3.

[0156] Table 1

[0157] project P1 P2 P3 DP1 DP2 DP3 Molybdenum (oil-soluble) content wt / % 17.93 17.82 17.17 16.69 15.40 14.84 Molybdenum metal yield / % 99.56 99.32 98.78 97.72 97.20 89.76 Water content / wt% trace 0.05 0.10 3.03 2.60 0.69 Impurity content / wt% 0.023 0.157 0.35 7.2 14.4 16.37 Blockage during synthesis none none none none none have

[0158] 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.

[0159] Table 2

[0160] project residual oil Element / wt% hydrogen 9.47 carbon 87.03 nitrogen 0.52 sulfur 2.97 Four components / wt% Saturated fraction 6.8 Aromatic components 43.2 gelatinous 40.3 Asphalt 9.7 Residual carbon / wt% 20.6 <![CDATA[Density at 20 °C / (kg / m 3 )]]> 1054.0 <![CDATA[wt(Ni) / (μg·g -1 )]]> 57.4 <![CDATA[wt(V) / (μg·g -1 )]]> 117

[0161] Table 3

[0162]

[0163]

[0164] 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.

[0165] 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, The method is implemented in a system containing a first reaction unit and a second reaction unit, wherein the first reaction unit is provided with at least two batch reactors connected in series; the batch reactor is a sleeve structure containing an inner cylinder and an outer cylinder; the inner cylinder and the outer cylinder are kept in communication so that the material in the inner cylinder can overflow into the outer cylinder; the method includes: (1) The molybdenum-containing stream is introduced from the upstream batch reactor and flows through each batch reactor connected in series in sequence, and is drawn out from the downstream batch reactor. Each batch reactor is provided with an organic ligand stream inlet so that the molybdenum-containing stream or the liquid stream from the adjacent upstream batch reactor can contact the organic ligand stream introduced from the organic ligand stream inlet to carry out the first reaction in the first reaction unit, and the liquid stream I is obtained from the outlet of the downstream batch reactor. (2) The organic ligand stream and the liquid stream I from step (1) are introduced into the second reaction unit to carry out a second reaction, resulting in gas phase II and liquid stream II as the organic homogeneous molybdenum-containing compound; 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), in each of the said batch reactors, the organic ligand stream introduced from the organic ligand stream inlet enters the inner and outer cylinders.

3. The method according to claim 1 or 2, wherein, In step (1), in the upstream batch reactor, the organic ligand stream introduced from the organic ligand stream inlet enters the inner and outer cylinders, and the weight ratio of the organic ligand streams entering the inner and outer cylinders is 0.5-8:

1.

4. The method according to claim 1, wherein, In step (1), except for the upstream batch reactor, all organic ligand streams introduced from the organic ligand stream inlet enter the outer cylinder.

5. The method according to claim 1 or 2, wherein, In step (1), in each batch reactor, except for the upstream batch reactor, the weight ratio of the liquid phase stream from the adjacent upstream batch reactor to the organic ligand stream introduced from the organic ligand stream inlet is independently 1:0.05-0.

5.

6. The method according to claim 1 or 2, wherein, In the first reaction unit, at least one of the batch reactors is provided with a liquid phase circulating stream, and the circulation-to-extraction ratio of the liquid phase circulating stream in the batch reactor is 0.1-6:1, 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.

7. The method according to claim 1 or 2, wherein, In step (1), the molybdenum-containing stream and the organic ligand stream in the upstream batch reactor are used in a weight ratio of 1:1-10.

8. The method according to claim 1 or 2, wherein, In step (2), the weight ratio of the liquid phase stream I to the organic ligand stream is 1:0.04-0.

5.

9. The method according to claim 1 or 2, wherein, The method further includes: obtaining gas phase I from the top of the batch reactor, and introducing at least a portion of gas phase I and / or at least a portion of gas phase II into a separation unit for separation to obtain gas and a liquid phase containing light components.

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

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

12. The method according to claim 1 or 2, wherein, 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, molybdate, molybdic acid, and molybdic anhydride.

13. The method according to claim 1 or 2, wherein, In step (1), the molybdenum-containing stream contains at least one molybdenum-containing raw material selected from ammonium dimolybdate, ammonium paramolybdate, ammonium tetramolybdate, molybdenum dioxide, and molybdenum trioxide.

14. The method according to claim 1 or 2, wherein, In step (1), the molybdenum-containing stream contains at least one molybdenum-containing raw material selected from dimolybdate, secondary molybdate, pentamolybdate, octamolybdate, and tetramolybdate.

15. The method according to claim 1 or 2, wherein, In step (1), the molybdenum-containing stream contains at least one molybdenum-containing raw material selected from molybdenum dioxide, molybdenum trioxide, molybdic acid, ammonium dimolybdate, ammonium 12-molybdenum phosphate, ammonium ammonium paramolybdate, molybdenum salts of monobasic acids of C1-C6 and molybdenum salts of dibasic acids of C1-C6.

16. The method according to claim 1 or 2, wherein, In step (1), the molybdenum-containing stream contains at least one molybdenum-containing raw material selected from C1-C6 dicarboxylic acid molybdenum salt, molybdic acid, ammonium secondary molybdate and ammonium tetramolybdate.

17. The method according to claim 1 or 2, wherein, The organic ligand stream is selected from C6-C. 28 Straight-chain oxygen-containing organic acids, C6-C 28 At least one of the branched oxygen-containing organic acids.

18. The method according to claim 1 or 2, wherein, The organic ligand stream is selected from C6-C. 28 Monocarboxylic acids, C6-C 28 It contains at least one of polycarboxylic acids, thiocarboxylic acids, and sulfonic acids.

19. The method according to claim 1 or 2, wherein, The organic ligand stream is selected from C6-C. 28 Dicarboxylic acids and / or petroleum acids.

20. The method according to claim 1 or 2, wherein, The organic ligand stream is 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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