A fixed-bed residue oil hydrotreating method

Abstract

The present invention discloses a fixed-bed residual oil hydroprocessing method, comprising the following steps: (1) residual oil feedstock is mixed with hydrogen and enters a rotating hydroprocessing pretreatment reaction zone heated simultaneously by ultrasonic and microwave emission sources to perform a hydrodemetallization reaction; (2) the reaction effluent enters the hydroprocessing reaction zone to perform hydrodesulfurization, nitrogen and carbon residue reactions; wherein the first and second hydroprocessing pretreatment reactors in the rotating hydroprocessing pretreatment reaction zone are connected in series and serve as the first and second stage online hydroprocessing pretreatment reactors, while the third hydroprocessing pretreatment reactor is in a cut-out state; the amount of a strong microwave absorbing material added to the hydrodemetallization catalyst in the two online hydroprocessing pretreatment reactors is gradually increased. The present invention can delay the deactivation rate of the catalyst in the hydroprocessing pretreatment reaction zone, thereby reducing the number of rotations of the hydroprocessing pretreatment reactors and increasing the operating cycle of the hydrogenation unit.

Description

Technical Field

[0001] The present invention relates to a fixed-bed residual oil hydroprocessing method, in particular to a rotary fixed-bed ultrasonic-microwave coordinated residual oil hydroprocessing method. Background Art

[0002] Fixed-bed residue hydrotreating technology is a deep-processing technology for heavy oils. It desulfurizes, denitrifies, and removes metals from atmospheric or vacuum residues under high-temperature, high-pressure, and hydrogen-containing conditions to maximize the production of lightweight products. It is a key method for lightweighting residues. Fixed-bed residue hydrotreating technology is gaining increasing popularity due to its advantages, including high liquid product yields, high product quality, strong production flexibility, minimal waste, environmental friendliness, and high return on investment.

[0003] Although fixed-bed residue oil hydrotreating technology has many advantages, when processing low-quality oil, a large amount of metal impurities, unsaturated components and scale in the residue oil raw materials are easily deposited on the surface of the catalyst and in the gaps between the catalyst particles, resulting in blockage of the protection and demetallization reactor beds, excessively rapid increase in pressure drop, and deactivation of the hydrotreating protection catalyst and the hydrodemetallization catalyst before the hydrodesulfurization main catalyst, resulting in problems such as shortened unit operation cycle and low main catalyst utilization efficiency.

[0004] CN110499188A discloses a method and system for hydrotreating residual oil in a series of rotating fixed-bed reactors. The method increases the weight ratio of the hydrodemetallization catalyst to the hydroprotectant in the non-online hydrotreating reactor each time the hydrotreating pretreatment reactor is rotated. By changing the catalyst gradation ratio in the rotating reactor, the main catalyst utilization efficiency and the stability of the device operation are improved, thereby extending the operating time of the hydrotreating reactor. However, in this method, the rotating reactor uses a conventional heating furnace. Since the operating temperature of the rotating reactor is higher than that of the main reactor, a large amount of metallic impurities, unsaturated components, and fouling in the residual oil feedstock are easily deposited on the surface of the rotating reactor catalyst and in the spaces between the catalyst particles, resulting in bed blockage, excessive pressure drop, short service life, and a high number of reactor rotations, which increases processing complexity and economic costs. Summary of the Invention

[0005] To address the shortcomings of the prior art, the present invention provides a fixed-bed residue hydroprocessing method. This method utilizes ultrasonic and microwave emission sources to synergistically act on a hydropretreatment reaction zone. As the residue hydroprocessing reaction proceeds, the ratio of ultrasonic and microwave power within the hydropretreatment reaction zone and the proportion of strong microwave-absorbing materials in the catalyst are adjusted to slow catalyst deactivation in the hydropretreatment reaction zone. This reduces the number of hydropretreatment reactor rotations and increases the operating cycle of the hydroprocessing unit.

[0006] The fixed-bed residue oil hydrotreating method of the present invention comprises the following steps: (1) the residue oil feedstock is mixed with hydrogen and enters a rotating hydrogenation pretreatment reaction zone where ultrasonic and microwave emission sources act simultaneously to perform a hydrogenation demetallization reaction; (2) the effluent of the rotating hydrogenation pretreatment reaction zone enters a hydrotreating reaction zone to perform a hydrodesulfurization, nitrogen and carbon residue reaction;

[0007] The rotatable hydrogenation pretreatment reaction zone includes three hydrogenation pretreatment reactors arranged in series.

[0008] The first hydrogenation pretreatment reactor and the second hydrogenation pretreatment reactor are connected in series and serve as the first and second stage online hydrogenation pretreatment reactors, while the third hydrogenation pretreatment reactor is in a cut-out state and serves as a non-online hydrogenation pretreatment reactor; when the pressure drop in the first hydrogenation pretreatment reactor rises to the pressure drop design upper limit or the catalyst activity is lower than the requirement, the first hydrogenation pretreatment reactor is cut out and serves as a non-online hydrogenation pretreatment reactor, and the second and third hydrogenation pretreatment reactors are connected in series in sequence, the second hydrogenation pretreatment reactor serves as the first stage online hydrogenation pretreatment reactor, and the third hydrogenation pretreatment reactor serves as the second stage online hydrogenation pretreatment reactor, and the hydrogenation pretreatment reaction is carried out again; when the pressure drop in the second hydrogenation pretreatment reactor rises to the pressure drop design upper limit or the catalyst activity is lower than the requirement, the second hydrogenation pretreatment reactor is cut out, and the third and first hydrogenation pretreatment reactors are connected in series in sequence and serve as the online hydrogenation pretreatment reactor again; rotating in the above manner can achieve uninterrupted hydrogenation pretreatment reaction;

[0009] A hydrogenation protective agent bed and a hydrogenation demetallization catalyst bed are provided in the reactor of the rotational hydrogenation pretreatment reaction zone, and a strong microwave absorbing material, such as one or more of NiO, CrN, Fe3O4, MnO2 or SiC, is added to the hydrogenation demetallization catalyst. The amount of the strong microwave absorbing material added is 1 wt% to 50 wt% based on the mass of the catalyst, preferably 1 wt% to 20 wt%. During the rotation process, the amount of the strong microwave absorbing material added to the hydrogenation demetallization catalyst in the two online hydrogenation pretreatment reactors is gradually increased. When the proportion of the microwave power of the reactor in the hydrogenation pretreatment reaction zone to the total power is less than 50%, the gradually increased ratio is 3 wt% to 5 wt%; when the proportion of the microwave power of the reactor in the hydrogenation pretreatment reaction zone to the total power is greater than or equal to 50%, the gradually increased ratio is 1 wt% to 2 wt%. The loading ratio of the hydrogenation demetallization agent to the hydrogenation protective agent is generally (0.1 to 10):1, preferably (0.2 to 5):1.

[0010] In the method of the present invention, the hydrogenation protective agent and the hydrodemetallization catalyst are generally supported by a porous refractory inorganic oxide such as alumina, and at least one oxide of a Group VIB and / or Group VIII metal such as W, Mo, Co, Ni, etc. is used as the active component; the strong microwave absorbing material is generally introduced during the kneading or impregnation process of preparing the hydrodemetallization catalyst, and the introduction method is well known to those skilled in the art.

[0011] In the method of the present invention, when the hydrogenation pretreatment reactor is used as an off-line hydrogenation pretreatment reactor, a new catalyst is replaced or the catalyst is regenerated.

[0012] In the method of the present invention, the ultrasonic frequency is 15KHz to 1500KHz, and the power is 100 to 2000W.

[0013] In the method of the present invention, the microwave frequency is 915 or 2450 MHz, and the power is 100-2000 W.

[0014] In the method of the present invention, after start-up, the ratio of ultrasonic power to microwave power in the reactor in the hydrogenation pretreatment reaction zone is 1 to 20:1, preferably 1 to 10:1; when the temperature of the reactor in the hydrogenation pretreatment reaction zone is greater than 370°C, every time the reaction temperature increases by 5°C, the ratio of microwave power to total power (microwave power + ultrasonic power) is increased by 1% to 20%, preferably 1% to 10%.

[0015] In the method of the present invention, the operating conditions of the hydrogenation pretreatment reaction zone are: reaction temperature of 350-420°C, reaction pressure of 10MPa-25MPa, hydrogen-to-oil volume ratio of 300-1500, raw oil-to-liquid volume space velocity of 0.15h -1 ~2.0h -1 Preferably, the reaction temperature is 360-400°C, the reaction pressure is 15MPa-25MPa, the hydrogen-to-oil volume ratio is 500-800, and the raw oil-liquid volume space velocity is 0.3h -1 ~1.0h -1 .

[0016] In the method of the present invention, after the start-up phase transitions to the normal operation phase (i.e., all periods of normal operation), the reaction temperature of the online hydrogenation pretreatment reactor is higher than the reaction temperature of the hydrotreatment reaction zone, preferably higher by 5-25°C.

[0017] In the method of the present invention, the operating conditions of the hydroprocessing reaction zone are: reaction temperature of 345-420°C, reaction pressure of 10MPa-25MPa, hydrogen-to-oil volume ratio of 300-1500, raw oil-liquid volume space velocity of 0.15h -1 ~0.80h -1Preferably, the reaction temperature is 355-410°C, the reaction pressure is 15MPa-25MPa, the hydrogen-to-oil volume ratio is 400-800, and the raw oil-liquid volume space velocity is 0.2 h -1 ~0.6 h -1 .

[0018] In the method of the present invention, the hydroprocessing reaction zone adopts a heating furnace heating method and includes 1 to 5 hydroprocessing reactors arranged in series, preferably 2 to 3 hydroprocessing reactors arranged in series; the hydrogenated product of the hydroprocessing reaction zone enters a fractionation system for fractionation.

[0019] In the method of the present invention, rotation can be performed when the pressure drop rises to the upper limit of the pressure drop design, which can be 0.6 to 1.0 MPa.

[0020] In the method of the present invention, whether to rotate the catalyst can be determined based on catalyst activity. The reaction temperature of the online hydrogenation pretreatment reactor is determined based on the metal content (Ni+V) of the hydrogenation pretreatment product to control the metal (Ni+V) content of the hydrogenation pretreatment product to below 50 μg / g, preferably below 30 μg / g. If the metal content cannot be controlled below 50 μg / g, preferably below 30 μg / g, by adjusting the reaction temperature, the catalyst activity is below the requirement and rotation is required. The reaction temperature of the hydrogenation pretreatment reaction zone can be adjusted within the range of 350-420°C based on the metal content of the hydrogenation pretreatment product. The reaction temperature can be gradually increased to gradually increase the catalyst activity until the metal content (as Ni+V) in the pretreatment product is below 50 μg / g.

[0021] In the method of the present invention, the hydroprocessing reaction zone can be loaded with a hydroprocessing catalyst conventionally used in the art, and one or more combinations of hydrodesulfurization catalysts, hydrodenitrogenation catalysts, and carbon residue removal conversion catalysts can be selected. These catalysts generally use porous refractory inorganic oxides such as alumina as a carrier and oxides of Group VIB and / or Group VIII metals such as W, Mo, Co, and Ni as active components. For example, the FZC series residue oil hydroprocessing catalysts produced by the Catalyst Branch of Sinopec are used. The loading order is generally to contact the feed oil with the protective agent, hydrodemetallization, hydrodesulfurization, and hydrodenitrogenation catalysts in sequence, or these catalysts can be mixed and loaded.

[0022] In the method of the present invention, the residual oil feedstock is atmospheric residue and / or vacuum residue, and contains no or one or more of straight-run wax oil, vacuum wax oil, secondary processed wax oil, and catalytic recycled oil. The residual oil feedstock has the following properties: a sulfur content of no more than 4 wt%, a nitrogen content of no more than 0.7 wt%, a metal content (Ni+V) of no more than 120 μg / g, a carbon residue of no more than 17 wt%, and an asphaltene content of no more than 5 wt%.

[0023] Those skilled in the art are well aware that the cavitation effect of ultrasound effectively promotes sufficient contact between each reactant and catalyst, thereby increasing the chemical reaction rate. The unique thermal and non-thermal effects of microwaves can directly act on the inside of the catalyst, dissipating heat outward with the catalyst as the center, and the catalyst is evenly distributed inside the reactor. Unlike liquid materials that are prone to bias flow, it is beneficial to reduce temperature fluctuations and reduce the generation of radial temperature differences. However, simply applying these two methods or simply combining them in chemical reactions often does not produce good results. After a large number of experimental studies, the inventors applied microwaves and ultrasound to the residual oil hydrogenation rotation reaction process simultaneously based on the characteristics of the fixed-bed residual oil hydrogenation rotation reaction. By adjusting the ratio of ultrasound to microwave power in the hydrogenation pretreatment reaction zone and the ratio of strong microwave absorbing substances in the catalyst, the purpose of delaying the deactivation rate of the catalyst in the hydrogenation pretreatment reaction zone, reducing the number of rotations of the hydrogenation pretreatment reactor, and improving the economic benefits and operating cycle of the hydrogenation unit was achieved, and unexpected technical effects were achieved. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a schematic diagram of the process flow of the present invention;

[0025] Among them, 1 is the first hydrogenation pretreatment reactor; 2 is the second hydrogenation pretreatment reactor; 3 is the third hydrogenation pretreatment reactor; 4 is the heating furnace; 5 and 6 are the hydrogenation treatment reactors; 7 is the ultrasonic emission source; 8 is the microwave emission source; 21-30 are valves. DETAILED DESCRIPTION

[0026] The present invention is further described in detail below with reference to the accompanying drawings and embodiments.

[0027] like Figure 1As shown, at startup, the feedstock enters the top of the first hydropretreatment reactor 1, where ultrasonic-microwave synergistic hydrotreatment occurs in the presence of a catalyst. The hydrotreated oil flows through the bottom of the second hydropretreatment reactor 2 and enters the heating furnace 4. The third hydropretreatment reactor 3 then serves as a standby reactor. The heated oil and gas are then piped from the top of the reactor into hydroprocessing reactors 5 and 6, respectively, for hydroprocessing. The final hydrogenated product is then piped into the fractionation system. After a period of operation, when the pressure drop in the first hydropretreatment reactor 1 reaches the design upper limit, the first hydropretreatment reactor 1 is disconnected and replaced with the third hydropretreatment reactor 3. The second and third hydropretreatment reactors 2 and 3 are connected in series, with the first hydropretreatment reactor 1 now serving as the off-line hydropretreatment reactor, completing the first rotation. After a further period of operation, when the pressure drop in the second hydropretreatment reactor 2 reaches the design upper limit, the second hydropretreatment reactor 2 is disconnected and replaced with the first hydropretreatment reactor 1, completing the second rotation. After the device continues to operate for a period of time, when the pressure drop of the third hydrogenation pretreatment reactor 3 reaches the design upper limit, the third hydrogenation pretreatment reactor 3 is disconnected and the second hydrogenation pretreatment reactor 2 is connected. The first hydrogenation pretreatment reactor 1 and the second hydrogenation pretreatment reactor 2 are connected in series, completing the third rotation. In this way, the three hydrogenation pretreatment reactors are sequentially cycled out, rotated, and put online, allowing the hydrogenation pretreatment process to operate uninterrupted until the main reactor is shut down.

[0028] Example 1

[0029] The raw material used in this embodiment is typical Middle Eastern residual oil, and its properties are shown in Table 1. The ratio of the demetallizing agent to the protective agent in the first hydrogenation pretreatment reactor 1, the second hydrogenation pretreatment reactor 2, and the third hydrogenation pretreatment reactor 3 is 1:1, and the catalyst ratio remains unchanged each time it is rotated. When the reactor temperature in the hydrogenation pretreatment reaction zone is greater than 370°C, every time the reaction temperature is increased by 5°C, the proportion of microwave power in the total power is increased by 10%. When the proportion of microwave power in the total power is less than 50%, the weight ratio of the amount of strong microwave absorbing material added is preferably increased by 3wt% each time the hydrogenation pretreatment reactor is rotated. When the proportion of microwave power in the total power is higher than 50%, the weight ratio of the amount of strong microwave absorbing material added is preferably increased by 1wt% each time the hydrogenation pretreatment reactor is rotated. The process flow is as follows:

[0030] (1) Loading reactors: The first hydrogenation pretreatment reactor 1 is filled with a hydrogenation protective agent FZC-103D and a hydrodemetallization catalyst containing a strong microwave absorbing material SiC. The catalyst mainly contains 2.0wt% SiC, 4.0wt% Mo, 0.8wt% Ni, and the balance is an alumina carrier. The second hydrogenation pretreatment reactor 2 is filled with a hydrogenation protective agent FZC-103D and a hydrodemetallization catalyst containing a strong microwave absorbing material SiC. The catalyst mainly contains 3.0wt% SiC, 4.0wt% Mo, 0.8wt% Ni, and the balance is an alumina carrier. The third hydrogenation pretreatment reactor 3 is filled with a hydrogenation protective agent FZC-103D and a hydrodemetallization catalyst containing a strong microwave absorbing material SiC. The catalyst mainly contains 6.0wt% SiC, 4.0wt% Mo, 0.8wt% Ni, and the balance is an alumina carrier. The strong microwave absorbing material is generally introduced into the hydrodemetallization catalyst during the kneading or impregnation process of preparing the hydrodemetallization catalyst. The above-mentioned introduction method is well known to those skilled in the art.

[0031] During operation, valves 21, 25, and 27 are opened, and the remaining valves are closed. First and second hydroprocessing reactors 1 and 2 are connected in series and function as the first and second online hydroprocessing reactors, respectively. Third hydroprocessing reactor 3 is disconnected and functions as an offline pre-hydroprocessing reactor. The reaction feed first enters second hydroprocessing reactors 1 and 2, and then enters hydroprocessing reactors 5 and 6, where it undergoes further hydroprocessing to produce a reaction product.

[0032] After operation began, the hydrogenation pretreatment reaction was carried out under the simultaneous action of ultrasound and microwaves. The ultrasonic frequency was 20 kHz and the power was 1800 W, while the microwave frequency was 2450 MHz and the power was 200 W. When the reaction temperature reached 370°C, the ultrasonic power was adjusted to 1600 W and the microwave power to 400 W. When the reaction temperature reached 375°C, the ultrasonic power was adjusted to 1400 W and the microwave power to 600 W. When the reaction temperature reached 380°C, the ultrasonic power was adjusted to 1200 W and the microwave power to 800 W.

[0033] (2) After the device has been running for a period of time, when the pressure drop of the first hydrogenation pretreatment reactor 1 reaches the design upper limit, close the valve bodies 21, 25, and 27, cut out the first hydrogenation pretreatment reactor 1, and open the valve bodies 22, 26, and 28 at the same time. The remaining valves are closed and the third hydrogenation pretreatment reactor 3 is connected. The second hydrogenation pretreatment reactor 2 and the third hydrogenation pretreatment reactor 3 are connected in series. In this way, the second hydrogenation pretreatment reactor 2 serves as the first stage, the third hydrogenation pretreatment reactor 3 serves as the second stage, and the first hydrogenation pretreatment reactor 1 serves as the non-online hydrogenation pretreatment reactor, completing the first rotation. At this time, the reaction feed first enters the second hydrogenation pretreatment reactor 2 and the third hydrogenation pretreatment reactor 3 in sequence, and then enters the hydrogenation reactors 5 and 6 in sequence, and further undergoes hydrogenation reaction to obtain the reaction product.

[0034] When the reaction temperature reached 385°C, the ultrasonic power in the hydrogenation pretreatment reactor was adjusted to 1000 W and the microwave power was adjusted to 1000 W. When the reaction temperature reached 390°C, the ultrasonic power in the hydrogenation pretreatment reactor was adjusted to 800 W and the microwave power was adjusted to 1200 W.

[0035] During the period when the first hydrogenation pretreatment reactor 1 serves as an off-line hydrogenation pretreatment reactor, a fresh catalyst is replaced. The first hydrogenation pretreatment reactor 1 is filled with a hydrogenation protective agent FZC-103D and a hydrodemetallization catalyst containing a strong microwave absorbing material SiC. The catalyst mainly contains SiC with a content of 7.0wt%, Mo with a content of 4.0wt%, Ni with a content of 0.8wt%, and the balance is an alumina carrier.

[0036] (3) After the device has been running for a period of time, when the pressure drop of the second hydrogenation pretreatment reactor 2 reaches the design upper limit, valve bodies 22, 26, and 28 are closed, the second hydrogenation pretreatment reactor 2 is cut out, and valve bodies 23, 24, and 29 are opened at the same time. The remaining valves are closed and the first hydrogenation pretreatment reactor 1 is connected to complete the second rotation. The reaction feed first enters the third hydrogenation pretreatment reactor 3 and the first hydrogenation pretreatment reactor 1 in sequence, and then enters the hydrotreatment reactors 5 and 6 in sequence, and further undergoes hydrotreatment reaction to obtain the reaction product.

[0037] When the reaction temperature reached 395°C, the ultrasonic power in the hydrogenation pretreatment reactor was adjusted to 600 W and the microwave power was adjusted to 1400 W. When the reaction temperature reached 400°C, the ultrasonic power in the hydrogenation pretreatment reactor was adjusted to 400 W and the microwave power was adjusted to 1600 W.

[0038] During the period when the second hydrogenation pretreatment reactor 2 serves as a non-online hydrogenation pretreatment reactor, a fresh catalyst is replaced. The second hydrogenation pretreatment reactor 2 is filled with a hydrogenation protective agent FZC-103D and a hydrodemetallization catalyst containing a strong microwave absorbing material SiC. The catalyst mainly contains SiC with a content of 8.0wt%, Mo with a content of 4.0wt%, Ni with a content of 0.8wt%, and the balance is an alumina carrier.

[0039] (4) After the device has been running for a period of time, when the pressure drop of the third hydrogenation pretreatment reactor 3 reaches the design upper limit, the valve bodies 23, 24, and 29 are closed, the third hydrogenation pretreatment reactor 3 is cut out, and the valve bodies 21, 25, and 27 are opened at the same time. The remaining valve bodies are closed and the second hydrogenation pretreatment reactor 2 is connected. The first hydrogenation pretreatment reactor 1 and the second hydrogenation pretreatment reactor 2 are connected in series and serve as the first and second stage online hydrogenation pretreatment reactors, while the third hydrogenation pretreatment reactor 3 is in the cut-out state and serves as a non-online pre-hydrogenation pretreatment reactor, completing the third rotation. The reaction feed first enters the first hydrogenation pretreatment reactor 1, then enters the second hydrogenation pretreatment reactor 2, and then enters the hydrogenation reactors 5 and 6 in sequence, and is further hydrogenated to obtain the reaction product.

[0040] When the reaction temperature reaches 405°C, the ultrasonic power in the hydrogenation pretreatment reactor is adjusted to 200W and the microwave power is adjusted to 1800W.

[0041] In this embodiment, the reaction temperature of the hydrogenation pretreatment reactor is adjusted according to the metal (Ni+V) content of the hydrogenation pretreatment product. The reaction temperature can be gradually increased to ensure that the metal (Ni+V) content is no more than 20 μg / g.

[0042] The first hydroprocessing reactor 5 was loaded with FZC-33B catalyst, while the second hydroprocessing reactor 6 was loaded with FZC-41B catalyst. The reaction temperatures of the hydroprocessing reactors were adjusted based on the sulfur content of the hydroprocessed oil, maintaining a sulfur content of 0.40 wt%. For example, 100 hours after start-up, the reaction temperatures of the first hydroprocessing reactor 1 were 364°C, the second hydroprocessing reactor 2 was 367°C, and the reaction temperatures of hydroprocessing reactors 5 and 6 were 353°C and 355°C, respectively. The reaction temperatures of each reactor were subsequently adjusted according to the aforementioned control principles during operation.

[0043] Table 1 Properties of raw materials

[0044]

[0045] Table 2 Main operating conditions of the hydrogenation pretreatment reactor in Example 1

[0046]

[0047] Table 3 Switching conditions and switching time of the hydrogenation pretreatment reaction zone in Example 1

[0048]

[0049] Example 2

[0050] This example uses the reaction system, reaction materials, and reactor rotation method of Example 1, with the following difference: when the reactor temperature in the hydrogenation pretreatment reaction zone exceeds 370°C, the microwave power is increased by 5% of the total power every time the reaction temperature increases by 5°C. The process flow is as follows:

[0051] (1) The catalyst strong microwave absorbing material in the first hydrogenation pretreatment reactor 1 mainly contains SiC with a content of 1.0 wt%. The catalyst strong microwave absorbing material in the second hydrogenation pretreatment reactor 2 mainly contains SiC with a content of 3.0 wt%.

[0052] After operation, the hydrogenation pretreatment reaction was carried out under the simultaneous action of ultrasound and microwaves. The ultrasonic frequency was 20 kHz and the power was 1800 W, while the microwave frequency was 2450 MHz and the power was 200 W. When the reaction temperature reached 370°C, the ultrasonic power was adjusted to 1700 W and the microwave power to 300 W. When the reaction temperature reached 375°C, the ultrasonic power was adjusted to 1600 W and the microwave power to 400 W. When the reaction temperature reached 380°C, the ultrasonic power was adjusted to 1500 W and the microwave power to 500 W.

[0053] (2) After the device has been running for a period of time, when the pressure drop of the first hydrogenation pretreatment reactor 1 reaches the design upper limit, the first hydrogenation pretreatment reactor 1 is disconnected and the third hydrogenation pretreatment reactor 3 is connected, completing the first rotation. At this time, the catalyst strong microwave absorbing material in the third hydrogenation pretreatment reactor 3 mainly contains SiC with a content of 6.0 wt%.

[0054] When the reaction temperature reached 385°C, the ultrasonic power in the hydrogenation pretreatment reactor was adjusted to 1400 W and the microwave power was adjusted to 600 W. When the reaction temperature reached 390°C, the ultrasonic power in the hydrogenation pretreatment reactor was adjusted to 1300 W and the microwave power was adjusted to 700 W.

[0055] (3) After the device has been running for a period of time, when the pressure drop of the second hydrogenation pretreatment reactor 2 reaches the design upper limit, the second hydrogenation pretreatment reactor 2 is disconnected and connected to the first hydrogenation pretreatment reactor 1, completing the second rotation. At this time, the catalyst strong microwave absorbing material in the first hydrogenation pretreatment reactor 1 mainly contains SiC with a content of 9.0 wt%.

[0056] When the reaction temperature reached 395°C, the ultrasonic power in the hydrogenation pretreatment reactor was adjusted to 1200 W and the microwave power was adjusted to 800 W. When the reaction temperature reached 400°C, the ultrasonic power in the hydrogenation pretreatment reactor was adjusted to 1100 W and the microwave power was adjusted to 900 W.

[0057] (4) After the device has been running for a period of time, when the pressure drop of the third hydrogenation pretreatment reactor 3 reaches the design upper limit, the third hydrogenation pretreatment reactor 3 is disconnected and the second hydrogenation pretreatment reactor 2 is connected, completing the third rotation. At this time, the catalyst strong microwave absorbing material in the second hydrogenation pretreatment reactor 2 mainly contains SiC with a content of 12.0 wt%.

[0058] When the reaction temperature reaches 405° C., the ultrasonic power and microwave power in the hydrogenation pretreatment reactor are adjusted to 1000 W and 1000 W, respectively.

[0059] Table 4 Main operating conditions of the hydrogenation pretreatment reactor in Example 2

[0060]

[0061] Table 5 Switching conditions and switching time of the hydrogenation pretreatment reaction zone in Example 2

[0062]

[0063] Example 3

[0064] This example adopts the reaction system, reaction raw materials, and reactor rotation method of Example 1, with the following differences: When the microwave power accounts for less than 50% of the total power, the weight ratio of the strong microwave absorbing material added is preferably increased by 4 wt% each time the hydrogenation pretreatment reactor is rotated. When the microwave power accounts for more than 50% of the total power, the weight ratio of the strong microwave absorbing material added is preferably increased by 2 wt% each time the hydrogenation pretreatment reactor is rotated. The process flow is as follows:

[0065] (1) The catalyst strong microwave absorbing material in the first hydrogenation pretreatment reactor 1 mainly contains SiC with a content of 1.0 wt%. The catalyst strong microwave absorbing material in the second hydrogenation pretreatment reactor 2 mainly contains SiC with a content of 5.0 wt%.

[0066] After operation began, the hydrogenation pretreatment reaction was carried out under the simultaneous action of ultrasound and microwaves. The ultrasonic frequency was 20 kHz and the power was 1800 W, while the microwave frequency was 2450 MHz and the power was 200 W. When the reaction temperature reached 370°C, the ultrasonic power was adjusted to 1600 W and the microwave power to 400 W. When the reaction temperature reached 375°C, the ultrasonic power was adjusted to 1400 W and the microwave power to 600 W. When the reaction temperature reached 380°C, the ultrasonic power was adjusted to 1200 W and the microwave power to 800 W.

[0067] (2) After the device has been running for a period of time, when the pressure drop of the first hydrogenation pretreatment reactor 1 reaches the design upper limit, the first hydrogenation pretreatment reactor 1 is disconnected and the third hydrogenation pretreatment reactor 3 is connected, completing the first rotation. At this time, the catalyst strong microwave absorbing material in the third hydrogenation pretreatment reactor 3 mainly contains SiC with a content of 9.0 wt%.

[0068] When the reaction temperature reached 385°C, the ultrasonic power in the hydrogenation pretreatment reactor was adjusted to 1000W and the microwave power was adjusted to 1000W. When the reaction temperature reached 390°C, the ultrasonic power in the hydrogenation pretreatment reactor was adjusted to 800W and the microwave power was adjusted to 1200W. When the reaction temperature reached 395°C, the ultrasonic power in the hydrogenation pretreatment reactor was adjusted to 600W and the microwave power was adjusted to 1400W.

[0069] (3) After the device has been running for a period of time, when the pressure drop of the second hydrogenation pretreatment reactor 2 reaches the design upper limit, the second hydrogenation pretreatment reactor 2 is disconnected and connected to the first hydrogenation pretreatment reactor 1, completing the second rotation. At this time, the catalyst strong microwave absorbing material in the first hydrogenation pretreatment reactor 1 mainly contains SiC with a content of 11.0 wt%.

[0070] When the reaction temperature reached 400°C, the ultrasonic power in the hydrogenation pretreatment reactor was adjusted to 400 W and the microwave power was adjusted to 1600 W. When the reaction temperature reached 405°C, the ultrasonic power in the hydrogenation pretreatment reactor was adjusted to 200 W and the microwave power was adjusted to 1800 W.

[0071] Table 6 Main operating conditions of the hydrogenation pretreatment reactor in Example 3

[0072]

[0073] Table 7 Switching conditions and switching time of the hydrogenation pretreatment reaction zone in Example 3

[0074]

[0075] Comparative Example 1

[0076] This embodiment adopts the reaction system, reaction raw materials and catalyst gradation of Example 1, with the difference that the hydrogenation pretreatment reaction zone adopts a conventional heating furnace heating method.

[0077] Comparative Example 2

[0078] This embodiment adopts the reaction system, reaction raw materials and catalyst gradation of Example 1, except that the hydrogenation pretreatment reaction zone only performs hydrogenation pretreatment reaction under the action of ultrasound, the ultrasound frequency is 20KHz, and the ultrasound power is constant at 2000W.

[0079] Comparative Example 3

[0080] This embodiment adopts the reaction system, reaction raw materials and catalyst gradation of Example 1, except that the hydrogenation pretreatment reaction zone is only carried out under the action of microwaves, the microwave frequency is 2450 MHz, and the microwave power is constant at 2000 W.

[0081] Comparative Example 4

[0082] This embodiment adopts the reaction system, reaction raw materials and catalyst gradation of Example 1, except that the ultrasonic power in the hydrogenation pretreatment reaction zone is constant at 1000W and the microwave power is constant at 1000W.

[0083] The properties of the oil produced by hydrogenation of the residual oil obtained in the hydroprocessing reaction zone and the operating cycle of the reactor are shown in Table 8.

[0084] Table 8 Properties and operating cycle of the hydroprocessing residue oil produced in the hydroprocessing reaction zone

[0085]

[0086] It should be noted that the various specific technical features described in the above specific embodiments can be arbitrarily combined in any appropriate manner, which also falls within the scope disclosed by the present invention. In addition, the various different embodiments of the present invention can also be arbitrarily combined, as long as it does not violate the concept of the present invention, it should also be regarded as the content disclosed by the present invention.

Claims

1. A fixed bed residue oil hydrotreating method, characterized in that The method includes the following contents: (1) the residual oil feedstock is mixed with hydrogen and enters a rotating hydrogenation pretreatment reaction zone where ultrasonic and microwave emission sources act simultaneously to carry out a hydrogenation demetallization reaction; (2) the effluent of the rotating hydrogenation pretreatment reaction zone enters a hydrotreatment reaction zone to carry out a hydrodesulfurization, denitrification and residual carbon reaction; The rotatable hydrogenation pretreatment reaction zone includes three hydrogenation pretreatment reactors arranged in series, wherein the first hydrogenation pretreatment reactor and the second hydrogenation pretreatment reactor are connected in series and serve as the first and second online hydrogenation pretreatment reactors, while the third hydrogenation pretreatment reactor is in a cut-out state and serves as a non-online hydrogenation pretreatment reactor; when the pressure drop in the first hydrogenation pretreatment reactor rises to the pressure drop design upper limit or the catalyst activity is lower than the requirement, the first hydrogenation pretreatment reactor is cut out and serves as a non-online hydrogenation pretreatment reactor, and the second and third hydrogenation pretreatment reactors are connected in series in sequence, the second hydrogenation pretreatment reactor serves as the first-stage online hydrogenation pretreatment reactor, and the third hydrogenation pretreatment reactor serves as the second-stage online hydrogenation pretreatment reactor, and the hydrogenation pretreatment reaction is carried out again; when the pressure drop in the second hydrogenation pretreatment reactor rises to the pressure drop design upper limit or the catalyst activity is lower than the requirement, the second hydrogenation pretreatment reactor is cut out, and the third and first hydrogenation pretreatment reactors are connected in series in sequence and serve as the online hydrogenation pretreatment reactors again; rotating in the above manner can achieve uninterrupted hydrogenation pretreatment reaction; The reactor in the rotating hydrogenation pretreatment reaction zone is provided with a hydrogenation protective agent bed and a hydrodemetallization catalyst bed. A strong microwave absorbing material selected from one or more of NiO, CrN, Fe3O4, MnO2 or SiC is added to the hydrodemetallization catalyst. The amount of the strong microwave absorbing material added is 1wt% to 50wt% based on the mass of the catalyst. During the rotation process, the amount of the strong microwave absorbing material added to the hydrodemetallization catalyst in the two online hydrogenation pretreatment reactors is gradually increased. When the proportion of the microwave power of the reactor in the hydrogenation pretreatment reaction zone to the total power is less than 50%, the proportion is gradually increased by 3wt% to 5wt%; when the proportion of the microwave power of the reactor in the hydrogenation pretreatment reaction zone to the total power is greater than or equal to 50%, the proportion is gradually increased by 1wt% to 2wt%. After the start of operation, the ratio of ultrasonic and microwave power of the reactor in the hydrogenation pretreatment reaction zone is 1 to 20:1; when the temperature of the reactor in the hydrogenation pretreatment reaction zone is greater than 370°C, every time the reaction temperature increases by 5°C, the proportion of microwave power to the total power is increased by 1% to 20%.

2. The method according to claim 1, wherein: The hydrogenation protective agent and the hydrodemetallization catalyst use porous refractory inorganic oxide as carrier and Group VIB and / or Group VIII metal oxide as active component; the strong microwave absorbing material is introduced during the kneading or impregnation process of preparing the hydrodemetallization catalyst.

3. The method according to claim 1, wherein: The hydrogenation protective agent and the hydrodemetallization catalyst use alumina as a carrier and at least one of W, Mo, Co and Ni oxides as an active component.

4. The method according to claim 1, wherein: The filling ratio of the hydrogenation demetallization agent and the hydrogenation protective agent is 0.1 to 10:

1.

5. The method according to claim 1, wherein: When the hydrogenation pretreatment reactor is used as an off-line hydrogenation pretreatment reactor, a new catalyst is replaced or the catalyst is regenerated.

6. The method according to claim 1, wherein: The ultrasonic frequency is 15KHz to 1500KHz, and the power is 100 to 2000W.

7. The method according to claim 1, wherein: The microwave frequency is 915 or 2450 MHz, and the power is 100-2000 W.

8. The method according to claim 1, wherein: The operating conditions of the hydrogenation pretreatment reaction zone are: reaction temperature of 350-420°C, reaction pressure of 10MPa-25MPa, hydrogen-to-oil volume ratio of 300-1500, raw oil-to-liquid volume space velocity of 0.15h -1 ~2.0h -1 .

9. The method according to claim 1, wherein: After the start-up phase is transferred to the normal operation phase, the reaction temperature of the online hydrogenation pretreatment reactor is 5 to 25° C. higher than the reaction temperature of the hydrotreatment reaction zone.

10. The method according to claim 1, wherein: The operating conditions of the hydroprocessing reaction zone are: reaction temperature of 345-420°C, reaction pressure of 10MPa-25MPa, hydrogen-to-oil volume ratio of 300-1500, raw oil-to-liquid volume space velocity of 0.15h -1 ~0.80 h -1 .

11. The method according to claim 1, wherein: The hydroprocessing reaction zone adopts a heating furnace heating method and includes 1 to 5 hydroprocessing reactors arranged in series; the hydrogenated products of the hydroprocessing reaction zone enter the fractionation system for fractionation.

12. The method according to claim 1, wherein: When the pressure drop rises to the upper limit of the pressure drop design, rotation is carried out; the upper limit of the pressure drop design is 0.6~1.0MPa.

13. The method according to claim 1, wherein: Determine whether to rotate based on catalyst activity; determine the reaction temperature of the online hydrogenation pretreatment reactor based on the metal content Ni+V of the hydrogenation pretreatment product, so that the metal Ni+V content of the hydrogenation pretreatment product is controlled below 50μg / g. If the metal content cannot be controlled below 50μg / g by adjusting the reaction temperature, that is, the catalyst activity is lower than the requirement, and rotation is required; adjust the reaction temperature of the hydrogenation pretreatment reaction zone within the range of 350-420°C based on the metal content of the hydrogenation pretreatment product, gradually increase the reaction temperature, and gradually improve the activity of the catalyst, so that the metal content in the pretreatment product is below 50μg / g in terms of Ni+V.

14. The method according to claim 1, wherein: The hydroprocessing reaction zone is filled with a hydroprocessing catalyst, which is selected from one or more combinations of hydrodesulfurization catalysts, hydrodenitrogenation catalysts and carbon residue removal conversion catalysts; the above catalysts use porous refractory inorganic oxides as carriers and Group VIB and / or Group VIII metal oxides as active components.

15. The method according to claim 1, wherein: The residual oil raw material is atmospheric residue oil and / or vacuum residue oil, and contains no or one or more of straight-run wax oil, vacuum wax oil, secondary processed wax oil and catalytic recycled oil; the properties of the residual oil raw material are: sulfur content not more than 4wt%, nitrogen content not more than 0.7wt%, metal content Ni+V not more than 120μg / g, residual carbon value not more than 17wt%, and asphaltene content not more than 5wt%.

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