Hydrogenation reaction method

Abstract

The invention discloses a hydrogenation reaction method which comprises the following steps: step 1, mixing raw oil with a catalyst, and then conveying the mixture into a first supergravity microbubble generator; 2, hydrogen is conveyed into the first supergravity microbubble generator and a first reactor, the hydrogen conveyed into the first supergravity microbubble generator is broken into micron-sized bubbles, and the hydrogen conveyed into the first reactor is dispersed into millimeter-sized bubbles through a gas distributor; and step 3, conveying the raw oil, the catalyst and the hydrogen in the first supergravity microbubble generator to the first reactor for hydrogenation reaction. According to the invention, the supergravity microbubble generator is combined with the gas distributor, on one hand, gas-liquid inter-phase turbulence is enhanced through large bubbles, so that a catalyst is more uniformly distributed along the axial direction of the reactor, and on the other hand, the gas-liquid mass transfer process is enhanced through long retention time and large specific surface area of micron-sized bubbles, so that the use amount of hydrogen can be reduced.

Description

Technical Field

[0001] The invention belongs to the field of hydrogenation, and in particular relates to a hydrogenation reaction method. Background Art

[0002] In recent years, the difficulty of crude oil extraction has increased year by year worldwide, conventional crude oil resources have been significantly reduced, and the trend of heavy and inferior crude oil extracted has increased. The importance of heavy oil hydrogenation conversion has become increasingly prominent. At present, the heavy oil hydrogenation processes that are widely used in industry include fixed bed hydrogenation process, ebullating bed hydrogenation process, and slurry bed hydrogenation process. Due to its strong adaptability to raw materials and high conversion rate, slurry bed hydrogenation technology has obvious advantages in processing inferior heavy oil. Therefore, in recent years, slurry bed hydrogenation technology has received widespread attention at home and abroad. However, the heavy oil slurry bed hydrogenation process is severely restricted by gas-liquid mass transfer, resulting in a large hydrogen circulation volume and a high hydrogen-to-oil ratio; in addition, for the process of enhancing mass transfer by reducing the bubble size, the subsequent microbubbles are difficult to separate and still bring high energy consumption. Therefore, the development of a process that can achieve enhanced mass transfer in the heavy oil slurry bed hydrogenation process and facilitate gas-liquid separation is of great practical significance for achieving energy saving and consumption reduction in the heavy oil hydrogenation reaction process and improving the intrinsic safety of the process.

[0003] The Chinese patent application with application number 201710853235.9 discloses a multi-stage supergravity reactor heavy oil hydrogenation method, comprising the following steps: starting the supergravity reactor motor to drive the rotating disks of each stage to rotate, and at the same time opening the ultrasonic probe in the feed chamber; inputting hydrogen and heavy oil into the feed chamber for efficient gas-liquid two-phase mixing to form a gas-liquid mixture; spraying the gas-liquid mixture from the lower end of the feed chamber to the rotating disk of the first-stage rotor under the action of gas pressure and gravity, using the centrifugal force on the rotating disk to throw the gas-liquid mixture to the catalyst flowing through the rotor, completing the gas-liquid-solid three-phase hydrogenation reaction process, and the reaction product is transported from the liquid outlet at the bottom of the first-stage rotor to the rotating disk of the second-stage rotor to enter the second-stage rotor for reaction, and so on, until entering the N-stage rotor reaction and then discharged from the reactor from the liquid outlet at the bottom of the shell. The method of the invention can achieve deasphaltenes ≥ 50%, demetallization ≥ 80%, desulfurization rate ≥ 88%, and denitrification rate ≥ 45%. However, since this method uses an ultra-gravity reactor instead of the original reactor, the entire process needs to be designed and modified according to the ultra-gravity reactor. At the same time, the safety of the entire process must be re-evaluated, which makes the equipment investment high and the modification difficult.

[0004] The Chinese patent application with application number 201710852317.1 discloses a high-temperature and high-pressure ultra-gravity hydrogenation reactor and its application, which includes a motor, a main shaft, a rotor and a shell, wherein the main shaft at the output end of the motor passes through the bottom of the shell and extends into the shell, and the rotor is fixed on the upper part of the main shaft; the ultra-gravity hydrogenation reactor also includes a rotating disk and a feed chamber; the rotating disk is fixedly connected to the top of the main shaft, the feed chamber is arranged at the upper part of the shell, and its lower end extends into the shell and is arranged directly above the rotating disk, and a feed chamber outlet is arranged on the lower end surface of the feed chamber; an ultrasonic probe is arranged in the feed chamber; the reactor of the invention allows bubbles to exist in the liquid phase for a long time, the gas-liquid mass transfer efficiency is high, and the wetting fraction of the catalyst during the reaction can be purposefully adjusted; the partial pressure of hydrogen in the reactor can be appropriately reduced to improve the safety of the device; there is no need to connect in series with other large gas-liquid premixing equipment, reducing the equipment side. However, the reactor uses a single-layer module and is not suitable for processing gas-liquid-solid three-phase raw materials.

[0005] Therefore, further research on the hydrogenation reaction method using ultra-gravity is needed in this field. Summary of the invention

[0006] The main purpose of the present invention is to provide a hydrogenation reaction method using supergravity technology, which method has little change to existing hydrogenation equipment, low equipment investment, and can reduce the amount of hydrogen used.

[0007] In order to achieve the above object, the present invention provides a hydrogenation reaction method, comprising the following steps:

[0008] Step 1, mixing the crude oil with the catalyst, and then conveying them to the first supergravity microbubble generator;

[0009] Step 2, transporting hydrogen to the first supergravity microbubble generator and the first reactor respectively, the hydrogen transported to the first supergravity microbubble generator is broken into micron-sized bubbles, and the hydrogen transported to the first reactor is dispersed into millimeter-sized bubbles through a gas distributor;

[0010] Step 3: The crude oil, catalyst and hydrogen in the first supergravity microbubble generator are transported to the first reactor for hydrogenation reaction.

[0011] The hydrogenation reaction method of the present invention further comprises:

[0012] Step 4, transporting the hydrogen and the reaction mixture in the first reactor to a second supergravity microbubble generator, wherein the hydrogen transported to the second supergravity microbubble generator is broken into millimeter-sized bubbles;

[0013] Step 5: The mixture in the second supergravity microbubble generator is transported to the second reactor for hydrogenation reaction.

[0014] The hydrogenation reaction method of the present invention, wherein, in step 1, the feedstock oil is mixed with the catalyst after being heated, and the heating temperature is 100-600°C.

[0015] The hydrogenation reaction method described in the present invention, wherein the number of the gas distributors in the first reactor is at least one, distributed along the radial direction of the first reactor, the gas distributor in the first reactor is a cross structure, a cross structure, a well structure, a concentric circular ring structure or a concentric square ring structure, and the gas distributor is provided with an opening, and the size of the opening is 1-30 mm.

[0016] The hydrogenation reaction method of the present invention, wherein the rotation speed of the first supergravity microbubble generator is greater than 0 and less than or equal to 3000r / min, the rotation speed of the second supergravity microbubble generator is greater than 0 and less than or equal to 3000r / min, and the rotation speed of the first supergravity microbubble generator is higher than the rotation speed of the second supergravity microbubble generator.

[0017] In the hydrogenation reaction method of the present invention, the first reactor is a slurry bed reactor, the reaction temperature of the hydrogenation reaction in the first reactor is 100-600° C., and the reaction pressure is 1-30 MPa.

[0018] In the hydrogenation reaction method of the present invention, the second reactor is a slurry bed reactor, the reaction temperature of the hydrogenation reaction in the second reactor is 100-600° C., and the reaction pressure is 1-30 MPa.

[0019] In the hydrogenation reaction method of the present invention, a gas-liquid separation device is provided on the top of the first reactor and the second reactor, and part of the unreacted gas in the first reactor and the second reactor is discharged from the first reactor and the second reactor through the gas-liquid separation device.

[0020] In the hydrogenation reaction method of the present invention, the feedstock oil is a mixture of one or more of atmospheric residue oil, vacuum residue oil, thick crude oil, oil sand asphalt, catalytic cracking slurry, ethylene cracking tar and coal tar; and the catalyst is a liquid catalyst, an oil-soluble catalyst or a solid powder catalyst.

[0021] In the hydrogenation reaction method of the present invention, the hydrogen is transported to the first supergravity microbubble generator, the first reactor, and the second supergravity microbubble generator after being pressurized, and the pressurization pressure is 1-30 MPa.

[0022] Beneficial effects of the present invention:

[0023] The present invention combines a supergravity microbubble generator with a gas distributor, so that hydrogen forms micron-sized bubbles in the supergravity microbubble generator and millimeter-sized bubbles in the first reactor, so that a bubble flow of mixed sizes can be formed in the first reactor. On the one hand, the turbulence between the gas and liquid phases is strengthened by the large bubbles, so that the catalyst is more evenly distributed along the axial direction of the reactor. On the other hand, the long residence time and large specific surface area of ​​the micron-sized bubbles strengthen the gas-liquid mass transfer process, which can reduce the amount of hydrogen. In addition, the present invention can achieve flexible regulation of the size of microbubbles through the supergravity rotation speed without changing the operating conditions and the device structure, and jointly strengthen the heavy oil slurry bed hydrogenation reaction process in the first reactor, thereby reducing hydrogen circulation and saving energy consumption. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a process flow chart of hydrogenation reaction in one embodiment of the present invention;

[0025] Figure 2 Schematic diagram of a cross-structured gas distributor in one embodiment of the present invention.

[0026] Figure 3 This is a process flow chart of the hydrogenation reaction of Comparative Examples 1 and 2 of the present invention.

[0027] Wherein, the reference numerals are:

[0028] 1 Hydrogen compressor

[0029] 2 Heating device

[0030] 3. The first gas-liquid separation device

[0031] 4. The first liquid-solid separation device

[0032] 5 Gas distributor

[0033] 6. First Reactor

[0034] 7The first supergravity microbubble generator

[0035] 8 Second gas-liquid separation device

[0036] 9 Second liquid-solid separation device

[0037] 10 Second Reactor

[0038] 11The Second Supergravity Microbubble Generator

[0039] 12 Gas-liquid separator DETAILED DESCRIPTION

[0040] The technical scheme of the present invention is described in detail below. The following implementation modes are implemented on the premise of the technical scheme of the present invention, and a detailed implementation process is given. However, the protection scope of the present invention is not limited to the following implementation modes. The structures or experimental methods of specific conditions are not specified in the following implementation modes, and generally conventional conditions are followed.

[0041] The present invention provides a hydrogenation reaction method, which adopts supergravity technology and is used for hydrogenation of crude oil, especially for hydrogenation of heavy oil. Specifically, it can be used for hydrogenation of a mixture of one or more of atmospheric residue oil, vacuum residue oil, viscous crude oil, oil sand asphalt, catalytic cracking slurry, ethylene cracking tar and coal tar.

[0042] The hydrogenation reaction method of the present invention comprises the following steps:

[0043] Step 1, mixing the crude oil with the catalyst, and then conveying them to the first supergravity microbubble generator;

[0044] Step 2, transporting hydrogen to the first supergravity microbubble generator and the first reactor respectively, the hydrogen transported to the first supergravity microbubble generator is broken into micron-sized bubbles, and the hydrogen transported to the first reactor is dispersed into millimeter-sized bubbles through a gas distributor;

[0045] Step 3: The crude oil, catalyst and hydrogen in the first supergravity microbubble generator are transported to the first reactor for hydrogenation reaction.

[0046] The present invention combines a supergravity microbubble generator with a gas distributor, so that hydrogen forms micron-sized bubbles in the supergravity microbubble generator and millimeter-sized bubbles in the first reactor, so that a hydrogen bubble flow of mixed sizes can be formed in the first reactor. On the one hand, the turbulence between the gas and liquid phases is strengthened by the large bubbles, so that the catalyst is more evenly distributed along the axial direction of the reactor. On the other hand, the long residence time and large specific surface area of ​​the micron-sized bubbles strengthen the gas-liquid mass transfer process, which can reduce the amount of hydrogen. In addition, the present invention can achieve flexible regulation of the size of microbubbles through the supergravity rotation speed without changing the operating conditions and the device structure, and jointly strengthen the heavy oil slurry bed hydrogenation reaction process in the first reactor, thereby reducing hydrogen circulation and saving energy consumption.

[0047] In one embodiment, the hydrogenation reaction method of the present invention further comprises:

[0048] Step 4, transporting the hydrogen and the reaction mixture in the first reactor to a second supergravity microbubble generator, wherein the hydrogen transported to the second supergravity microbubble generator is broken into millimeter-sized bubbles;

[0049] Step 5: The mixture in the second supergravity microbubble generator is transported to the second reactor for hydrogenation reaction.

[0050] The present invention provides a second reactor and a second supergravity microbubble generator, which can further promote the depth of the hydrogenation reaction of the crude oil and reduce the number of microbubbles in the liquid phase on the one hand, and on the other hand, by extending the residence time and the carrying effect of large bubbles, the microbubbles retained in the liquid are aggregated and formed into millimeter bubbles to separate from the liquid phase system, which is beneficial to the subsequent gas-liquid separator for the gas-liquid separation process of the microbubble system, reduces the energy consumption of the subsequent gas-liquid separator and improves the safety of the hydrogenation process.

[0051] The present invention does not particularly limit the catalyst, which may be a liquid catalyst, an oil-soluble catalyst, or a solid powder catalyst. Preferably, the catalyst of the present invention is an oil-soluble catalyst, such as a conventional oil-soluble hydrogenation catalyst in the art.

[0052] In one embodiment, the hydrogenation reaction process schematic diagram of the present invention is as follows Figure 1 As shown, the raw oil is mixed with the catalyst after heating. For example, the raw oil is heated in a heating device 2, and the heating device 2 is, for example, a heating furnace. The heating temperature is, for example, 100-600° C., and the heating temperature only needs to meet the subsequent reaction temperature requirements. The present invention does not specifically limit the mixing ratio of the raw oil and the catalyst, and can be adjusted as needed. The raw oil and the catalyst are mixed to form a homogeneous or quasi-homogeneous mixture and then transported to the first supergravity microbubble generator 7.

[0053] Hydrogen is transported to the first supergravity microbubble generator 7 and the first reactor 6 respectively, and the hydrogen transported to the first supergravity microbubble generator 7 is broken into micron-sized bubbles, and the hydrogen transported to the first reactor 6 is dispersed into millimeter-sized bubbles through the gas distributor 5. The micron-sized bubbles in the first supergravity microbubble generator 7 are dispersed in the liquid phase (stock oil and catalyst), and the liquid phase exists in the form of a continuous phase. The mixed materials (stock oil, catalyst, hydrogen) are continuously discharged from the first supergravity microbubble generator and delivered to the first reactor. Wherein, in the present invention, "micron-sized" is generally 10-1000 microns, preferably 10-900 microns, and "millimeter-sized" is generally 2-50 mm.

[0054] The present invention does not particularly limit the structure of the first supergravity microbubble generator 7, and conventional supergravity microbubble generators in the art can be used. In the first supergravity microbubble generator 7 of the present invention, the feedstock oil, catalyst and hydrogen are greatly enhanced by the multiphase fluid transfer process and the microscopic mixing process under supergravity conditions, so that the hydrogen is broken into micron-sized bubbles. The present invention can achieve the purpose of regulating the size of hydrogen bubbles by adjusting the speed of the first supergravity microbubble generator 7. In one embodiment, the rotation speed of the first supergravity microbubble generator 7 of the present invention is greater than 0 and less than or equal to 3000r / min, and preferably, the rotation speed of the first supergravity microbubble generator 7 is 800-2400r / min.

[0055] In one embodiment, the first reactor 6 of the present invention is a slurry bed reactor, and a gas distributor 5 is provided in the first reactor 6. The number of gas distributors 5 is at least one, preferably 1-20, for example, 2, 3, 4, 5, 6, 7, etc. In another embodiment, the gas distributors 5 of the present invention are distributed along the radial direction of the first reactor 6, and can be uniformly distributed along the radial direction, or can be unevenly distributed, which is not particularly limited in the present invention. Preferably, the gas distributors 5 are uniformly distributed along the radial direction of the first reactor 6.

[0056] The present invention does not specifically limit the structure of the gas distributor 5 in the first reactor 6, and can be, for example, a cross structure, a crisscross structure, a well structure, a concentric circular ring structure, or a concentric square ring structure. Figure 2 As shown, it is a cross structure. In another embodiment, the gas distributor 5 is provided with an opening so that the gas entering the gas distributor 5 flows out from the opening into the first reactor 6, and the size of the opening is, for example, 1-30 mm. Among them, the opening sizes of the gas distributors 5 arranged from top to bottom along the radial direction of the first reactor 6 can be the same, increasing or decreasing. Preferably, the opening sizes of the gas distributors 5 arranged from top to bottom along the radial direction of the first reactor 6 increase.

[0057] In one embodiment, the hydrogen of the present invention is pressurized and transported to the first supergravity microbubble generator 7 and the first reactor 6, respectively. The pressurization pressure is, for example, 1-30 MPa, and the pressurization pressure only needs to meet the pressure requirements of the subsequent reactions. Specifically, Figure 1 As shown, the hydrogen of the present invention is pressurized by the hydrogen compressor 1 and then transported to the first supergravity microbubble generator 7 and the first reactor 6. The present invention does not particularly limit the ratio of hydrogen transported to the first supergravity microbubble generator 7 and the first reactor 6, and can be adjusted as needed, for example, 1:1.

[0058] The feedstock oil, catalyst and hydrogen in the first supergravity microbubble generator 7 are transported to the first reactor 6, mixed with the hydrogen entering through the gas distributor 5, and subjected to a hydrogenation reaction to complete the hydrogenation process of the feedstock oil. In one embodiment, the reaction temperature of the hydrogenation reaction in the first reactor is 100-600°C, preferably 300-500°C, and the reaction pressure is 1-30MPa, preferably 5-22MPa.

[0059] In one embodiment, the first reactor 6 of the present invention is further provided with a first gas-liquid separation device 3 and a first liquid-solid separation device 4. The first gas-liquid separation device 3 is, for example, provided at the top of the first reactor 6, and the first liquid-solid separation device 4 is, for example, provided at the upper middle part of the first reactor 6 near the side wall. The first gas-liquid separation device 3 can be filled with wire mesh fillers, porous foam fillers, spherical fillers, corrugated plate fillers, and the filler surface can be a partially hydrophilic or partially hydrophobic material. Preferably, the gas-liquid separation device is filled with a hydrophobic wire mesh filler.

[0060] The reaction mixture in the first reactor 6 flows upward in the reactor, passes through the first gas-liquid separation device 3, and the reaction mixture is separated into gas and liquid, and part of the unreacted gas enters the tail gas treatment section through the first gas-liquid separation device 3. The liquid-solid mixture passes through the first liquid-solid separation device 4, and the liquid enters the second supergravity microbubble generator 11.

[0061] A certain amount of hydrogen is delivered to the second supergravity microbubble generator 11, mixed with the reaction mixture entering the second supergravity microbubble generator 11, and the hydrogen is broken into millimeter-level bubbles by greatly strengthening the multiphase fluid transfer process and the microscopic mixing process under supergravity conditions. The present invention can achieve the purpose of regulating the size of hydrogen bubbles by adjusting the rotation speed of the second supergravity microbubble generator 11. In one embodiment, the rotation speed of the second supergravity microbubble generator 11 of the present invention is greater than 0 and less than or equal to 3000r / min, and preferably, the rotation speed of the second supergravity microbubble generator 11 is greater than 0 and less than or equal to 1000r / min. In one embodiment, the rotation speed of the first supergravity microbubble generator 7 is higher than the rotation speed of the second supergravity microbubble generator 11.

[0062] In one embodiment, the hydrogen of the present invention is transported to the second supergravity microbubble generator 11 after being pressurized, and the pressurized pressure is, for example, 1-30 MPa. Figure 1 As shown, the hydrogen of the present invention is pressurized by the hydrogen compressor 1 and then transported to the second supergravity micro bubble generator 11.

[0063] The mixture in the second supergravity microbubble generator 11 is transported to the second reactor 10 for hydrogenation reaction to complete the hydrogenation process of the crude oil. In one embodiment, the reaction temperature of the hydrogenation reaction in the second reactor is 100-600°C, preferably 300-500°C, and the reaction pressure is 1-30MPa, preferably 5-22MPa.

[0064] In one embodiment, the second reactor 10 of the present invention is further provided with a second gas-liquid separation device 8 and a second liquid-solid separation device 9. The second gas-liquid separation device 8 is, for example, provided at the top of the second reactor 10, and the second liquid-solid separation device 9 is, for example, provided at the middle and upper part of the second reactor 10 near the side wall. The second gas-liquid separation device 8 can be filled with wire mesh fillers, porous foam fillers, spherical fillers, corrugated plate fillers, and the filler surface can be a partially hydrophilic or partially hydrophobic material. Preferably, the second gas-liquid separation device 8 is filled with a hydrophobic wire mesh filler.

[0065] The mixture after the reaction in the second reactor 10 flows upward in the reactor, and the reaction mixture undergoes gas-liquid separation through the second gas-liquid separation device 8, and part of the unreacted gas enters the tail gas treatment section through the second gas-liquid separation device 8. The liquid-solid mixture passes through the second liquid-solid separation device 9, and the liquid enters the gas-liquid separator 12 for further gas-liquid separation. The obtained gas enters the tail gas treatment section from the top of the gas-liquid separator 12, and the liquid leaves the hydrogenation reaction system from the bottom of the gas-liquid separator 12.

[0066] In one embodiment, the inlet of the gas-liquid separator 12 can be fed tangentially, radially, or parallel to the radial direction. Preferably, the inlet of the gas-liquid separator 12 is fed tangentially.

[0067] Therefore, the present invention provides a hydrogenation reaction method. The method firstly strengthens the hydrogenation reaction process by synergistically using a supergravity microbubble generator and a gas distributor, and then further promotes the depth of the heavy oil hydrogenation reaction and reduces the number of microbubbles by setting a second reactor and a second supergravity microbubble generator, and causes the microbubbles retained in the liquid phase to aggregate and form millimeter bubbles to separate from the liquid phase system through a longer residence time and the carrying effect of large bubbles, which is beneficial to the subsequent separation process of the gas-liquid mixture containing microbubbles in the gas-liquid separator, thereby improving the safety of the hydrogenation process.

[0068] The technical solution of the present invention will be further described below by specific embodiments. Any range described in the present invention includes any end value and any numerical value between the end values ​​and any sub-range formed by the end value or any numerical value between the end values. Unless otherwise specified, each raw material in the present invention can be obtained by commercial purchase, and the equipment used in the present invention can be conventional equipment in the field or can be carried out with reference to the prior art in the field.

[0069] Various schematic diagrams of embodiments disclosed in the present invention are shown in the accompanying drawings. These figures are not drawn to scale, and some details are magnified and some details may be omitted for the purpose of clear expression. The shapes of various regions and layers shown in the figures and the relative sizes and positional relationships between them are only exemplary, and may deviate in practice due to manufacturing tolerances or technical limitations, and those skilled in the art may further design regions / layers with different shapes, sizes, and relative positions according to actual needs.

[0070] Example 1

[0071] A hydrogenation reaction method, using Figure 1 The process and Figure 2 The cross-shaped gas distributor shown comprises the following steps:

[0072] Atmospheric residue oil was used as the raw oil, an oil-soluble hydrogenation catalyst was used, the rotation speed of the first supergravity microbubble generator was 1200 r / min, the average diameter of the bubbles of hydrogen after passing through the first supergravity microbubble generator was 150 μm, the average diameter of the bubbles of hydrogen after passing through the gas distributor was 8 mm, the rotation speed of the second supergravity microbubble generator was 100 r / min, the average diameter of the bubbles of hydrogen after passing through the second supergravity microbubble generator was 1.2 mm, the reaction temperature and reaction pressure of the first slurry bed reactor and the second slurry bed reactor were both 430° C. and 15 MPa, and the total liquid volume space velocity entering the first and second slurry bed reactors was 0.15 h -1 The hydrogen-to-oil volume ratio entering the first slurry bed reactor is 450 Nm 3 / Nm 3 The ratio of hydrogen entering the first supergravity microbubble generator to hydrogen entering the first reactor through the gas distributor is 1:1, and the volume ratio of hydrogen entering the second slurry bed reactor to the feedstock oil (i.e., the feedstock oil entering the first slurry bed reactor) is 450Nm 3 / Nm 3 .

[0073] Example 2

[0074] A hydrogenation reaction method, using Figure 1 The process and Figure 2 The cross-shaped gas distributor shown comprises the following steps:

[0075] Atmospheric residue was used as the raw oil, and the same oil-soluble hydrogenation catalyst as in Example 1 was used. The rotation speed of the first supergravity microbubble generator was 2000 r / min, the average bubble diameter of hydrogen after passing through the first supergravity microbubble generator was 100 μm, and the average bubble diameter of hydrogen after passing through the gas distributor was 10 mm. The rotation speed of the second supergravity microbubble generator was 80 r / min, and the average bubble diameter of hydrogen after passing through the second supergravity microbubble generator was 1.4 mm. The reaction temperature and reaction pressure of the first slurry bed reactor and the second slurry bed reactor were both 430° C. and 15 MPa, and the total liquid volume space velocity entering the first and second slurry bed reactors was 0.15 h -1 The hydrogen-to-oil volume ratio entering the first slurry bed reactor is 450 Nm 3 / Nm 3 The ratio of hydrogen entering the first supergravity microbubble generator to hydrogen entering the first reactor through the gas distributor is 1.5:1, and the volume ratio of hydrogen entering the second slurry bed reactor to the feedstock oil (i.e., the feedstock oil entering the first slurry bed reactor) is 450Nm 3 / Nm 3 .

[0076] Example 3

[0077] A hydrogenation reaction method, using Figure 1 The process and Figure 2 The cross-shaped gas distributor shown comprises the following steps:

[0078] Atmospheric residue was used as the raw oil, and the same oil-soluble hydrogenation catalyst as in Example 1 was used. The rotation speed of the first supergravity microbubble generator was 2600 r / min, the average diameter of the bubbles of hydrogen after passing through the first supergravity microbubble generator was 60 μm, and the average diameter of the bubbles of hydrogen after passing through the gas distributor was 12 mm. The rotation speed of the second supergravity microbubble generator was 60 r / min, and the average diameter of the bubbles of hydrogen after passing through the second supergravity microbubble generator was 1.8 mm. The reaction temperature and reaction pressure of the first slurry bed reactor and the second slurry bed reactor were both 430° C. and 15 MPa, and the total liquid volume space velocity entering the first and second slurry bed reactors was 0.15 h -1 The hydrogen-to-oil volume ratio entering the first slurry bed reactor is 450 Nm 3 / Nm 3 The ratio of hydrogen entering the first supergravity microbubble generator to hydrogen entering the first reactor through the gas distributor is 2:1, and the volume ratio of hydrogen entering the second slurry bed reactor to the feedstock oil (i.e., the feedstock oil entering the first slurry bed reactor) is 450Nm 3 / Nm 3 .

[0079] Comparative Example 1

[0080] A hydrogenation reaction method, using Figure 3 The process and Figure 2 The cross-shaped gas distributor shown comprises the following steps:

[0081] Atmospheric residue was used as the feedstock oil, and the same oil-soluble hydrogenation catalyst as in Example 1 was used. The average diameter of the hydrogen bubbles after passing through the gas distributor was 8 mm. The reaction temperature and reaction pressure of the first slurry bed reactor and the second slurry bed reactor were both 430° C. and 15 MPa. The total liquid volumetric space velocity entering the first and second slurry bed reactors was 0.15 h -1 The hydrogen-to-oil volume ratio entering the first slurry bed reactor is 450 Nm 3 / Nm 3 Among the hydrogen entering the first slurry bed reactor, the ratio of hydrogen entering the bottom of the reactor to hydrogen entering the gas distributor is 1:1, and the volume ratio of hydrogen entering the second slurry bed reactor to the feedstock oil (i.e., the feedstock oil entering the first slurry bed reactor) is 450Nm 3 / Nm 3 .

[0082] Comparative Example 2

[0083] A hydrogenation reaction method, using Figure 3 The process and Figure 2 The cross-shaped gas distributor shown comprises the following steps:

[0084] Atmospheric residue was used as the feedstock oil, and the same oil-soluble hydrogenation catalyst as in Example 1 was used. The average diameter of the hydrogen bubbles after passing through the gas distributor was 8 mm. The reaction temperature and reaction pressure of the first slurry bed reactor and the second slurry bed reactor were both 430° C. and 15 MPa. The total liquid volumetric space velocity entering the first and second slurry bed reactors was 0.15 h -1 The hydrogen-to-oil volume ratio entering the first slurry bed reactor is 600 Nm 3 / Nm 3 The ratio of hydrogen entering the bottom of the first slurry bed reactor to hydrogen entering the gas distributor is 1:1, and the volume ratio of hydrogen entering the second slurry bed reactor to the feedstock oil (i.e., the feedstock oil entering the first slurry bed reactor) is 600 Nm 3 / Nm 3 .

[0085] The properties of the atmospheric residue oil used in the examples and comparative examples are shown in Table 1.

[0086] The reaction results of the examples and comparative examples are shown in Table 2.

[0087] Table 1 Raw oil properties

[0088]

[0089]

[0090] Table 2 Reaction results

[0091] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 >500℃ fraction conversion rate / % 68.5 68.7 68.9 67.2 68.4 Sulfur content of reaction product / w% 1.32 1.30 1.27 1.58 1.31 Nitrogen content of reaction product / w% 0.28 0.27 0.25 0.31 0.29 CCR / w% of reaction product 4.72 4.70 4.68 5.58 4.71 Toluene insoluble matter in the reaction product / w% 0.64 0.61 0.56 0.86 0.65

[0092] As shown in Table 2, Examples 1-3 and Comparative Example 1 hydroprocess the feedstock oil under the same reaction conditions (reaction temperature, reaction pressure, total liquid hourly volume space velocity, hydrogen to oil volume ratio), and Examples 1-3 of the present invention have higher feedstock oil conversion rates, lower product sulfur content, nitrogen content, residual carbon value, and toluene insoluble content. Examples 1-3 and Comparative Example 2 have similar reaction effects (conversion rate, product sulfur content, nitrogen content, residual carbon value, toluene insoluble content), and the hydrogen to oil ratio of Examples 1-3 of the present invention can be reduced by about 25% compared with Comparative Example 2.

[0093] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, technicians familiar with the field may make various corresponding changes and deformations based on the present invention, but these corresponding changes and deformations should all fall within the scope of protection of the claims of the present invention.

Claims

1. A hydrogenation reaction method, characterized in that: The steps include: Step 1, mixing the crude oil with the catalyst, and then conveying them to the first supergravity microbubble generator; Step 2, transporting hydrogen to the first supergravity microbubble generator and the first reactor respectively, the hydrogen transported to the first supergravity microbubble generator is broken into micron-sized bubbles, and the hydrogen transported to the first reactor is dispersed into millimeter-sized bubbles through a gas distributor; Step 3: The crude oil, catalyst and hydrogen in the first supergravity microbubble generator are transported to the first reactor for hydrogenation reaction.

2. The hydrogenation reaction method according to claim 1, characterized in that: Also includes: Step 4, transporting the hydrogen and the reaction mixture in the first reactor to a second supergravity microbubble generator, wherein the hydrogen transported to the second supergravity microbubble generator is broken into millimeter-sized bubbles; Step 5: The mixture in the second supergravity microbubble generator is transported to the second reactor for hydrogenation reaction.

3. The hydrogenation reaction method according to claim 1, characterized in that: In step 1, the crude oil is mixed with the catalyst after being heated, and the heating temperature is 100-600°C.

4. The hydrogenation reaction method according to claim 1, characterized in that: The number of gas distributors in the first reactor is at least one, which is distributed along the radial direction of the first reactor. The gas distributor in the first reactor is a cross structure, a Poisson structure, a well structure, a concentric circular ring structure or a concentric square ring structure. The gas distributor is provided with an opening, and the size of the opening is 1-30 mm.

5. The hydrogenation reaction method according to claim 2, characterized in that: The rotation speed of the first supergravity microbubble generator is greater than 0 and less than or equal to 3000 r / min, and the rotation speed of the second supergravity microbubble generator is greater than 0 and less than or equal to 3000 r / min, and the rotation speed of the first supergravity microbubble generator is higher than the rotation speed of the second supergravity microbubble generator.

6. The hydrogenation reaction method according to claim 1, characterized in that: The first reactor is a slurry bed reactor, and the temperature of the hydrogenation reaction in the first reactor is 100-600° C. and the pressure is 1-30 MPa.

7. The hydrogenation reaction method according to claim 2, characterized in that: The second reactor is a slurry bed reactor, and the temperature of the hydrogenation reaction in the second reactor is 100-600° C. and the pressure is 1-30 MPa.

8. The hydrogenation reaction method according to claim 2, characterized in that: A gas-liquid separation device is disposed on the top of the first reactor and the second reactor, and part of the unreacted gas in the first reactor and the second reactor is discharged from the first reactor and the second reactor through the gas-liquid separation device.

9. The hydrogenation reaction method according to claim 1, characterized in that: The raw oil is a mixture of one or more of atmospheric residue, vacuum residue, thick crude oil, oil sand asphalt, catalytic cracking slurry, ethylene cracking tar and coal tar; the catalyst is a liquid catalyst, an oil-soluble catalyst or a solid powder catalyst.

10. The hydrogenation reaction method according to claim 2, characterized in that: The hydrogen is transported to the first supergravity microbubble generator, the first reactor, and the second supergravity microbubble generator after being pressurized, and the pressurization pressure is 1-30 MPa.

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