CN115466628A - Liquid-phase hydrogenation reaction device and system and hydrocarbon oil liquid-phase hydrogenation method - Google Patents
Liquid-phase hydrogenation reaction device and system and hydrocarbon oil liquid-phase hydrogenation method Download PDFInfo
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- 239000007791 liquid phase Substances 0.000 title claims abstract description 137
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 123
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 66
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 66
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000001257 hydrogen Substances 0.000 claims abstract description 216
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 216
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 136
- 239000012071 phase Substances 0.000 claims abstract description 66
- 239000007789 gas Substances 0.000 claims abstract description 57
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- 239000006185 dispersion Substances 0.000 claims description 6
- -1 polypropylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 239000002283 diesel fuel Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 13
- 238000012546 transfer Methods 0.000 abstract description 8
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A liquid phase hydrogenation reaction device, a liquid phase hydrogenation reaction system and a hydrocarbon oil liquid phase hydrogenation method are provided, wherein in the liquid phase hydrogenation reaction device, a reactor comprises a hydrogen mixing area (3) and a reaction area (15), the bottom of the hydrogen mixing area is communicated with the reaction area, and a hydrogenation catalyst is filled in the reaction area, wherein the hydrogen mixing area is provided with a liquid phase inlet (1), a gas phase inlet (5), a gas phase outlet (12) and a pressure detection device (9); the gas phase inlet and the gas phase outlet are respectively provided with a flow control valve; the reaction zone is provided with a liquid phase outlet (17) and a flow control valve. The liquid phase hydrogenation reaction device provided by the invention has the advantages of simple structure and simple and convenient operation. The hydrocarbon oil liquid phase hydrogenation method can reduce the resistance in the process of mass transfer and heat transfer in the process of mixing hydrogen/dissolving hydrogen, and improve the efficiency of dissolving hydrogen. The supplement amount of the hydrogen can be automatically supplemented according to the dissolution consumption amount, and the discharge loss of the hydrogen is reduced to the maximum extent.
Description
Technical Field
The invention relates to a reactor and a reaction method in the field of petrochemical industry, in particular to a hydrocarbon oil continuous hydrogenation reaction device and a hydrocarbon oil continuous hydrogenation reaction method.
Background
The hydrotreating technology can effectively remove S, N, O, metals, carbon residue and other impurities in petrochemical products, aromatic hydrocarbons, olefins and dialkenes in saturated or partially saturated hydrocarbon products, and realize the reaction processes of isomerization, cyclization, aromatization, cracking and the like of hydrocarbon molecules, and has very important function in the petrochemical production process.
At present, the hydrotreating process mostly adopts the traditional trickle bed technology. Most hydrogenation processes are strongly exothermic, and in order to take reaction heat to control the temperature of the reactor and to suppress side reactions such as catalyst carbon deposition, a conventional method adopts a large amount of hydrogen circulation, and the method needs to be provided with a complex hydrogen circulation system, so that the volume of the corresponding reactor is large, and the investment of the device and the energy consumption of operation are increased.
In order to overcome the disadvantages of the trickle bed hydrogenation, a liquid phase hydrogenation technique is proposed by technical researchers, which is to dissolve hydrogen in the raw oil to satisfy the hydrogen required for the hydrogenation reaction, and to dissolve sufficient hydrogen through liquid circulation to satisfy the requirement of the hydrogenation reaction, wherein the reaction is carried out under the liquid phase condition. The liquid phase hydrogenation process technology saves a circulating compressor system, a high-speed system and corresponding equipment thereof, and can greatly save investment and energy consumption. Meanwhile, the liquid phase hydrogenation process technology can eliminate the influence of the wetting factor of the catalyst, and the specific heat capacity of the circulating oil is large, so that the utilization efficiency of the catalyst is improved, the temperature rise of the reactor is greatly reduced, and side reactions such as cracking and the like are reduced.
US6213835, US6428686 disclose a hydrotreating process in which fresh feedstock and diluent, i.e. a material having a high solubility for hydrogen, such as recycled hydrocracked products, are first mixed with a large amount of hydrogen, and the resulting mixture is separated by a gas-liquid separation device to remove excess gas, and then the separated gas is introduced into a reactor to contact with a catalyst and undergo a reaction. Although the reactor part is a liquid phase system, excessive hydrogen is still premixed with raw materials and circulating materials, and the excessive hydrogen is discharged outside through gas-liquid separation. CN101280217A, CN105647577A and CN101787305A also adopt similar flow paths, and a gas-liquid separation device is arranged in front of the reactor. For the pre-hydrogen mixing process before the reactor, different methods can be adopted, for example, CN105733662A proposes to adopt a micro-bubble generator, the mixer used in CN103773441A is selected from a vortex mixer, a static mixer, or a jet mixer, and CN103666547A injects hydrogen into hydrocarbon oil through holes with average pore diameter of nanometer size, so as to achieve high dispersion of hydrogen and dissolve in hydrocarbon oil at a fast speed. CN208583196U discloses a novel hydrogen dissolver, which adopts a multilayer structure, each layer is provided with a dispersion plate, a membrane layer and an overflow baffle, wherein the membrane layer has micropores with nanometer-scale pore diameters. CN109731512A further adopts a micro-channel mixer with a complicated structure for mixing hydrocarbon oil and hydrogen.
From the prior art, the process of mixing hydrogen and dissolving hydrogen in reaction materials is an important link and a key step of a liquid phase hydrogenation technology. For the above-mentioned hydrogen mixing process, the most adopted method is to use hydrocarbon material flow as continuous phase, hydrogen as dispersed phase, and the dispersion of gas in hydrocarbon oil liquid phase is often uneven, so that the effect of hydrogen mixing and dissolving process is not good, and further the performance of catalyst and final reaction effect are affected, and the discharge of excessive hydrogen is also a waste of material and energy.
Disclosure of Invention
The invention aims to solve the technical problem of providing a liquid phase hydrogenation reaction device and a hydrocarbon oil hydrogenation method based on the prior art. By strengthening the dissolving and transferring processes of the hydrogen, the rapid dissolving balance of the hydrogen is realized, and the hydrogen utilization rate and the reaction efficiency in the hydrogenation process are improved.
The invention provides a liquid phase hydrogenation reaction device, which comprises a hydrogen mixing area I and a reaction area II, wherein the bottom of the hydrogen mixing area is communicated with the reaction area, and a hydrogenation catalyst is filled in the reaction area, wherein the hydrogen mixing area is provided with a liquid phase inlet 1, a gas phase inlet 5, a gas phase outlet 12 and a liquid level detection device 13, and the gas phase inlet and the gas phase outlet are respectively provided with a flow control valve; the reaction zone is provided with a liquid phase outlet 17 and a flow control valve, and the opening of the flow control valve in the reaction zone is interlocked with the liquid level of the hydrogen mixing zone.
A liquid phase hydrogenation reaction system is formed by connecting at least two liquid phase hydrogenation reaction devices in series or in parallel.
A hydrocarbon oil liquid phase hydrogenation method, adopt the above-mentioned liquid phase hydrogenation reaction unit, the hydrocarbon oil raw materials enter and mix the hydrogen zone and fully contact with hydrogen in disperse phase form to get the hydrocarbon oil raw materials of dissolving hydrogen, mix hydrogen zone keep liquid level height and mix hydrogen zone diameter ratio to be 0.2-1.0; the raw material of the hydrogen-dissolved hydrocarbon oil enters the reaction zone from the bottom of the hydrogen mixing zone and contacts with the hydrogenation catalyst to react to obtain a hydrocarbon oil hydrogenation product.
The liquid phase hydrogenation reaction device, the system and the method provided by the invention have the beneficial effects that:
compared with the prior art, the liquid phase hydrogenation reaction device provided by the invention has the advantages of simple structure and convenience in operation.
The liquid-phase hydrogenation reaction method for the hydrocarbon oil provided by the invention adopts a liquid-phase hydrogenation method, so that a complex circulating hydrogen system can be omitted, and the operation is simpler and easier. In the process of mixing hydrogen/dissolving hydrogen, liquid is used as a dispersion phase, and gas is used as a continuous phase, so that the resistance in the process of mass and heat transfer can be greatly reduced, and the hydrogen dissolving efficiency is improved. The supplement amount of the hydrogen can be automatically supplemented according to the dissolution consumption amount, and the discharge loss of the hydrogen is reduced to the maximum extent.
Drawings
FIG. 1 is a schematic flow diagram of a first embodiment of a liquid phase hydrogenation reactor;
FIG. 2 is a schematic diagram of a control scheme of a liquid phase hydrogenation reaction apparatus;
fig. 3 is a schematic flow chart of comparative examples 1 and 2.
Wherein:
1-liquid phase inlet 2-liquid distributor 3-hydrogen mixing zone
4-hydrogen mixing zone packing 5-gas phase inlet 6, 11, 16-flow regulating valve
7. 10-flow detection device 8-gas distributor 9-pressure detection device
12-gas phase outlet 13-liquid level detection equipment 14-pipeline
15-reaction zone 17- liquid phase outlets 18, 19, 20-control signals
21. 22, 23-control module 24-circulation line 25-circulation pump
26-static mixer
Detailed Description
The following describes the embodiments of the present invention in detail.
In a first aspect, the invention provides a liquid phase hydrogenation reaction device, wherein a reactor comprises a hydrogen mixing area I and a reaction area II, the bottom of the hydrogen mixing area is communicated with the reaction area, and a hydrogenation catalyst is filled in the reaction area, wherein the hydrogen mixing area is provided with a liquid phase inlet 1, a gas phase inlet 5, a gas phase outlet 12 and a liquid level detection device 13, and the gas phase inlet and the gas phase outlet are respectively provided with a flow control valve; the reaction zone is provided with a liquid phase outlet 17 and a flow control valve, and the opening of the flow control valve of the reaction zone is interlocked with the liquid level of the hydrogen mixing zone.
In the liquid phase hydrogenation reaction device provided by the invention, the top of the hydrogen mixing zone 3 is provided with a liquid phase inlet 1 and a gas phase outlet 12, and the bottom of the hydrogen mixing zone is provided with a gas phase inlet; the bottom of the hydrogen mixing zone is communicated with the bottom of the reaction zone through a pipeline, and the top of the reaction zone is provided with a liquid phase outlet.
Preferably, the hydrogen mixing area is provided with a pressure detection device (9) which is respectively provided with a flow control valve, and the opening degrees of the gas phase inlet flow control valve and the gas phase outlet flow control valve are interlocked with the pressure detection device.
Preferably, the liquid phase inlet is provided with a liquid distributor, the gas phase inlet is provided with a gas distributor, and the hydrogen mixing area is filled with a filler;
preferably, the liquid phase inlet is also provided with a pressure spraying device;
preferably, the filler is selected from polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) or surface modified metal fillers.
Preferably, the volume ratio of the hydrogen mixing area to the reaction area is (0.02-0.3) to 1, and the diameter ratio of the hydrogen mixing area to the reaction area is (0.5-2): 1; the height-diameter ratio of the catalyst bed layer in the reaction zone is (5-50): 1, and more preferably (8-30): 1.
Preferably, the reaction zone is filled with more than two catalyst beds, such as two different hydrogenation catalysts, or a hydrogenation protectant and a hydrogenation catalyst.
Preferably, a circulating pipeline and a circulating pump are arranged between the liquid phase outlet of the reaction zone and the liquid phase inlet of the hydrogen mixing zone.
Preferably, a feeding pump and a heat exchange device are further arranged and connected with the liquid phase inlet in series.
In the liquid phase hydrogenation reaction device provided by the invention, the reactor consists of a hydrogen mixing area and a reaction area, and the bottom of the hydrogen mixing area is communicated with the reaction area. The hydrogen mixing area is provided with pressure detection equipment and a liquid level meter, and the opening degree of the liquid phase outlet flow control valve of the reaction area and a liquid level monitoring signal of the hydrogen mixing area form a linkage control loop, so that the hydrogen mixing area can maintain stable liquid level.
In the first embodiment of the liquid phase hydrogenation reaction apparatus provided by the present invention, the hydrogen mixing zone and the reaction zone are respectively two independent cylinders, wherein the bottom of the hydrogen mixing zone is communicated with the bottom of the reaction zone through a pipeline, the fluid in the reaction zone adopts an upflow type, and the top of the reaction zone is provided with a liquid phase outlet. In the operation process of the device, after hydrocarbon oil raw materials enter the hydrogen mixing zone to complete hydrogen mixing and dissolving, reaction materials enter the reaction zone, pass through the hydrogenation catalyst bed layer from bottom to top, and are discharged from a liquid phase outlet at the top of the reaction zone. The opening degree of a flow control valve at the liquid phase outlet is interlocked with the liquid level of the hydrogen mixing area to control and maintain the full liquid phase operation of the reaction area, and the ratio of the liquid level height of the hydrogen mixing area to the hydrogen mixing area is controlled (0.2-1.0): 1.
In the second embodiment of the liquid phase hydrogenation reaction device provided by the invention, the bottom of the hydrogen mixing zone is communicated with the top of the reaction zone through a pipeline, the bottom of the reaction zone is provided with a liquid phase outlet, and the fluid in the reaction zone adopts an upflow type.
In a third embodiment of the liquid-phase hydrogenation reaction apparatus provided by the present invention, the hydrogen-mixing zone and the reactor share a cylinder, that is, in the same reactor, the upper part is the hydrogen-mixing zone, the lower part is the reaction zone, the top of the hydrogen-mixing zone is provided with a liquid-phase inlet and a gas-phase outlet, the bottom of the hydrogen-mixing zone is provided with a gas-phase inlet, the hydrogen-mixing zone is provided with a pressure detection device and a liquid level detection device, the bottom of the reaction zone is provided with a liquid-phase outlet, and the reaction zone is filled with a hydrogenation catalyst bed. In the operation process of the device, hydrocarbon oil raw materials enter the hydrogen mixing zone from a liquid phase inlet to complete hydrogen mixing and dissolving, then enter the reaction zone from the bottom of the hydrogen mixing zone and pass through the hydrogenation catalyst bed layer, and a liquid phase outlet at the bottom of the reaction zone discharges materials after reaction. The flow control valve at the outlet of the reaction zone and the liquid level of the hydrogen mixing zone are controlled in linkage and the full liquid phase operation of the reaction zone is maintained, and the ratio of the liquid level height of the hydrogen mixing zone to the hydrogen mixing zone is controlled to be (0.2-1.0): 1.
In the liquid phase hydrogenation reaction device provided by the invention, a hydrogenation catalyst is filled in the reaction zone, or the hydrogenation catalyst and other catalysts are filled in the reaction zone, and the other catalysts include but are not limited to a protective agent, an isomerization catalyst and the like. The catalyst in the reaction zone is preferably packed in a fixed bed and the reaction zone is packed with at least one bed of hydrogenation catalyst.
In the liquid phase hydrogenation reaction device provided by the invention, a liquid phase inlet is arranged at the top of the hydrogen mixing zone, preferably a liquid distributor is arranged at the liquid phase inlet, the liquid distributor is selected from, but not limited to, a coil pipe type, a calandria type and a branch pipe type liquid distributor, and a hydrocarbon oil raw material enters the hydrogen mixing zone from the liquid phase inlet at the top and the liquid distributor after being pressurized and subjected to heat exchange/heating by a feed pump. The liquid distributor preferably adopts pressure spraying equipment, the pressure drop of the distributor is 0.05 MPa-1.0 MPa, and the average diameter of the sprayed liquid drops is less than 2.0mm. The hydrocarbon oil feedstock is sprayed into the hydrogen-mixing zone in the form of droplets.
In the liquid phase hydrogenation reaction device provided by the invention, a gas phase inlet pipeline of the hydrogen mixing area is provided with a flow control valve, hydrogen enters the hydrogen mixing area through the gas phase inlet and the flow control valve, and the opening degree of the gas phase inlet flow control valve is controlled by the pressure detection or flow detection linkage of the hydrogen mixing area so as to control the flow of the supplemented hydrogen. And the opening of the flow control valve is interlocked with the pressure detection of the hydrogen mixing area to control the outflow flow of the hydrogen or the opening is set to fix the outflow displacement. The pressure in the hydrogen mixing zone is higher than that in the reaction zone, and the pressure difference is the static pressure difference of the liquid level at the bottom of the hydrogen mixing zone. Preferably, a gas phase inlet and a gas distributor are arranged at the bottom of the hydrogen mixing area, so that hydrogen uniformly enters the hydrogen mixing area, and preferably, gas-liquid countercurrent contact is performed.
In the hydrogen mixing area, the hydrocarbon oil material is preferably sprayed into liquid drops through a liquid distributor to enlarge the mass transfer surface with hydrogen, the hydrogen is a continuous phase, and the liquid is a dispersed phase. Another way to disperse the liquid is to fill the packing in the hydrogen mixing zone and disperse the liquid phase across the surface of the packing to provide a larger mass and heat transfer surface. The filler is regular or random, for hydrogenation of hydrocarbon oil, lipophilic filler is preferably used, and the average liquid film thickness on the surface of the filler is controlled to be less than 2.0mm.
Preferably, a circulating pipeline and a circulating pump are arranged between the liquid phase outlet of the reaction zone and the liquid phase inlet of the hydrogen mixing zone. Returning a part of the liquid phase circulating material to the liquid phase inlet of the hydrogen mixing zone. If the saturated dissolved hydrogen amount of the fresh hydrocarbon oil feed can satisfy the reaction hydrogen consumption, the liquid phase circulation loop may not be provided.
In a second aspect, the present invention provides a liquid phase hydrogenation reaction system, wherein a plurality of liquid phase hydrogenation reaction apparatuses are connected in series or in parallel. When the serial connection is adopted, the hydrogenation depth can be gradually increased; the device is connected in parallel, and when one liquid phase hydrogenation device is in the regeneration stage of the hydrogenation catalyst, at least one liquid phase hydrogenation device is in the reaction stage process, so that the continuous operation of the device is realized.
In a third aspect, the invention provides a hydrocarbon oil liquid phase hydrogenation method, which adopts the above liquid phase hydrogenation reaction device, wherein a hydrocarbon oil raw material enters a hydrogen mixing zone in a dispersion phase form and fully contacts with hydrogen to obtain a hydrogen-soluble hydrocarbon oil raw material, and the ratio of the height of a liquid level in the hydrogen mixing zone to the ratio of the height of the hydrogen mixing zone to the diameter of the hydrogen mixing zone (0.2-1.0) is 1; the hydrogen-dissolved hydrocarbon oil raw material enters the reaction zone from the bottom of the hydrogen mixing zone and contacts with the hydrogenation catalyst to react to obtain a hydrocarbon oil hydrogenation product.
Preferably, the reaction zone operating conditions are: the temperature is 50-500 ℃, the pressure is 0.5-25 MPa, and the total volume airspeed of the hydrocarbon oil is 0.1-20 h -1 Chemical reaction hydrogen consumption is 0.01 percent to 5 percent (w/w); the hydrogen consumption of the chemical reaction refers to the mass of hydrogen consumed by chemical reactions such as olefin saturation, desulfurization, denitrification, deoxidation, demetalization and the like in unit mass of feed.
Preferably, the pressure drop of the pressure spraying equipment at the top of the mixing zone is 0.05 MPa-1.0 MPa, and the average diameter of the sprayed liquid drops is less than 2.0mm.
Preferably, the proportion of recycled material is from 0.5 to 10, more preferably from 1 to 6.
In the liquid-phase hydrogenation method for hydrocarbon oil provided by the invention, the hydrocarbon oil raw material is selected from one or a mixture of more of C1-C4 light hydrocarbon, naphtha, gasoline, aviation kerosene, diesel oil, VGO and residual oil.
In the method for liquid-phase hydrogenation of hydrocarbon oil provided by the invention, the hydrocarbon oil raw material firstly passes through the hydrogen mixing zone to complete hydrogen mixing and dissolving and then flows to the reaction zone for reaction. In the process of carrying out hydrogen mixing and dissolving in the hydrogen mixing zone, the preferable method is that the feeding amount of hydrogen is automatically supplemented according to the dissolving consumption and the carrying amount of the liquid phase, and no hydrogen is discharged from the top of the hydrogen mixing zone or only a small amount of hydrogen is discharged to control the impurity level in the gas phase.
The reaction zone is filled with hydrogen or other catalyst, preferably in the form of a fixed bed, and the reaction zone comprises at least one catalyst bed. After the hydrogen mixing and dissolving in the hydrogen mixing zone, the materials can be fed up and discharged down or fed down and discharged up and down on the catalyst bed layer, and the reaction zone is maintained to be full of liquid phase by adopting different connection modes of the hydrogen mixing zone and the reaction zone and a system linkage control scheme, so that the reaction is carried out under the condition of full liquid phase.
When the reaction materials are in an upper inlet and lower outlet mode, the hydrogen mixing zone and the reaction zone preferably share one cylinder and are arranged up and down, and the volume ratio of the hydrogen mixing zone to the reaction zone is (0.02-0.3): 1, the ratio of the diameter of the hydrogen mixing zone to the diameter of the reaction zone (0.5-2): 1. the gas phase in the hydrogen mixing area is a continuous phase, the liquid is a dispersed phase, and the air inflow can be controlled by flow or can be automatically supplemented by pressure control; the continuous phase in the reaction zone is hydrogen saturated liquid, and the liquid level control of the hydrogen mixing zone is linked with an outlet pipeline control valve of the reaction zone; when the reaction materials are in a downward-feeding and upward-discharging mode, the hydrogen mixing zone and the reaction zone are preferably arranged in a split mode, the bottom of the hydrogen mixing zone is communicated with a liquid phase inlet at the bottom of the reaction zone through a pipeline, a gas phase in the hydrogen mixing zone is a continuous phase, a liquid phase is a dispersed phase, and a certain liquid level is maintained at the bottom of the hydrogen mixing zone. After hydrogen mixing and dissolving are completed in the hydrogen mixing area, the material enters the reaction area from the bottom through a pipeline to be in contact reaction with the hydrogenation catalyst, and a liquid phase outlet control valve of the reaction area is interlocked with the liquid level of the hydrogen mixing area so as to control the liquid level stability of the hydrogen mixing area.
Preferably, a part of the liquid phase recycle material is returned to the liquid phase inlet of the hydrogen mixing zone to increase the total amount of hydrogen dissolved in the liquid phase stream and reach the required level of reaction hydrogen consumption. If the saturated dissolved hydrogen content of the fresh hydrocarbon oil feed can satisfy the reaction hydrogen consumption, the proportion of the recycled materials can be reduced.
The hydrogenation reaction can be a reaction process requiring hydrogen participation, such as hydrotreating, hydrofining, hydrocracking, hydrogenation saturation, hydroisomerization and the like.
The following describes in detail embodiments of the present invention with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration and explanation only and are not intended to limit the scope of the invention.
FIG. 1 is a schematic flow diagram of one embodiment of a liquid phase hydrogenation reactor. As shown in FIG. 1, the hydrogenation reaction system is divided into a hydrogen mixing zone 3 and a reaction zone 15, which are communicated with each other through a pipeline 14. The top of the hydrogen mixing area 3 is provided with a liquid phase inlet 1 and a gas phase outlet 12, and the hydrocarbon oil raw material enters the hydrogen mixing area 3 from the liquid phase inlet 1 through a liquid distributor 2. Regular or random packing is filled in the hydrogen mixing area 3. The bottom of the hydrogen mixing area is provided with a gas phase inlet 5 and a flow control valve 6, and hydrogen enters and fills the hydrogen mixing area through the gas phase inlet 5 and the flow control valve 6 and is in gas-liquid countercurrent contact with the hydrocarbon oil raw material for mass transfer. The reaction material after the hydrogen mixing and dissolving in the hydrogen mixing zone enters a reaction zone 15 through a pipeline 14, a hydrogenation catalyst is filled in the reaction zone, and the reaction material passes through a catalyst bed layer from bottom to top and contacts with the hydrogenation catalyst to carry out liquid-phase hydrogenation reaction. The top of the reaction zone 15 is provided with a liquid phase outlet 17 and a liquid phase outlet flow valve 16. A material circulating pipeline 24 and a circulating pump 25 are arranged between the liquid phase outlet 17 and the liquid phase inlet 1, and part of hydrogenated materials are circularly returned to the hydrogen mixing area 3 to increase the total hydrogen dissolving amount of liquid phase material flow and reach the required level of reaction hydrogen consumption. The pressure stability of the hydrogen mixing zone is controlled by controlling the opening degree of the gas phase inlet flow control valve 6 and the flow control valve 11 of the gas phase outlet.
FIG. 2 is a schematic diagram of a control system for a liquid phase hydrogenation reactor. As shown in FIG. 2, a liquid level detection device 13 is arranged at the bottom of the hydrogen mixing area 3. The liquid phase outlet flow valve is interlocked with the liquid level detection equipment of the hydrogen mixing area to control the opening of the flow valve, maintain stable liquid level in the hydrogen mixing area 3 and operate in full liquid phase in the reaction area 15. The hydrogen mixing area 3 is also provided with a pressure detection device 9, the gas phase inlet is also provided with a flow monitoring device 7, the gas phase outlet is provided with a flow monitoring control device 10, the opening degree of the gas phase inlet flow control valve 6 and the opening degree of the gas phase outlet flow control valve 11 in the hydrogen mixing area are in interlocking control with the pressure detection device, and the inflow and outflow of hydrogen are controlled so as to maintain the pressure stability in the hydrogen mixing area 3.
The present invention is further illustrated by the following examples. And the invention is not to be restricted in any way thereby.
Comparative example 1
Comparative example 1 is a hydrogenation and de-olefination process of reformate using a liquid phase hydrogenation mode. The hydrocarbon oil raw material adopts reformed oil obtained from Yanshan petrochemical company of China petrochemical company, the properties of the raw oil are shown in Table 1, and the hydrogenation catalyst is produced by Chang mountain division of China petrochemical catalyst company, the trade name of which is TORH-1.
The process flow is shown in figure 3, a hydrogenation catalyst bed layer is filled in a hydrogenation reactor 15, and the height-diameter ratio of the reactor is 20. The hydrocarbon oil raw material 1 is subjected to heat exchange, mixed with hydrogen 5 through a static mixer 26, and then fed into a hydrogenation reactor 15 to contact with a hydrogenation catalyst for hydrogenation reaction, and the reacted material is discharged through a product outlet 17. The reaction temperature is 120 ℃, the reaction pressure is 2.0MPa, and the mass space velocity is 10.0h -1 The hydrogen-oil volume ratio was 6.0, and no circulation was provided for the liquid feed in comparative example 1. The reaction product properties are shown in Table 2.
Example 1
The liquid phase hydrogenation reaction device shown in the attached figure 1 is adopted, wherein a hydrogen mixing zone is communicated with a reaction zone through a pipeline 14, the volume ratio of the hydrogen mixing zone to the reaction zone is 0.2, the hydrogen mixing zone and the reaction zone have the same diameter, and Polytetrafluoroethylene (PTFE) corrugated packing, necessary packing support plates, liquid distributors and other members are arranged in the hydrogen mixing zone. The reaction zone was filled with a hydrogenation catalyst, and the height/diameter ratio of the catalyst bed was 20. The gas phase inlet at the bottom of the hydrogen mixing area is provided with a single-ring tubular gas distributor, and the diameter of a gas hole is 2mm.
The hydrocarbon oil raw material enters a hydrogen mixing zone 3 from a liquid phase inlet 1 through a liquid distributor 2. Hydrogen enters and fills the hydrogen mixing area through the gas phase inlet 5 and the flow control valve 6, and is in gas-liquid countercurrent contact mass transfer with hydrocarbon oil raw material. The reaction material after dissolving hydrogen in mixed hydrogen enters the reaction zone 15 through the pipeline 14, passes through the catalyst bed layer from bottom to top, and contacts with the hydrogenation catalyst to carry out liquid phase hydrogenation reaction. The hydrogenated material is discharged through a liquid phase outlet 17 without material circulation. The opening of the gas-phase inlet flow control valve 6 and the pressure of the hydrogen mixing area are interlocked to control the hydrogen feeding to be automatically supplemented, the hydrogen at the top of the hydrogen mixing area is not extracted, and the actually measured hydrogen-oil volume ratio is 5.5. The opening degree of a flow regulating valve at a liquid phase outlet of the reaction zone is controlled in linkage with the liquid level of the hydrogen mixing zone, and the liquid level control height of the hydrogen mixing zone is 0.5 times of the diameter of the hydrogen mixing zone.
The hydrocarbon oil feedstock, hydrogenation catalyst and other reaction conditions were the same as in comparative example 1. The reaction results are shown in Table 2.
Comparative example 2
Comparative example 2 is a diesel hydrofinishing process. The process flow is shown in figure 3, the height-diameter ratio of the reactor 15 is 16, and a hydrogenation catalyst bed layer is filled. The hydrocarbon oil raw material 1 and the low-pressure degassed circulating oil from the circulating pipeline 24 and the hydrogen 5 enter from the bottom of the reactor 15 after being mixed by the static mixer 26, contact with the hydrogenation catalyst to carry out hydrogenation reaction, the reacted material is discharged through the product outlet 17, and part of the reacted material returns to the reactor through the circulating pipeline 24. The reaction temperature is 365 ℃, the reaction pressure is 8.0MPa, and the volume space velocity is 1.6h -1 The volume ratio of hydrogen to oil is 150, and the circulation ratio of the circulating material to the hydrocarbon oil raw material is 3. The reaction product properties are shown in Table 4.
Wherein, the hydrocarbon oil raw material adopts diesel oil fraction taken from Yanshan petrochemical company of China petrochemical company Limited, and the properties are shown in Table 3. The commercial brand of the hydrogenation catalyst is RS-1000, and is produced by catalyst division of China petrochemical Co.
Example 2
Example 2a liquid phase hydrogenation reaction apparatus shown in fig. 2 was used, in which the volume ratio of the hydrogen mixing zone to the reaction zone was 0.1, the hydrogenation catalyst was packed in the reaction zone, and the height/diameter ratio of the catalyst bed was 16. The top of the hydrogen mixing area is provided with a spray type liquid distributor, the diameter of a spray hole is 3.5mm, and the spray pressure drop is 0.15MPa. The hydrogen mixing zone is not filled with filler. The hydrogen mixing area is provided with a pressure detection device 9 and a liquid level detection device 13. The opening degree of a gas phase outlet flow regulating valve at the top of the hydrogen mixing area is interlocked with the pressure of the hydrogen mixing area to maintain the reaction pressure, the flow of a hydrogen inlet is fixed, and the hydrogen-oil ratio at the inlet is controlled to be 150. The opening degree of a liquid phase outlet flow regulating valve of the reaction area is linked with the liquid level at the bottom of the hydrogen mixing area, so that the liquid level in the hydrogen mixing area is maintained to be stable, and the liquid level height of the hydrogen mixing area is controlled to be 0.6 times of the diameter of the hydrogen mixing area, so that the liquid phase hydrogenation reaction in the reaction area is facilitated.
The hydrocarbon oil raw material enters a hydrogen mixing zone 3 from a liquid phase inlet 1 through a liquid distributor 2. Hydrogen enters and fills the hydrogen mixing area through the gas phase inlet 5 and the flow control valve 6, and is in gas-liquid countercurrent contact mass transfer with hydrocarbon oil raw material. The reaction material after dissolving hydrogen in mixed hydrogen enters the reaction zone 15 through the pipeline 14, passes through the catalyst bed layer from bottom to top, and contacts with the hydrogenation catalyst to carry out liquid phase hydrogenation reaction. The hydrogenated material is discharged through a liquid phase outlet 17, and part of the hydrogenated material returns to the hydrogen mixing area through a circulating pipeline 24 and a circulating pump 25.
Wherein, the hydrocarbon oil raw material, the hydrogenation catalyst and other reaction conditions were the same as in comparative example 2. The reaction results are shown in Table 4. As can be seen from table 4, the hydrogenation effect of example 2 was improved when the hydrogen oil volume ratio was decreased.
TABLE 1 reformate feedstock Properties
TABLE 2 reformate hydrogenation results
| Item | Comparative example 1 | Example 1 |
| Aromatic loss in wt% | 0.05 | 0.03 |
| Bromine index of hydrogenated product, mgBr/100g | 230 | 120 |
TABLE 3 Diesel feedstock Properties
TABLE 4 Diesel oil hydrorefining reaction results
| Item | Comparative example 2 | Example 2 |
| Sulfur content, μ g/ |
12 | 6 |
| Nitrogen content,. Mu.g/g | 0.4 | ＜0.2 |
Claims (12)
1. The liquid phase hydrogenation reaction device is characterized in that a reactor comprises a hydrogen mixing area (3) and a reaction area (15), the bottom of the hydrogen mixing area is communicated with the reaction area, a hydrogenation catalyst is filled in the reaction area, wherein the hydrogen mixing area is provided with a liquid phase inlet (1), a gas phase inlet (5), a gas phase outlet (12) and a liquid level detection device (13), and the gas phase inlet and the gas phase outlet are respectively provided with a flow control valve; the reaction zone is provided with a liquid phase outlet (17) and a flow control valve, and the opening degree of the flow control valve of the liquid phase outlet of the reaction zone is controlled by the liquid level linkage of the hydrogen mixing zone.
2. The liquid phase hydrogenation reaction apparatus according to claim 1, wherein the top of the hydrogen mixing zone (3) is provided with a liquid phase inlet (1) and a gas phase outlet (12), and the bottom of the hydrogen mixing zone is provided with a gas phase inlet (5); the bottom of the hydrogen mixing zone is communicated with the bottom of the reaction zone through a pipeline, and the top of the reaction zone is provided with a liquid phase outlet (17).
3. The liquid phase hydrogenation reaction apparatus according to claim 1, wherein said hydrogen-mixing zone is provided with a pressure detecting means (9) respectively provided with a flow control valve, and the opening degrees of said gas phase inlet flow control valve and said gas phase outlet flow control valve are interlocked with said pressure detecting means.
4. The liquid-phase hydrogenation reaction apparatus according to claim 1, 2 or 3, wherein said liquid-phase inlet is provided with a liquid distributor, said gas-phase inlet is provided with a gas distributor, and said hydrogen-mixing zone is filled with a filler;
preferably, the liquid phase inlet is also provided with a pressure spraying device;
preferably, the filler is selected from polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) or surface modified metal fillers.
5. The liquid-phase hydrogenation reaction apparatus according to claim 1, 2 or 3, wherein the volume ratio of the hydrogen-mixing zone to the reaction zone is (0.02 to 0.3): 1, and the diameter ratio of the hydrogen-mixing zone to the reaction zone is (0.5 to 2): 1; the height-diameter ratio of the catalyst bed layer in the reaction zone is (5-50): 1;
preferably, the height-diameter ratio of the catalyst bed layer in the reaction zone is (8-30): 1;
preferably, the reaction zone is filled with more than two catalyst beds.
6. The liquid-phase hydrogenation reaction apparatus according to claim 1, 2 or 3, wherein a circulation line and a circulation pump are provided between the liquid-phase outlet of said reaction zone and the liquid-phase inlet of said hydrogen-mixing zone.
7. A liquid phase hydrogenation reaction system characterized in that at least two liquid phase hydrogenation reaction apparatuses according to any one of claims 1 to 6 are connected in series or in parallel.
8. A liquid phase hydrogenation method for hydrocarbon oil adopts the liquid phase hydrogenation reaction device of any one of claims 1 to 6, the hydrocarbon oil raw material enters a hydrogen mixing area in a dispersion phase form and fully contacts with hydrogen to obtain a hydrogen-dissolved hydrocarbon oil raw material, the ratio of the liquid level height in the hydrogen mixing area to the hydrogen mixing area is maintained to be (0.2-1.0): 1, and the hydrogen-dissolved hydrocarbon oil raw material enters a reaction area from the bottom of the hydrogen mixing area and contacts with a hydrogenation catalyst to carry out hydrogenation reaction to obtain a hydrocarbon oil hydrogenation product.
9. The liquid phase hydrogenation method for hydrocarbon oil according to claim 8, wherein the hydrocarbon oil raw material enters the hydrogen mixing zone in a dispersed phase form through a pressure spraying device, the pressure drop of the pressure spraying device is 0.05MPa to 1.0MPa, and the average diameter of the sprayed liquid drops is less than 2.0mm.
10. The liquid-phase hydrogenation process for hydrocarbon oil according to claim 8 or 9, wherein the temperature of the reaction zone is 50 ℃ to 500 ℃The pressure is 0.5-25 MPa, and the total volume airspeed of the hydrocarbon oil is 0.1-20 h -1 The hydrogen consumption of the chemical reaction is 0.01 percent to 5 percent (w/w);
preferably, the pressure difference between the hydrogen mixing zone and the reaction zone is 0.005-0.05MPa.
11. The liquid-phase hydrogenation method for hydrocarbon oil according to claim 8, wherein the hydrocarbon oil feedstock is selected from one or more of C1-C4 light hydrocarbons, naphtha, gasoline, aviation kerosene, diesel oil, VGO, and residual oil.
12. The liquid-phase hydrogenation method for hydrocarbon oil according to claim 8, wherein a part of the product of hydrogenation of hydrocarbon oil is returned to the hydrogen-mixing zone as a recycle material, and the weight ratio of the recycle material to the hydrocarbon oil raw material is 0.5 to 10; preferably 1 to 6.
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