CN115960625B - Fixed bed heavy oil hydrogenation process - Google Patents
Fixed bed heavy oil hydrogenation process Download PDFInfo
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 62
- 239000000295 fuel oil Substances 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 96
- 238000006243 chemical reaction Methods 0.000 claims abstract description 86
- 238000001465 metallisation Methods 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000003921 oil Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000003223 protective agent Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000013461 design Methods 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 239000011358 absorbing material Substances 0.000 claims description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000009849 deactivation Effects 0.000 abstract description 4
- 230000001934 delay Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention discloses a fixed bed heavy oil hydrogenation process, which comprises the following steps: mixing heavy oil raw materials with hydrogen, entering an up-flow reaction zone for hydrodemetallization reaction, and then entering a fixed bed reaction zone for hydrodesulphurization, nitrogen and carbon residue reaction; wherein the up-flow reaction zone adopts the simultaneous action of ultrasonic wave and microwave, and every time a period of time, the actual metal deposition amount of the up-flow catalyst is measured, and the ultrasonic wave and microwave power is regulated. The invention keeps the bed expansion rate of the upflow reaction zone in an ideal range by a special control mode, reduces the radial temperature difference, delays the deactivation speed of the catalyst of the upflow reaction zone, and improves the operation period of the fixed bed heavy oil hydrogenation device.
Description
Technical Field
The invention belongs to the field of petroleum processing, and particularly relates to a fixed bed heavy oil hydrogenation process.
Background
As crude oil becomes increasingly heavier and worse, more and more heavy oil and residuum need to be processed. The main purpose of the residuum hydrotreatment process is to greatly reduce the contents of sulfur, nitrogen, metal and other impurities in the residuum raw materials through hydrotreatment, to hydrogenate and convert non-ideal components such as polycyclic aromatic hydrocarbon, colloid, asphaltene and the like, to increase the hydrogen-carbon ratio, to reduce the content of carbon residue and to obviously improve the cracking performance.
The fixed bed residual oil hydrogenation technology has the advantages of high liquid product yield, good product quality, strong production flexibility, less waste, environmental protection, high return on investment and the like, and is widely and widely applied. In the fixed bed residuum hydrotreatment technology, the reactor types can be classified into a general fixed bed reactor, i.e., a downflow mode reactor and an upflow reactor, depending on the flow mode of the reactant stream within the reactor. The upflow reactor is generally arranged before the fixed bed reactor (downflow mode), so that the metal content in the feed entering the downflow fixed bed reactor can be greatly reduced, and the fixed bed reactor catalyst is protected from being deactivated prematurely. The upflow type reactor is technically characterized in that reactant flows from bottom to top to slightly expand a catalyst bed layer, so that the pressure drop is small, the problem of large initial and final pressure drop changes when a conventional fixed bed reactor processes inferior residuum is solved, and the operation period is prolonged.
However, the upflow fixed bed residuum hydrogenation reaction system has certain limitations in the actual operation process. If the micro-expansion of the up-flow catalyst bed is uneven, the material bias flow can be easily caused, the temperature fluctuation of the up-flow catalyst bed is caused, the radial temperature difference is increased, the catalyst utilization rate is reduced, and the potential safety hazard can be caused. Meanwhile, as the running time of the device is prolonged, metal impurities in the raw oil are continuously removed through hydrogenation reaction and deposited on the catalyst, the actual weight of the catalyst is continuously increased, the expansion rate is gradually reduced, and the catalyst can not maintain a micro-expansion state gradually, so that the running period of the device is not prolonged.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a fixed bed heavy oil hydrogenation process. The invention keeps the bed expansion rate of the upflow reaction zone in an ideal range by a special control mode, reduces the radial temperature difference, delays the deactivation speed of the catalyst of the upflow reaction zone, and improves the operation period of the fixed bed heavy oil hydrogenation device.
The fixed bed heavy oil hydrogenation process of the invention comprises the following steps: mixing heavy oil raw materials with hydrogen, entering an up-flow reaction zone for hydrodemetallization reaction, and then entering a fixed bed reaction zone for hydrodesulphurization, nitrogen and carbon residue reaction; wherein the up-flow reaction zone adopts the simultaneous action of ultrasonic wave and microwave, and the actual metal deposition amount of the up-flow catalyst is measured at intervals according to the following relational expression:adjusting ultrasonic wave and microwave power; wherein,εrepresenting the expansion rate of the catalyst bed;u gas representing the actual value of the up-flow gas linear velocity;u 0 representing design value of up-flow gas linear velocity；Me a Representing the actual metal deposition amount of the upflow catalyst;Me t representing the theoretical metal deposition amount of the upflow catalyst;UT p representing ultrasonic power;MW p representing microwave power;UT p +MW p representing the total power, wherein the total power is 500-3000W, preferably 1000-2000W;A、Brepresenting the correlation coefficient, which is related to the property of the raw oil, the property of the catalyst and the like, wherein the density of the raw oil at 20 ℃ is 950-1000 kg/m 3 The viscosity value range of 100 ℃ is 60-150 mm/s,Ais constant 2.1; the catalyst bulk density is 400-600 kg/m 3 ，BIs constant 2.0.
In the process of the invention, the actual value of the gas linear velocity is controlled under the general conditionu gas With the design value of the gas linear velocityu 0 The ratio range is 1 to 1.1. If the gas phase line speed is too high, the fluctuation of the up-flow catalyst bed layer is increased, and radial temperature difference is easy to generate; if the gas phase linear velocity is too slow, the hydrogen-oil ratio of the up-flow inlet needs to be reduced, which can lead to the accelerated coking speed of the up-flow catalyst and the accelerated deactivation speed of the catalyst.
In the process, the expansion rate of the upflow reaction zone is 2 percent or lessεLess than or equal to 5 percent, preferably 2 percent or lessε≤3%。
In the process of the invention, the ultrasonic frequency is 15-1500 kHz, and the power is 100-2000W.
In the process of the invention, the microwave frequency is 915 or 2450MHz, and the power is 100-2000W.
In the process, the interval time for measuring the actual metal deposition amount of the upflow catalyst is 5-1000 h, preferably 10-200 h.
In the process, the heating mode of the upflow reaction zone is a mode of simultaneously heating an ultrasonic wave and a microwave emission source; the fixed bed reaction zone adopts a heating furnace heating mode.
In the process, the upflow reaction zone is used for carrying out hydrodemetallization reaction on heavy oil raw materials to remove impurities such as metallic nickel, vanadium, iron, calcium and the like contained in the raw materials; wherein, the reactor comprises 1-2 upflow reactors which are arranged in series, and preferably 1 upflow reactor.
In the process, the fixed bed reaction zone is used for carrying out hydrodesulfurization, nitrogen and carbon residue reaction on the effluent of the upflow reaction zone; wherein, the reactor comprises 1 to 5 fixed bed reactors which are arranged in series, preferably 2 to 4 fixed bed reactors which are arranged in series; the hydrogenation product in the fixed bed reaction zone enters a fractionating system for fractionating.
In the process of the invention, one or more of a hydrogenation protecting agent and a hydrodemetallization catalyst can be filled in the reactor of the upflow reaction zone. Preferably, the upflow reactors are provided with a hydrogenation protecting agent bed layer and a hydrogenation demetallization catalyst bed layer, wherein the hydrogenation protecting agent bed layer is filled with a hydrogenation protecting agent, and the hydrogenation demetallization catalyst bed layer is filled with a hydrogenation demetallization catalyst. The hydrogenation protecting agent and hydrodemetallization catalyst generally take porous refractory inorganic oxide such as alumina as a carrier, at least one of the oxides of VIB group and/or VIII group metals such as W, mo, co, ni and the like as an active component, and preferably, strong microwave absorbing substances such as NiO, crN, fe are added into the hydrogenation protecting agent and/or hydrodemetallization catalyst 3 O 4 、MnO 2 Or one or more of SiC and the like, and the addition amount of the strong microwave absorbing substance is 1-90 wt% based on the mass of the catalyst.
In the process of the invention, the operation conditions of the upflow reaction zone are as follows: the reaction temperature is 300-500 ℃, the reaction pressure is 10-25 MPa, the volume ratio of hydrogen to oil is 200-2000, and the hourly space velocity of the raw oil is 0.1h -1 ～5.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the reaction temperature is 350-420 ℃, the reaction pressure is 15-25 MPa, the volume ratio of hydrogen to oil is 200-1000, and the hourly space velocity of the raw oil is 0.15h -1 ～2.0h -1 。
In the process of the invention, the operation conditions of the fixed bed reaction zone are as follows: the reaction temperature is 340-500 ℃, the reaction pressure is 10-25 MPa, the volume ratio of hydrogen to oil is 300-1500, and the hourly space velocity of the raw oil is 0.15h -1 ～0.80 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the reaction temperature is 350℃to 350%430 ℃, the reaction pressure is 15 MPa-25 MPa, the hydrogen-oil volume ratio is 400-800, and the raw oil liquid hourly space velocity is 0.2 h -1 ～0.6 h -1 。
In the process of the invention, the fixed bed reaction zone can be filled with a hydrotreating catalyst which is conventionally used in the field, and one or more combinations of a hydrodesulfurization catalyst, a hydrodenitrogenation catalyst and a carbon residue removal conversion catalyst can be selected. The catalyst is generally prepared by taking porous refractory inorganic oxide such as alumina as a carrier, oxide of VIB group and/or VIII group metal such as W, mo, co, ni and the like as an active component, such as FZC series residuum hydrogenation catalyst produced by catalyst division company of China petrochemical Co., ltd, and the filling sequence is generally that raw oil is sequentially contacted with a protecting agent, hydrodemetallization, hydrodesulphurisation and hydrodenitrogenation catalyst, or the catalysts are mixed and filled.
In the process, the heavy oil raw material is normal pressure residual oil and/or vacuum residual oil, and does not contain or contains one or more of straight-run wax oil, vacuum wax oil, secondary processing wax oil and catalytic recycle oil. The properties of the residuum feedstock are: the sulfur content is not more than 4wt%, the nitrogen content is not more than 0.7wt%, the metal content (Ni+V) is not more than 120 mug/g, the carbon residue value is not more than 17wt%, and the asphaltene content is not more than 5wt%.
It is well known to those skilled in the art that ultrasonic cavitation is beneficial to the removal of carbon deposits on the surface of the catalyst and the maintenance of the dispersion of solids between the catalysts, and to the maintenance of the bed expansion rate of the upflow reactor catalyst, thereby slowing down the rise of the pressure drop of the upflow reactor bed; the special thermal effect and non-thermal effect of the microwaves can directly act inside the catalyst to radiate heat outwards by taking the catalyst as the center, and the catalyst is uniformly distributed inside the reactor, which is different from the liquid materials, is easy to bias flow, is favorable for reducing temperature fluctuation and radial temperature difference. However, the simple application or combination of these two modes in chemical reactions often does not give good results, especially in upflow fixed bed reactors. Through a great deal of experimental researches, the inventor applies microwaves and ultrasound to the whole residual oil hydrogenation upflow reaction process according to the characteristics of the heavy oil hydrogenation reaction and the upflow reactor, finds the relation between the gas flow rate, the upflow metal deposition amount and the ultrasonic wave-microwave cooperative control bed expansion rate and the power through a great deal of experimental researches and data regression, and obtains unexpected technical effects.
Drawings
FIG. 1 is a schematic flow diagram of a fixed bed heavy oil hydrogenation process of the present invention;
wherein, 1-up-flow reactor; 2-a first fixed bed reactor; 3-a second fixed bed reactor; 4-a heating furnace; 5-an ultrasonic emission source; 6-a microwave emission source.
Detailed Description
The invention will be described in further detail with reference to the drawings and examples.
The density of the raw oil at 20 ℃ is GB/T13377 by adopting an analysis method, and the viscosity at 100 ℃ is GB/T11177 by adopting an analysis method; the catalyst bulk density was SH/T0958 by analytical method;Me a indicating the actual metal deposition amount of the upflow catalyst,Me a subtracting the metal amount of the product at the outlet of the upflow reaction zone from the metal amount of the raw material in a certain operation time, wherein the analysis method is GB/T18608;Me t the theoretical metal deposition amount of the upflow catalyst is expressed, the calculation method is to subtract the metal amount of the outlet product of the upflow reaction zone from the metal amount of the raw materials in the whole process from the beginning of operation to the complete deactivation of the catalyst in the catalyst evaluation process, and the analysis method is GB/T18608.
As shown in fig. 1, the reaction raw materials enter from the bottom of an up-flow reactor 1, ultrasonic-microwave co-hydrotreating reaction is carried out in the presence of a catalyst, hydrogenation product oil flows out from the top of the up-flow reactor and enters a heating furnace 4, heating oil gas sequentially enters a first fixed bed reactor 2 from the top of the reactor through a pipeline for hydrotreating, hydrogenation product oil enters a second fixed bed reactor 3 from the top of the reactor through a pipeline for hydrotreating, and finally the hydrogenation product enters a fractionation system through a pipeline.
Example 1
The raw material used in this example is middle east residue, the properties of which are shown in Table1, the main operating conditions of the upflow reactor 1 are shown in table 2, and the actual value of the control gas linear velocity is the same as the design value of the gas linear velocity. The process flow is as follows: the reactor was charged, and the up-flow reactor 1 was charged with a hydrogen addition protecting agent FZC-103D (bulk density: 410 kg/m) 3 ) And hydrodemetallization catalyst (bulk density 450 kg/m) containing strong microwave absorbing material SiC 3 ) The catalyst mainly contains 2.4wt% of Si, 4.0wt% of Mo, 0.79wt% of Ni and the balance of alumina carrier. The grading weight proportion is hydrodemetallization catalyst: hydrogenation protectant=1:1. The hydrodemetallization catalyst preparation of the strong microwave absorbing material is generally introduced during the kneading or impregnation process for preparing the hydrodemetallization catalyst, and the introduction modes are well known to those skilled in the art.
According to the properties of the raw oil and the catalyst, the expansion rate formula of the up-flow bed layer is obtained as follows:
(1) After startup, the ultrasonic wave and the microwave simultaneously act to perform an up-flow hydrogenation reaction, the ultrasonic wave frequency is 20KHz, the power is 200W, the microwave frequency is 2450MHz, the power is 1800W, and the total power is 2000W constantly. At this time, the expansion rate of the bed layerε=2.3。
(2) The device runs for 970 hours, the actual metal deposition amount of the upflow catalyst reaches 10 percent of the theoretical metal deposition amount of the upflow catalyst, and the expansion rate of the bed layer is at the momentε=2.1. Then adjusting the ultrasonic power in the up-flow reactor to 400W, the microwave power to 1600W, and adjusting the expansion rate of the back bed layerε=2.3。
(3) The device runs for 2120 hours, the actual metal deposition amount of the upflow catalyst reaches 20 percent of the theoretical metal deposition amount of the upflow catalyst, and the expansion rate of the bed layer is increasedε=2.1. Then adjusting the ultrasonic power in the up-flow reactor to 600W, the microwave power to 1400W, and adjusting the expansion rate of the back bed layerε=2.3。
According to the above steps, every time the ratio of the actual metal deposition amount of the up-flow catalyst to the theoretical metal deposition amount of the up-flow catalyst is increased by 10%, the ultrasonic power is adjusted to be increased by 200w until the shutdown.
The reaction feed sequentially enters a first fixed bed reactor 2 and a second fixed bed reactor 3 after passing through an upflow reactor 1, and then the reaction product is obtained after further hydrogenation reaction.
In this embodiment, the reaction temperature of the upflow reactor is adjusted according to the metal (Ni+V) content of the reaction product of the upflow reactor, and the reaction temperature can be gradually increased so that the metal (Ni+V) content is not more than 30 μg/g.
The catalyst filled in the first fixed bed reactor 2 is FZC-33B; the second fixed bed reactor 3 was packed with FZC-41B. The reaction temperature of the hydrotreatment reactor is adjusted according to the sulfur content of the hydrogenated oil, so that the sulfur content of the hydrogenated oil is kept at 0.50wt%. For example, 100 hours after start-up, the reaction temperature of the upflow reactor 1 is 360 ℃, the reaction temperatures of the first and second fixed bed reactors are 365 ℃ and 370 ℃ respectively, and then the reaction temperatures of the reactors in the operation process are adjusted according to the control principle.
TABLE 1 Properties of the feedstock
TABLE 2 Primary operating conditions for the upflow reactor in example 1
Example 2
The reaction system, reaction materials and catalyst composition of example 1 were used in this example, except that: the initial power of the ultrasonic wave and the initial power of the microwave of the upflow reactor 1 are different, and the total power is constant to 1800w. The main operating conditions of the upflow reactor 1 are shown in Table 3, and the process flow is as follows:
(1) After starting, the up-flow hydrogenation reaction is carried out under the simultaneous action of ultrasonic wave and microwave, and the ultrasonic frequency is 20KHzFor power 180W, microwave frequency is 2450MHz, power 1620W, and total power is 1800W. At this time, the expansion rate of the bed layerε=2.3。
(2) The device is operated for 960 hours, the actual metal deposition amount of the upflow catalyst reaches 10 percent of the theoretical metal deposition amount of the upflow catalyst, and the expansion rate of the bed layer is increasedε=2.1. Then adjusting the ultrasonic power in the up-flow reactor to 360W and the microwave power to 1440W, and adjusting the expansion rate of the back bed layerε=2.3。
(3) The device is operated for 2110 hours, the actual metal deposition amount of the upflow catalyst reaches 20 percent of the theoretical metal deposition amount of the upflow catalyst, and the expansion rate of the bed layer is increasedε=2.1. Then adjusting the ultrasonic power in the up-flow reactor to 540W and the microwave power to 1260W, and adjusting the expansion rate of the back bed layerε=2.3。
According to the above steps, every time the ratio of the actual metal deposition amount of the up-flow catalyst to the theoretical metal deposition amount of the up-flow catalyst is increased by 10%, the ultrasonic power is adjusted to be increased by 180w until the shutdown.
TABLE 3 Primary operating conditions for the upflow reactor in example 2
Example 3
The reaction system, reaction materials and catalyst composition of example 1 were used in this example, except that: controlling the actual value of the gas linear velocityu gas With the design value of the gas linear velocityu 0 The ratio was 1.05. The main operating conditions of the upflow reactor 1 are shown in Table 4, and the process flow is as follows:
(1) After startup, the ultrasonic wave and the microwave simultaneously act to perform an up-flow hydrogenation reaction, wherein the ultrasonic wave frequency is 20KHz, the power is 200W, the microwave frequency is 2450MHz, the power is 1800W, and the total power is 2000W. At this time, the expansion rate of the bed layerε=2.4。
(2) The device is operated for 930 hours, and the actual metal deposition amount of the upflow catalyst reaches the theoretical metal deposition of the upflow catalyst10% of the amount, at which time the bed expansion rateε=2.2. Then adjusting the ultrasonic power in the up-flow reactor to 400W, the microwave power to 1600W, and adjusting the expansion rate of the back bed layerε=2.4。
(3) The device runs for 2050 hours, the actual metal deposition amount of the upflow catalyst reaches 20 percent of the theoretical metal deposition amount of the upflow catalyst, and the expansion rate of the bed layer is increasedε=2.2. Then adjusting the ultrasonic power in the up-flow reactor to 600W, the microwave power to 1400W, and adjusting the expansion rate of the back bed layerε=2.4。
According to the above steps, every time the ratio of the actual metal deposition amount of the up-flow catalyst to the theoretical metal deposition amount of the up-flow catalyst is increased by 10%, the ultrasonic power is adjusted to be increased by 200w until the shutdown.
TABLE 4 Primary operating conditions for the upflow reactor in example 3
Comparative example 1
The reaction system, reaction materials and catalyst composition of example 1 were used in this example, except that: the ultrasonic power of the upflow reactor is constant at 1000W, and the microwave power is constant at 1000W.
Comparative example 2
The reaction system, reaction materials and catalyst composition of example 1 were used in this example, except that: after startup, the upflow reactor performs hydrogenation pretreatment reaction under the alternating action of ultrasonic waves and microwaves. The ultrasonic wave and the microwave are replaced once every 100h, when the ultrasonic wave works, the ultrasonic power is constant at 2000w, and the microwave power is 0; when the microwave works, the microwave power is constant at 2000w, and the ultrasonic power is 0.
Comparative example 3
The reaction system, reaction materials and catalyst composition of example 1 were used in this example, except that: and adjusting ultrasonic wave power and microwave power in fixed time, and increasing the ultrasonic wave power by 200w every 800h after starting up until stopping working.
The examples 1-3 and comparative examples 1-3 of the present invention were run for 8000 hours, and the properties of the hydrogenated oil from the residuum obtained in the fixed bed reaction zone and the run time of the reactor are shown in Table 5.
TABLE 5 properties and run time of residuum hydrogenation oil obtained in fixed bed reaction zone
Claims (17)
1. The fixed bed heavy oil hydrogenation process is characterized by comprising the following steps: mixing heavy oil raw materials with hydrogen, entering an up-flow reaction zone for hydrodemetallization reaction, and then entering a fixed bed reaction zone for hydrodesulphurization, nitrogen and carbon residue reaction; wherein the up-flow reaction zone adopts the simultaneous action of ultrasonic wave and microwave, and the actual metal deposition amount of the up-flow catalyst is measured at intervals according to the following relational expression:adjusting ultrasonic wave and microwave power, and controlling the expansion rate of the catalyst bed; wherein,εrepresenting the expansion rate of the catalyst bed;u gas representing the actual value of the up-flow gas linear velocity;u 0 representing an up-flow gas linear velocity design value;Me a representing the actual metal deposition amount of the upflow catalyst;Me t representing the theoretical metal deposition amount of the upflow catalyst;UT p representing ultrasonic power;MW p representing microwave power;UT p +MW p representing the total power;A、Brepresenting the correlation coefficient; wherein the density value range of the heavy oil raw oil at 20 ℃ is 950-1000 kg/m 3 The viscosity value range of 100 ℃ is 60-150 mm/s,Ais constant 2.1; the catalyst bulk density is 400-600 kg/m 3 ，BIs constant 2.0.
2. The fixed bed heavy oil hydrogenation process according to claim 1, wherein: upflow typeThe expansion rate of the catalyst bed layer in the reaction zone is 2 percent or lessε≤5%。
3. The fixed bed heavy oil hydrogenation process according to claim 1, wherein: the said processUT p +MW p The total power is 500-3000W.
4. The fixed bed heavy oil hydrogenation process according to claim 1, wherein: controlling the actual value of the gas linear velocityu gas With the design value of the gas linear velocityu 0 The ratio of (2) is 1 to 1.1.
5. The fixed bed heavy oil hydrogenation process according to claim 1, wherein: the heating mode of the upflow reaction zone is that of an ultrasonic wave and microwave emission source simultaneously; the fixed bed reaction zone adopts a heating furnace heating mode.
6. The fixed bed heavy oil hydrogenation process according to claim 1, wherein: the upflow reaction zone is used for carrying out hydrodemetallization reaction on heavy oil raw materials and removing metallic nickel, vanadium, iron and calcium impurities contained in the raw materials; wherein, the reactor comprises 1-2 upflow reactors which are arranged in series.
7. The fixed bed heavy oil hydrogenation process according to claim 1, wherein: the fixed bed reaction zone is used for carrying out hydrodesulfurization, nitrogen and carbon residue reaction on the effluent of the upflow reaction zone; wherein, the reactor comprises 1 to 5 fixed bed reactors which are arranged in series; the hydrogenation product in the fixed bed reaction zone enters a fractionating system for fractionating.
8. The fixed bed heavy oil hydrogenation process according to claim 1, wherein: the ultrasonic frequency is 15-1500 kHz, and the power is 100-2000W.
9. The fixed bed heavy oil hydrogenation process according to claim 1, wherein: the microwave frequency is 915 or 2450MHz, and the power is 100-2000W.
10. The fixed bed heavy oil hydrogenation process according to claim 1, wherein: the interval time for measuring the actual metal deposition amount of the upflow catalyst is 5-1000 hours.
11. The fixed bed heavy oil hydrogenation process according to claim 1, wherein: one or more of a hydrogenation protective agent and a hydrodemetallization catalyst are filled in a reactor of the upflow reaction zone.
12. The fixed bed heavy oil hydrogenation process according to claim 11, wherein: a hydrogenation protective agent bed layer and a hydrogenation demetallization catalyst bed layer are arranged in the reactor of the upflow reaction zone, wherein the hydrogenation protective agent bed layer is filled with a hydrogenation protective agent, and the hydrogenation demetallization catalyst bed layer is filled with a hydrogenation demetallization catalyst; the hydrogenation protective agent and the hydrodemetallization catalyst take porous refractory inorganic oxide as a carrier and VIB and/or VIII metal as an active component.
13. The fixed bed heavy oil hydrogenation process according to claim 11 or 12, wherein: adding strong microwave absorbing material selected from NiO, crN, fe to hydrogenation protecting agent and/or hydrodemetallization catalyst 3 O 4 、MnO 2 Or one or more of SiC, and the addition amount of the strong microwave absorbing substances is 1-90 wt% based on the mass of the catalyst.
14. The fixed bed heavy oil hydrogenation process according to claim 1, wherein: the operation conditions of the upflow reaction zone are as follows: the reaction temperature is 300-500 ℃, the reaction pressure is 10-25 MPa, the volume ratio of hydrogen to oil is 200-2000, and the hourly space velocity of the raw oil is 0.1h -1 ～5.0h -1 。
15. The solid according to claim 1The fixed bed heavy oil hydrogenation process is characterized in that: the operation conditions of the fixed bed reaction zone are as follows: the reaction temperature is 340-500 ℃, the reaction pressure is 10-25 MPa, the volume ratio of hydrogen to oil is 300-1500, and the hourly space velocity of the raw oil is 0.15h -1 ～0.80 h -1 。
16. The fixed bed heavy oil hydrogenation process according to claim 1, wherein: and one or more of a hydrodesulphurisation catalyst, a hydrodenitrogenation catalyst and a carbon residue removal conversion catalyst are filled in the fixed bed reaction zone.
17. The fixed bed heavy oil hydrogenation process according to claim 1, wherein: the heavy oil raw material is normal pressure residual oil and/or vacuum residual oil, and does not contain or contains one or more of straight-run wax oil, vacuum wax oil, secondary processing wax oil and catalytic cycle oil; the properties of the heavy oil feedstock are: the sulfur content is not more than 4wt%, the nitrogen content is not more than 0.7wt%, the sum of the contents of metal Ni and metal V is not more than 120 mug/g, the carbon residue value is not more than 17wt%, and the asphaltene content is not more than 5wt%.
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