Steady flow organic homogeneous molybdenum-containing compounds, methods of synthesis and use thereof

Abstract

The application relates to the technical field of metal organic compound production, and discloses a steady flow organic homogeneous molybdenum-containing compound and a synthesis method and application thereof. The method comprises the following steps: (1) introducing a raw material flow into a raw material pretreatment unit for pretreatment to obtain a liquid phase flow I; the raw material flow contains a molybdenum-containing flow and optionally contains a dispersant and / or an acidic dispersant; the pretreatment conditions at least meet the following conditions: the temperature is 45 DEG C-120 DEG C, the pressure is 0 KPa-100 KPa, and the average residence time is 25 min to 12 h; (2) respectively introducing an organic ligand flow and the liquid phase flow I into a reactor to perform a contact reaction in the reactor to obtain the organic homogeneous molybdenum-containing compound. The technical scheme of the application can improve the utilization rate of the molybdenum-containing flow, reduce the production cost, and obtain the organic homogeneous molybdenum-containing compound with high dispersity.

Description

Technical Field

[0001] This invention relates to the technical field of organometallic compound production, specifically to a steady-state flow organic homogeneous molybdenum-containing compound, its synthesis method, and its 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. Therefore, the utilization of unconventional oil resources has attracted increasing attention from various countries. In the future, with the continuous advancement of oil extraction technology and the continuous increase in heavy oil production, the efficient conversion and utilization of heavy oil is gradually becoming a research topic for major oil companies.

[0003] Heavy oil, including crude oil with an API gravity of less than 20, atmospheric residue, vacuum residue, and unconventional crude oil obtained from secondary oil recovery, is characterized by high sulfur, nitrogen, metal, and asphaltenes content, requiring processing to reduce its weight before reuse. The weighting process primarily involves decarbonization and hydrotreating. These processes redistribute hydrocarbons to alter the carbon-to-hydrogen ratio in the residue, refining 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. Among hydrotreating processes, slurry-bed hydrocracking has fewer limitations on feedstocks and can process high-precision feedstocks; therefore, this technology is currently receiving close attention in China.

[0004] Unlike conventional supported catalysts, slurry-bed residue hydrotreating catalysts are primarily dispersed catalysts. Early methods primarily used solid catalysts, including granular and powdered forms, with powdered catalysts exhibiting better reaction performance than granular catalysts. Subsequently, water-soluble and oil-soluble catalysts were developed. However, water-soluble catalysts face challenges in dispersion and sulfidation during use; oil-soluble catalysts, being homogeneous, can be uniformly dispersed in residue oil and undergo in-situ sulfidation decomposition, generating micron-sized catalyst particles that readily react with the residue oil. The dispersion performance of the catalyst in residue oil determines its reaction performance; therefore, homogeneous oil-soluble catalysts exhibit significantly higher catalytic activity than their counterparts in solid powder and water-soluble forms. The main types of homogeneous oil-soluble catalysts are group IV-VIII organometallic compounds, with Mo exhibiting higher hydrogenation activity than other transition metals (such as Ni, V, and Co).

[0005] Oil-soluble organic molybdenum commonly used in the lubricating oil field generally has high sulfur, nitrogen, and phosphorus content, making it unsuitable as a catalyst precursor for slurry bed residue oil hydrogenation processes.

[0006] CN110876932A discloses a method for producing a catalyst for slurry-bed residue hydroconversion technology. The method involves reacting raw materials with sorbitol compounds and sulfides at 100℃-350℃, with stirring performed using a mechanical stirrer in the reactor until the reaction is complete. The reactants are then dried in air at 60℃-80℃ for 2-24 hours and cooled to room temperature to obtain the catalyst for slurry-bed residue hydroconversion technology. The dried catalyst is then pulverized in a pulverizing device equipped with a filter to screen the catalyst particles. The screened catalyst is then bagged and transported to a designated area. However, because this slurry-bed catalyst is granular, even with a particle size less than 1mm, high dispersion requirements are still placed on the catalyst after it enters the residue hydroconversion system.

[0007] CN112745353A discloses a method for preparing an oil-soluble molybdate complex. This process involves reacting ammonium molybdate, 2-ethyl-1,3-hexanediol, xylene, and dimethylformamide under reflux for 5-9 hours, followed by cooling, filtration under suction, and then removing the solvent and organic amine catalyst by vacuum distillation at approximately 160°C and approximately 0.25 mm pressure to obtain a concentrated molybdate complex. However, this preparation process is inefficient, with incomplete raw material conversion and a low conversion rate, thus having certain limitations.

[0008] Therefore, existing methods for synthesizing homogeneous organic compounds suffer from problems such as low feed conversion rates and poor product dispersibility in hydrocarbon oil systems. Summary of the Invention

[0009] The purpose of this invention is to overcome the shortcomings of existing methods for synthesizing homogeneous organic compounds, such as low raw material conversion rate and poor product dispersibility in hydrocarbon oil systems.

[0010] To achieve the above objectives, a first aspect of the present invention provides a method for synthesizing a homogeneous organic molybdenum-containing compound. The method includes:

[0011] (1) The raw material stream is introduced into the raw material pretreatment unit for pretreatment to obtain liquid stream I; the raw material stream contains molybdenum-containing stream and optionally contains dispersant and / or acidic co-dispersant; the pretreatment conditions are at least: temperature of 45℃-120℃, pressure of 0KPa-100KPa, and average residence time of 25min to 12h;

[0012] (2) The organic ligand stream and the liquid stream I are introduced into the reactor respectively to carry out a contact reaction in the reactor to obtain the organic homogeneous molybdenum-containing compound; wherein the liquid stream I is introduced into the reactor through a feed distributor provided on the reactor;

[0013] The temperature of the organic ligand stream is 160°C-280°C before contact with the liquid stream I; and the temperature of the contact reaction is 170°C-285°C; and

[0014] The structure of the feed distributor ensures that the average droplet size of the liquid phase stream I entering the reaction unit is 1.5-3 mm.

[0015] A second aspect of the present invention provides an organic homogeneous molybdenum-containing compound obtained by the preparation method described in the first aspect above.

[0016] A third aspect of the present invention provides the application of the aforementioned homogeneous molybdenum-containing organic compound as a catalyst in the hydrogenation reaction of residual oil.

[0017] Compared with the prior art, the technical solution of the present invention has at least the following advantages:

[0018] (1) The organic homogeneous molybdenum-containing compound obtained by the technical solution of the present invention can be highly dispersed in heavy feedstock oil, which is beneficial to the reaction mass transfer of the subsequent hydrogenation process;

[0019] (2) The method provided by the present invention can improve the mass transfer problem in the reaction process, improve the mass transfer efficiency, effectively remove the non-polar components generated in the reaction process, and improve the reaction conversion rate. While overcoming the scale-up effect of complex reaction systems, it also has the characteristics of simple process, flexible operation and low energy consumption of equipment.

[0020] (3) The reaction apparatus described in this invention is not limited to the synthesis of homogeneous organic molybdenum-containing compounds, but can also be used to synthesize other organic metal-containing compounds. Attached Figure Description

[0021] 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.

[0022] Figure 1 This is a schematic diagram of the process flow for synthesizing a homogeneous organic molybdenum-containing compound according to a preferred embodiment of the present invention.

[0023] Figure 2(a) is a top view schematic diagram of a distributor according to a preferred embodiment of the present invention;

[0024] Figure 2(b) is a schematic cross-sectional view of a distributor according to a preferred embodiment of the present invention;

[0025] Figure 2(c) is a schematic diagram of a preferred embodiment of the present invention showing a tongue-shaped plate;

[0026] Figure 3These are photographs showing the dispersibility of the homogeneous organic molybdenum-containing compound P1 prepared in this invention in residual oil.

[0027] Figure 4 These are photographs showing the dispersibility of the homogeneous organic molybdenum-containing compound P2 prepared in this invention in residual oil.

[0028] Figure 5 These are photographs showing the dispersibility of the homogeneous organic molybdenum-containing compound P3 prepared in this invention in residual oil.

[0029] Figure 6 These are photographs showing the dispersibility of the organic homogeneous molybdenum-containing compound P4 prepared in this invention in residual oil.

[0030] Figure 7 These are photographs showing the dispersibility of the homogeneous organic molybdenum-containing compound DP1 prepared in this invention in residual oil.

[0031] Figure 8 This is a photograph showing the dispersion of the organic homogeneous molybdenum-containing compound DP2 prepared in this invention in residual oil.

[0032] Explanation of reference numerals in the attached figures

[0033] PR1: Raw material pretreatment unit; R1: Reaction unit

[0034] D1: Separation Unit 1: Molybdenum-containing stream

[0035] 2: Dispersant 3: Acidic co-dispersant

[0036] 4: Gas phase I 5: Liquid phase I

[0037] 6: Organic ligand stream 7: Gas phase II

[0038] 8: Homogeneous organic compounds containing molybdenum 9: Gases

[0039] 10: Liquid phase containing light components

[0040] a: Material inlet b: Liquid distribution tank

[0041] c: Channel structure d: Annular inlet pipe

[0042] e: Annular liquid distribution pipe; f: Connector

[0043] g: Tongue-shaped plate; h: Feed line

[0044] α: Angle between l4 and the horizontal direction; l4: Central axis of the tongue-shaped plate.

[0045] β: The angle between l3 and the straight line containing the liquid distribution trough

[0046] l3: The line connecting the center of the material inlet and the center of the circle containing the annular liquid inlet pipe. Detailed Implementation

[0047] 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.

[0048] As previously described, a first aspect of the present invention provides a method for synthesizing a steady-state flow organic homogeneous molybdenum-containing compound. The method includes:

[0049] (1) The raw material stream is introduced into the raw material pretreatment unit for pretreatment to obtain liquid stream I; the raw material stream contains molybdenum-containing stream and optionally contains dispersant and / or acidic co-dispersant; the pretreatment conditions are at least: temperature of 45℃-120℃, pressure of 0KPa-100KPa, and average residence time of 25min to 12h;

[0050] (2) The organic ligand stream and the liquid stream I are introduced into the reactor respectively to carry out a contact reaction in the reactor to obtain the organic homogeneous molybdenum-containing compound; wherein the liquid stream I is introduced into the reactor through a feed distributor provided on the reactor;

[0051] The temperature of the organic ligand stream is 160°C-280°C before contact with the liquid stream I; and the temperature of the contact reaction is 170°C-285°C; and

[0052] The structure of the feed distributor ensures that the average droplet size of the liquid phase stream I entering the reaction unit is 1.5-3 mm.

[0053] It should be noted that in this invention, the "pressure" or "reaction pressure" refers to relative pressure.

[0054] Preferably, the temperature of the liquid phase stream I is 45-120°C before contact with the organic ligand stream.

[0055] According to a preferred embodiment, the method of the present invention includes: in step (2), firstly, introducing the organic ligand stream into the reactor, and then introducing the liquid stream I into the reactor through the feed distributor to carry out a contact reaction in the reaction unit.

[0056] More preferably, the method of the present invention includes: in step (2), an organic ligand stream is first introduced into the reactor from the top of the reactor and heated to 160°C-280°C, and then the liquid phase stream I at a temperature of 45-120°C is introduced into the reactor through the feed distributor to carry out a contact reaction in the reaction unit.

[0057] In a preferred embodiment, the feed distributor includes:

[0058] A ring-shaped inlet pipe with a material inlet; and

[0059] At least two sets of liquid distribution grooves are arranged radially along the annular liquid inlet pipe, and each set of liquid distribution grooves is kept in communication with the annular liquid inlet pipe;

[0060] At least one set of annular liquid distribution pipes is disposed below the plane of the liquid distribution tank, the annular liquid distribution pipes and the annular liquid inlet pipes forming a concentric ring; and each set of annular liquid distribution pipes is in communication with at least one set of liquid distribution tanks; each set of annular liquid distribution pipes is provided with a channel structure, so that the material introduced into the feed distributor from the material inlet can be led out of the feed distributor through the channel structure.

[0061] According to a preferred embodiment, in the feed distributor, in the

[0062] On the annular liquid distribution pipe, tongue-shaped plates are provided on more than 30% of the total number of pore structures. The angle between the central axis of the tongue-shaped plate and the horizontal direction is α, and α is 20°-70°.

[0063] In a preferred embodiment, the liquid distribution tanks in each group are symmetrically arranged, that is, the included angle between any two adjacent groups of liquid distribution tanks is the same.

[0064] According to a preferred embodiment, three sets of liquid distribution grooves are provided radially along the annular liquid inlet pipe.

[0065] Preferably, on each group of the annular liquid distribution pipes, the number of the channel structures makes the opening ratio of the annular liquid distribution pipe 30-55%; the opening ratio = the total projected area of ​​the channel structures / the total projected area of ​​the annular liquid distribution pipe * 100%.

[0066] In a preferred embodiment, the inner diameter of the annular liquid inlet pipe is defined as d1; the inner diameter of the liquid distribution trough is defined as d2; and the inner diameter of the annular liquid distribution pipe is defined as d3.

[0067] The proportional relationship between d1, d2, and d3 satisfies: 1:0.5-0.85:0.3-0.6.

[0068] Preferably, the distance between the center point of the annular inlet pipe and the center of the circle containing the annular inlet pipe is defined as l1; the distance between the center point of the annular distribution pipe adjacent to the annular inlet pipe and the center of the circle containing the annular distribution pipe is defined as l2.

[0069] The ratio between l1 and l2 satisfies: 1:1.15-4;

[0070] It should be noted that the center point of the annular inlet pipe is the circle point of any cross-section of the annular inlet pipe, and the center point of the annular distribution pipe is the center of any cross-section of the annular distribution pipe.

[0071] Preferably, the line connecting the center of the material inlet and the center of the annular liquid inlet pipe is defined as l3, and the angle between l3 and the straight line of the liquid distribution trough is β, where β is 30-150°.

[0072] A preferred embodiment of the distributor of the present invention will be described below with reference to Figures 2(a), 2(b), and 2(c). Specifically:

[0073] The feed distributor includes:

[0074] An annular inlet pipe d is provided with a material inlet a, wherein the material inlet a is connected to the feed line h via a connector f; and

[0075] Three sets of liquid distribution troughs b are arranged radially along the annular liquid inlet pipe d, and each set of liquid distribution troughs b is kept in communication with the annular liquid inlet pipe d;

[0076] Three sets of annular liquid distribution pipes e are arranged below the plane where the liquid distribution tank d is located. The annular liquid distribution pipes e and the annular liquid inlet pipe d form a concentric ring. Each set of annular liquid distribution pipes e is connected to each set of liquid distribution tanks b. Each set of annular liquid distribution pipes e is provided with a channel structure c, so that the material introduced into the feed distributor from the material inlet can be led out of the feed distributor through the channel structure c.

[0077] On the annular liquid distribution pipe, tongue-shaped plates g are provided on 100% of the total number of pore structures, with the included angle α being 45° and the included angle β being 60°.

[0078] The liquid distribution tanks in each group are arranged symmetrically.

[0079] Preferably, in step (2), the conditions for the contact reaction are at least: the introduction time of the liquid phase stream I is 1h-16h, the reaction pressure is 0KPa-3MPa, and the reaction time is 0.5h-8h. It should be noted that the reaction time is the time between the end of the introduction of the liquid phase stream I and the end of the contact reaction.

[0080] In a preferred embodiment, in step (2), the weight ratio of the organic ligand stream to the molybdenum-containing stream is 0.5-9:1.

[0081] In a preferred embodiment, in step (1), the weight ratio of the dispersant to the molybdenum-containing stream is 0.01-15:1.

[0082] Preferably, in step (1), the mass ratio of the acidic dispersant to the molybdenum-containing stream is 0.01-8:1.

[0083] In 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.

[0084] 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.

[0085] More preferably, the molybdenum-containing raw material is a C1-C6 dicarboxylic acid molybdenum salt, molybdenum trioxide, molybdic acid, ammonium paramolybdate, or ammonium tetramolybdate.

[0086] Preferably, in step (1), the dispersant is selected from at least one of water and C1-C8 alcohols.

[0087] According to a preferred embodiment, in step (1), the acidic dispersant is selected from at least one of inorganic acids and C1-C6 organic acids.

[0088] Preferably, the acidic dispersant is selected from at least one of phosphoric acid, nitric acid, hydrochloric acid, sulfuric acid, C1-C6 monocarboxylic acids, C1-C6 dicarboxylic acids, and C1-C6 polycarboxylic acids.

[0089] More preferably, the acidic dispersant is selected from at least one of citric acid, oxalic acid, and hydrochloric acid.

[0090] According to a preferred embodiment, in step (2), the organic ligand stream contains components selected from C6-C6. 28 Straight-chain oxygen-containing organic acids, C6-C 28 Organic ligand raw material of at least one of branched oxygen-containing organic acids.

[0091] Preferably, the organic ligand raw material 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.

[0092] More preferably, the organic ligand raw material is selected from at least one of 2-propylheptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, dodecylbenzenesulfonic acid, naphthenic acid, n-nonanoic acid, n-hexanoic acid, isohexanoic acid, and isononanoic acid.

[0093] Preferably, in step (1), gas phase I can also be obtained in the raw material pretreatment unit.

[0094] In a preferred embodiment, in step (2), gas phase II can also be obtained in the reaction unit.

[0095] 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.

[0096] 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:

[0097] (1) The raw material stream is introduced into the raw material pretreatment unit PR1 for pretreatment to obtain liquid stream I; the raw material stream contains molybdenum stream 1, dispersant 2, and acidic co-dispersant 3;

[0098] In particular, gaseous I4 can also be obtained in the raw material pretreatment unit PR1.

[0099] (2) First, the organic ligand stream 6 is introduced into the reactor of the reaction unit R1 from the top of the reaction unit R1, and then the liquid stream I 5 is introduced into the reactor through the feed distributor to carry out a contact reaction in the reaction unit to obtain the organic homogeneous molybdenum-containing compound 8; wherein, gas phase II 7 can also be obtained in the reaction unit R1, and the feed distributor is set in the middle and upper part of the reactor.

[0100] All of the gas phase I 4 and all of the gas phase II 7 are introduced into the separation unit D1 along the flow direction for separation to obtain gas 9 and liquid phase 10 containing light components.

[0101] It should be noted that the raw material pretreatment unit described in this invention includes a pretreatment reactor, which is a continuous reactor. The continuous reactor can be either a continuous tubular reactor or a continuous batch reactor. Preferably, the pretreatment reactor is a continuous batch reactor, which can be composed of 1-3 stages of reactors connected in series, or it can consist of multiple stages of stirring within a single reactor.

[0102] It should be noted that, in this invention, there are no specific requirements for the method of introducing the molybdenum-containing material. It can be exemplarily described as follows: the molybdenum-containing material is introduced into the raw material pretreatment unit through a solid feed port via a transmission device; the transmission device is a vacuum feeder or a screw conveyor, and a raw material metering unit is set downstream of the transmission device along the flow direction of the material; the pipeline of the transmission device is a closed pipeline.

[0103] According to a preferred embodiment, the method further includes: when the acidic dispersant is a solid phase, introducing the acidic dispersant into the raw material pretreatment unit using the same introduction method as the molybdenum-containing stream.

[0104] According to a preferred embodiment, the method further includes: mixing the molybdenum-containing stream and / or the acidic dispersant after passing through the raw material metering unit in a static mixer and then introducing it into the raw material pretreatment unit through a solid feed inlet.

[0105] It should be noted that in the method provided by the present invention, the raw material pretreatment unit and / or reaction unit can be operated independently in a single system, a series connection of two systems, or a parallel connection of two systems, or can be operated in an online switching manner during operation.

[0106] According to a preferred embodiment, the method further includes: applying the liquid phase stream I to a residue oil hydrogenation reaction and / or applying the organic homogeneous molybdenum-containing compound as an additive to a lubricating oil.

[0107] As previously stated, a second aspect of the present invention provides an organic homogeneous molybdenum-containing compound obtained by the preparation method described in the first aspect.

[0108] As previously stated, the third aspect of the present invention provides the application of the aforementioned organic homogeneous molybdenum-containing compound as a catalyst in the hydrogenation reaction of residue oil.

[0109] 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.

[0110] 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.

[0111] The inventors have 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.

[0112] 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.

[0113] In the following examples, unless otherwise specified, all chemical reagents used are products of Sinopharm Chemical Reagent Co., Ltd.

[0114] The feedstock is residual oil, and its properties are shown in Table 1.

[0115] Molybdenum content determination: Inductively coupled plasma atomic emission spectrometry (ICP-AES) was used.

[0116] Gas phase fluctuation amplitude / % = (maximum instantaneous gas phase flow rate - minimum instantaneous gas phase flow rate) / maximum instantaneous gas phase flow rate * 100%;

[0117] The determination of the maximum instantaneous flow rate and the minimum instantaneous flow rate of the gas phase was carried out using a wet gas flow meter.

[0118] The model of the inductively coupled plasma atomic emission spectrometer is SPECTRO ARCOS SOP.

[0119] The microscope images were taken at 1000x magnification using a COIC XSZ-11 microscope from Chongqing Optoelectronics.

[0120] 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%.

[0121] The maximum instantaneous flow rate of the gas phase during the contact reaction was determined for some of the examples below, and the content of metallic molybdenum was determined for some of the products in the examples, and the results are listed in Table 2.

[0122] The product obtained in the following example was mixed with residue oil at a mass ratio of 1:10, and the dispersibility of the product in the residue oil was observed using a microscope.

[0123] Unless otherwise specified, the following examples use Figure 1 The process flow shown is the same as that of the distributors shown in Figures 2(a), 2(b), and 2(c);

[0124] Specifically, the distributor is configured as follows:

[0125] A ring-shaped inlet pipe with a material inlet; and

[0126] Three sets of liquid distribution grooves are arranged radially along the annular liquid inlet pipe, and each set of liquid distribution grooves is kept in communication with the annular liquid inlet pipe;

[0127] Three sets of annular liquid distribution pipes are arranged below the plane of the liquid distribution tank, and the annular liquid distribution pipes form a concentric ring with the annular liquid inlet pipe; and each set of annular liquid distribution pipes is connected to each set of liquid distribution tanks; each set of annular liquid distribution pipes is provided with a channel structure, so that the material introduced into the feed distributor from the material inlet can be led out of the feed distributor through the channel structure.

[0128] On the annular liquid distribution pipe, tongue-shaped plates are provided on 100% of the total number of pore structures, with the included angle α being 45° and the included angle β being 60°.

[0129] The liquid distribution tanks in each group are symmetrically arranged;

[0130] On each group of the annular liquid distribution pipes, the number of the channel structures makes the opening ratio of the annular liquid distribution pipe 35%.

[0131] The proportional relationship between d1, d2, and d3 satisfies: 1:0.65:0.4;

[0132] The ratio between l1 and l2 is 1:2.

[0133] Example 1

[0134] This embodiment illustrates the method for synthesizing steady-state flow organic homogeneous molybdenum-containing compounds provided by the present invention. The specific steps are as follows:

[0135] (1) The raw material stream is introduced into the raw material pretreatment unit for pretreatment to obtain liquid phase stream I and gas phase I; the raw material stream contains molybdenum-containing stream (molybdenum trioxide), dispersant (water) and acidic co-dispersant (citric acid); the pretreatment conditions are: temperature of 70℃, pressure of 30KPa, and average residence time of 10h;

[0136] In step (1), the weight ratio of the dispersant to the molybdenum-containing fluid is 5:1.

[0137] The mass ratio of the acidic dispersant to the molybdenum-containing stream is 1.5:1;

[0138] The pretreatment reactor in the raw material pretreatment unit is a continuous reactor, consisting of two reactors connected in series.

[0139] In this process, the molybdenum-containing material and the acidic dispersant are mixed in a static mixer and then introduced into the raw material pretreatment unit through the solid feed port via a vacuum feeder.

[0140] (2) First, the organic ligand stream (isononanoic acid) is introduced into the reactor of the reaction unit from the top of the reaction unit and heated to 190°C. Then, the liquid phase stream I, heated to 80°C, is introduced into the reactor through the feed distributor and heated to the contact reaction temperature of 210°C to carry out the contact reaction, so as to obtain the organic homogeneous molybdenum-containing compound and gas phase II. The feed distributor is set in the middle and upper part of the reactor.

[0141] The structure of the feed distributor ensures that the average droplet size of the liquid phase stream I entering the reaction unit is 2.1 mm;

[0142] In step (2), the weight ratio of the organic ligand stream to the molybdenum-containing stream is 6:1.

[0143] The liquid phase stream I was introduced over a period of 4 hours, the reaction pressure was 0.5 MPa, and the reaction time was 7 hours.

[0144] (3) All of the gas phase I and all of the gas phase II are introduced into the separation unit along the flow direction for separation to obtain gas and liquid phase containing light components;

[0145] The raw material pretreatment unit and the reaction unit are configured as a dual-system series connection.

[0146] Among them, the organic homogeneous molybdenum-containing compound obtained in step (2) is named P1, as shown in Table 2. The content of metallic molybdenum by element is 9.5 wt%, the gas phase fluctuation amplitude during the reaction is 9.2%, and the reaction process is stable.

[0147] Figure 3 The dispersibility of P1 in the residue oil is shown in the photograph. It can be seen that P1 is uniformly dispersed in the residue oil and there are no obvious two phases.

[0148] Example 2

[0149] This embodiment illustrates the method for synthesizing steady-state flow organic homogeneous molybdenum-containing compounds provided by the present invention. The specific steps are as follows:

[0150] (1) The raw material stream is introduced into the raw material pretreatment unit for pretreatment to obtain liquid stream I and gas stream I; the raw material stream contains molybdenum-containing stream (ammonium molybdate) and dispersant (water); the pretreatment conditions are: temperature is 80℃, pressure is 40KPa, and average residence time is 1h;

[0151] In step (1), the weight ratio of the dispersant to the molybdenum-containing fluid is 1:1.

[0152] The pretreatment reactor in the raw material pretreatment unit is a continuous reactor, consisting of two reactors connected in series.

[0153] In this process, the molybdenum-containing material and the acidic dispersant are mixed in a static mixer and then introduced into the raw material pretreatment unit through the solid feed port via a vacuum feeder.

[0154] (2) First, the organic ligand stream (isononanoic acid) is introduced into the reactor of the reaction unit from the top of the reaction unit and heated to 225°C. Then, the liquid phase stream I at 80°C is introduced into the reactor through the feed distributor and heated to the contact reaction temperature of 225°C to carry out the contact reaction, so as to obtain the organic homogeneous molybdenum-containing compound and gas phase II. The feed distributor is set in the middle and upper part of the reactor.

[0155] The structure of the feed distributor ensures that the average droplet size of the liquid phase stream I entering the reaction unit is 1.65 mm.

[0156] In step (2), the weight ratio of the organic ligand stream to the molybdenum-containing stream is 3:1.

[0157] The liquid phase stream I was introduced over a period of 12 hours, the reaction pressure was 0.03 MPa, and the reaction time was 3 hours.

[0158] (3) All of the gas phase I and all of the gas phase II are introduced into the separation unit along the flow direction for separation to obtain gas and liquid phase containing light components;

[0159] The raw material pretreatment unit and the reaction unit are configured as a dual-system series connection.

[0160] Among them, the organic homogeneous molybdenum-containing compound obtained in step (2) is named P2, as shown in Table 2. The content of metallic molybdenum is 20.90 wt% based on elemental composition, the gas phase fluctuation amplitude is 6.8% during the reaction, and the reaction process is stable.

[0161] Figure 4 The photographs showing the dispersion of P2 in the residue oil demonstrate that P2 is uniformly dispersed in the residue oil, with no obvious two phases.

[0162] Example 3

[0163] This embodiment uses the same method as in embodiment 1, except that in step (2), the introduction time of liquid phase stream I is 8 hours.

[0164] Among them, the organic homogeneous molybdenum-containing compound obtained in step (2) is named P3, as shown in Table 2. The content of metallic molybdenum is 9.8 wt% based on elemental composition, the gas phase fluctuation amplitude is 5.7% during the reaction, and the reaction process is stable.

[0165] Figure 5 The dispersibility of P3 in the residue oil is shown in the photograph. It can be seen that P3 is uniformly dispersed in the residue oil and there are no obvious two phases.

[0166] Example 4

[0167] This embodiment uses the same method as in embodiment 2, except that the introduction time of liquid phase stream I is 8 hours.

[0168] Among them, the organic homogeneous molybdenum-containing compound obtained in step (2) is named P4, as shown in Table 2. The content of metallic molybdenum is 20.94 wt% based on elemental composition, the gas phase fluctuation amplitude is 7.2% during the reaction, and the reaction process is stable.

[0169] Figure 6 The dispersibility of P4 in the residue oil is shown in the photograph. It can be seen that P4 is uniformly dispersed in the residue oil and there are no obvious two phases.

[0170] Comparative Example 1

[0171] This comparative example was carried out using the same method as in Example 1, except that the average dwell time of the pretreatment in step (1) was 15 min.

[0172] Among them, the organic homogeneous molybdenum-containing compound obtained in step (2) is named DP1, as shown in Table 2. The content of metallic molybdenum is 5.34 wt% based on elemental composition. The gas phase fluctuation amplitude during the reaction is 39.6%, and the reaction process is prone to fluctuation.

[0173] Figure 7 The dispersibility of DP1 in residue oil is shown in the photograph. It can be seen that the synthetic product is not uniformly dispersed in residue oil.

[0174] Comparative Example 2

[0175] This comparative example was conducted using the same method as in Example 1, except that the liquid phase stream I was not introduced using the distributor. Specifically, step (2) was performed as follows:

[0176] First, the organic ligand stream (isononanoic acid) is introduced into the reactor of the reaction unit from the top of the reaction unit. Then, the liquid stream I is introduced directly into the reactor without passing through the feed distributor, so as to carry out a contact reaction in the reaction unit to obtain the organic homogeneous molybdenum-containing compound and gas phase II.

[0177] Among them, the organic homogeneous molybdenum-containing compound obtained in step (2) is named DP2, as shown in Table 2. The content of metallic molybdenum is 8.16 wt% based on elemental composition. The gas phase fluctuation amplitude during the reaction is 47.7%, and the contact reaction process is prone to fluctuation.

[0178] Figure 8 The dispersibility of DP2 in residue oil is shown in the photograph. It can be seen that the synthetic product is not uniformly dispersed in residue oil.

[0179] Test Example 1

[0180] 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.

[0181] This test case uses product P1 obtained from the aforementioned examples for testing, including the following steps:

[0182] S1: In the presence of hydrogen, organic homogeneous molybdenum-containing compounds and preheated feed oil are added to a high-pressure autoclave hydrogenation reactor at a mass ratio of 0.012:1 to carry out a residue hydrogenation reaction, obtaining hydrogenation reaction products (including gaseous products and liquid products); the conditions for the residue hydrogenation reaction are: reaction pressure of 16 MPa, reaction temperature of 425℃, and reaction time of 3 h;

[0183] 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.

[0184] In each example of application, the amount of the organic homogeneous molybdenum-containing compound used is 1200 μg / g, calculated as metallic molybdenum.

[0185] The content and composition analysis results of the products from the hydrogenation reaction of residual oil are shown in Table 3.

[0186] Test Example 2

[0187] This test case was conducted using the same method as Test Case 1. The difference was that DP2, the product obtained in the previous example, was used instead of P1 for the residue hydrogenation reaction. The product yield and distribution are shown in Table 3.

[0188] Test Example 3

[0189] This test case was conducted using the same method as Test Case 1. The difference was that no organic homogeneous molybdenum-containing compound P1 was added during the hydrogenation reaction of the residue oil. The product yield and distribution are shown in Table 3.

[0190] Table 1

[0191]

[0192] Note: Yield of liquid fraction at 549℃ / wt% = weight of liquid fraction at 549℃ / initial weight of residue before fractionation * 100%.

[0193] Table 2

[0194] Example number Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 The molybdenum content in the product (wt%) 9.5 20.9 9.8 20.94 5.34 8.16 Gas phase fluctuation amplitude / % 9.2 6.8 5.7 7.2 39.6 47.7

[0195] Table 3

[0196] project Test Example 1 Test Example 2 Test Example 3 Gas, wt% 9.36 8.32 6.84 Gasoline (<180℃), wt% 13.89 11.15 7.86 Diesel fuel (180–350℃), wt% 29.57 22.98 13.78 Wax oil (350~524℃), wt% 34.44 28.38 16.57 Slag reduction (>524℃), wt% 12.22 24.79 46.59 Toluene insoluble matter, wt% 0.52 4.38 8.36 Light oil yield, wt% 43.46 34.13 21.64

[0197] The results above show that the method provided by this invention not only has a high raw material conversion rate and low production cost, but also produces organic molybdenum-containing compounds with high dispersibility. When applied to the hydrogenation process of inferior oil, it has the advantages of improving the yield of light oil, the conversion rate of inferior oil, and reducing coking in the process.

[0198] 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 includes: (1) The raw material stream is introduced into the raw material pretreatment unit for pretreatment to obtain liquid phase stream I; the raw material stream contains a molybdenum-containing stream and contains a dispersant and an acidic co-dispersant; the pretreatment conditions are at least: temperature of 45℃-120℃, pressure of 0KPa-100KPa, and average residence time of 25min to 12h; the weight ratio of the dispersant to the molybdenum-containing stream is 0.01-15:1; the mass ratio of the acidic co-dispersant to the molybdenum-containing stream is 0.01-8:1; the molybdenum-containing stream contains at least one molybdenum-containing raw material selected from molybdate, molybdic acid, molybdenum dioxide, and molybdenum trioxide; the dispersant is selected from at least one of water and C1-C8 alcohols; the acidic co-dispersant is selected from at least one of inorganic acids and C1-C6 organic acids; (2) The organic ligand stream and the liquid stream I are introduced into the reactor respectively to carry out a contact reaction in the reactor to obtain the organic homogeneous molybdenum-containing compound; wherein, the liquid stream I is introduced into the reactor through a feed distributor provided on the reactor; the contact reaction conditions are at least satisfied as follows: the introduction time of the liquid stream I is 1h-16h, the reaction pressure is 0KPa-3MPa, and the reaction time is 0.5h-8h; the weight ratio of the organic ligand stream to the molybdenum-containing stream is 0.5-9:1; the organic ligand stream contains compounds selected from C6-C6. 28 Straight-chain oxygen-containing organic acids or C6-C 28 Organic ligand raw material of at least one of branched oxygen-containing organic acids; The temperature of the organic ligand stream is 160°C-280°C before contact with the liquid stream I; and the temperature of the contact reaction is 170°C-285°C; and The structure of the feed distributor ensures that the average droplet size of the liquid phase stream I entering the reactor is 1.5-3 mm; The feed distributor includes: A ring-shaped inlet pipe with a material inlet; and At least two sets of liquid distribution grooves are arranged radially along the annular liquid inlet pipe, and each set of liquid distribution grooves is kept in communication with the annular liquid inlet pipe; At least one set of annular liquid distribution pipes is disposed below the plane of the liquid distribution tank, the annular liquid distribution pipes and the annular liquid inlet pipes forming a concentric ring; and each set of annular liquid distribution pipes is in communication with at least one set of liquid distribution tanks; each set of annular liquid distribution pipes is provided with a channel structure, so that the material introduced into the feed distributor from the material inlet can be led out of the feed distributor through the channel structure.

2. The method according to claim 1, wherein, In the feed distributor, in the On the annular liquid distribution pipe, tongue-shaped plates are provided on more than 30% of the total number of pore structures. The angle between the central axis of the tongue-shaped plate and the horizontal direction is α, and α is 20°-70°.

3. The method according to claim 1 or 2, wherein, The liquid distribution tanks in each group are arranged symmetrically.

4. The method according to claim 1 or 2, wherein, Three sets of liquid distribution tanks are arranged radially along the annular liquid inlet pipe.

5. The method according to claim 1 or 2, wherein, On each group of the annular liquid distribution pipes, the number of the channel structures makes the opening ratio of the annular liquid distribution pipe 30-55%; the opening ratio = the total projected area of ​​the channel structures / the total projected area of ​​the annular liquid distribution pipe * 100%.

6. The method according to claim 1 or 2, wherein, The inner diameter of the annular liquid inlet pipe is defined as d1; the inner diameter of the liquid distribution trough is defined as d2; and the inner diameter of the annular liquid distribution pipe is defined as d3. The proportional relationship between d1, d2, and d3 satisfies: 1:0.5-0.85:0.3-0.

6.

7. The method according to claim 1 or 2, wherein, The distance between the center point of the annular inlet pipe and the center of the circle containing the annular inlet pipe is defined as l1; the distance between the center point of the annular distribution pipe adjacent to the annular inlet pipe and the center of the circle containing the annular distribution pipe is defined as l2. The ratio between l1 and l2 satisfies: 1:1.15-4.

8. The method according to claim 1, wherein, The molybdate is selected from at least one of dimolybdate, secondary molybdate, pentamolybdate, octamolybdate, tetramolybdate, and ammonium 12-molybdate phosphate.

9. The method according to claim 8, wherein, The dimolybdate is ammonium dimolybdate; the secondary molybdate is ammonium secondary molybdate; and the tetramolybdate is ammonium tetramolybdate.

10. The method according to claim 9, 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, and ammonium paramolybdate.

11. The method according to claim 9, wherein, The molybdenum-containing raw material is molybdenum trioxide, molybdic acid, ammonium paramolybdate, or ammonium tetramolybdate.

12. The method according to claim 1, wherein, The acidic dispersant is selected from at least one of phosphoric acid, nitric acid, hydrochloric acid, sulfuric acid, C1-C6 monocarboxylic acids, and C1-C6 polycarboxylic acids.

13. The method according to claim 12, wherein, The acidic dispersant is selected from at least one of citric acid, oxalic acid, and hydrochloric acid.

14. The method according to claim 1, wherein, The organic ligand raw material is selected from C6-C. 28 Monocarboxylic acids, C6-C 28 At least one of the polycarboxylic acids.

15. The method according to claim 14, wherein, The organic ligand raw material is selected from at least one of 2-propylheptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, hexanoic acid, isohexanoic acid, and isononanoic acid.

16. The method according to claim 1 or 2, wherein, The method includes: in step (2), first introducing the organic ligand stream into the reactor, and then introducing the liquid stream I into the reactor through the feed distributor to carry out the contact reaction in the reactor.

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