CN218290813U - Hydrocarbon oil hydrogenation reaction device - Google Patents

Abstract

The utility model provides a hydrocarbon oil hydrogenation reaction unit, including first reactor and second reactor, wherein from top to bottom set up in the first reactor and dissolve hydrogen section and at least one section catalyst bed, the raw materials entry and the setting at reactor top dissolve the spray liquid distributor intercommunication in the hydrogen section, it is equipped with the gas phase entry to dissolve the hydrogen section, the export of first reactor bottom is through export flow control valve (9) and the raw materials entry intercommunication at second reactor top, still be equipped with make-up hydrogen pipeline (4) intercommunication second reactor, be equipped with the catalyst bed in the second reactor, second reactor bottom export intercommunication gas-liquid separation equipment (12). The utility model provides a hydrocarbon oil hydrotreating system can carry out nimble adjustment according to the difference of hydrogenation process mass transfer control step, improves hydrogenation reaction efficiency.

Description

Hydrocarbon oil hydrogenation reaction device

Technical Field

The utility model relates to a reaction unit in petrochemical field, more specifically say, relate to a continuous hydrotreating reaction unit of hydrocarbon oil.

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 reaction processes of isomerization, cyclization, aromatization, cracking and the like of hydrocarbon molecules, and has very important function in the production process of the petrochemical products.

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 a 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 a reactor is greatly reduced, and side reactions such as cracking and the like are reduced.

The main difficulty of liquid phase hydrogenation is the dissolution and make-up of hydrogen. US6213835, US6428686 disclose a hydrotreating process in which a fresh feedstock and a diluent, which is a substance having a high solubility for hydrogen, such as a recycled hydrocracked product, are 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 react with the catalyst. Similar procedures are also adopted in chinese patents CN101280217A, CN105647577A and CN101787305A, but different methods can be adopted for the pre-mixing hydrogen process before the reactor, for example, CN105733662A proposes to use a micro bubble generator, CN103773441A uses a mixer selected from a vortex mixer, a static mixer, or a jet mixer, and CN103666547A injects hydrogen into the hydrocarbon oil through a through hole with a nanometer size average aperture, so as to achieve high dispersion of hydrogen and dissolve the hydrogen in the hydrocarbon oil at a faster speed.

Among the two different technologies, the trickle bed technology generally requires a large hydrogen circulation amount in order to control reaction heat, and the device energy consumption is relatively high, but simultaneously has high mass transfer efficiency due to the characteristics of high fluid flow rate, small liquid film mass transfer resistance, fast catalyst surface updating and the like in the operation process. The liquid phase hydrogenation technology does not need a gas compressor, the reactor is small in size, the reaction temperature rise is small by adopting a liquid phase main body to absorb heat, but the liquid phase mass transfer resistance is large, the primary hydrogen dissolving amount cannot meet the requirement of chemical consumption, and the like, so that the application range of the liquid phase hydrogenation technology is influenced.

SUMMERY OF THE UTILITY MODEL

The to-be-solved technical problem of the utility model is to the problem that current trickle bed or liquid phase hydrogenation process exist, provide a hydrocarbon oil hydrogenation reaction unit.

The utility model provides a hydrocarbon oil hydrogenation reaction unit, including first reactor and second reactor, wherein set up from top to bottom in the first reactor and dissolve hydrogen section and one section at least catalyst bed, the raw materials entry and the fountain liquid distributor intercommunication of setting in dissolving the hydrogen section at reactor top, it is equipped with the gaseous phase entry to dissolve the hydrogen section, the export of first reactor bottom is through the raw materials entry intercommunication at export flow control valve and second reactor top, still be equipped with supplementary hydrogen pipeline intercommunication second reactor, be equipped with the catalyst bed in the second reactor, export intercommunication gas-liquid separation equipment bottom the second reactor.

The utility model provides an application method of hydrocarbon oil hydrogenation reaction device, hydrogen is introduced into the first reactor from the gas phase inlet, hydrocarbon oil raw materials enter the first reactor from the raw material inlet, and are dispersed into tiny liquid drops through the spray type liquid distributor, and the liquid drops contact with hydrogen in the hydrogen dissolving section to reach hydrogen saturation; the hydrocarbon oil saturated by hydrogen takes a liquid phase as a continuous phase to contact with a catalyst bed layer to carry out hydrogenation reaction, the reacted hydrocarbon oil and the supplementary hydrogen are mixed and then enter a second reactor, the hydrogen is taken as the continuous phase, the hydrocarbon oil contacts with the catalyst in a trickle mode to further carry out hydrogenation reaction, and a reaction product enters gas-liquid separation equipment from a bottom outlet to carry out gas-liquid separation, so that the hydrotreated hydrocarbon oil is obtained.

The hydrocarbon oil hydrogenation reaction device and the application method provided by the utility model have the beneficial effects that:

compared with the prior art, the utility model provides a hydrocarbon oil hydrogenation reaction unit adopts liquid phase hydrogenation ware and gas phase bed hydrogenation ware series connection, simple structure, convenient operation. A hydrogen dissolving section is arranged in the liquid phase hydrogenation reactor, and a spray type liquid distributor is adopted to carry out micro-dispersion on the liquid phase hydrocarbon oil raw material, so that an extremely large gas-liquid mass transfer specific surface is obtained, and the dissolution saturation of hydrogen in hydrocarbon oil is accelerated. The device provided by the utility model be applied to hydrocarbon oil hydrogenation reaction technology, can exert liquid phase hydrogenation and gas phase bed hydrogenation's advantage separately, overcome not enough each other, reduce the reaction temperature rise, reduced circulating oil and circulating hydrogen quantity, obviously improve mass transfer and reaction efficiency.

Drawings

FIG. 1 is a schematic flow diagram of a hydrocarbon oil hydrogenation reactor provided by the present invention.

FIG. 2 is a schematic diagram of an intermediate gas distributor.

Fig. 3 is a schematic diagram of a micro-nano porous tube installation method.

Wherein:

a-first reactor B-second reactor 1-feed inlet

2-spray type liquid distributor 3-hydrogen main pipe 4-supplementary hydrogen pipeline

5-gas phase inlet 6-intermediate hydrogen pipeline 7-gas phase inlet flow regulating valve

8-intermediate gas distributor 9-outlet flow regulating valve 10, 11, 13, 14-pipeline

12-gas-liquid separation apparatus

FIG. 4 is a schematic flow chart of a hydrocarbon oil hydrotreating process employed in comparative example 1.

FIG. 5 is a schematic flow chart of a process for hydrotreating a hydrocarbon oil employed in comparative example 2.

Wherein:

1-raw material pipeline 2-hydrogen pipeline 3-hydrogenation reactor

4-gas-liquid separation tank 5-gas phase pipeline 6-liquid phase pipeline

7-line 8-reactor top outlet 9-static mixer

Detailed Description

The following describes the embodiments of the present invention in detail.

In the present application, the terms "upper", "lower" and "bottom" are used in reference to the relative positional relationship of the container or the member. Wherein, the bottom refers to the position of 0-10% of the container from bottom to top, and the top refers to the position of 90-100% of the container from bottom to top.

The utility model provides a hydrocarbon oil hydrogenation reaction unit, including first reactor and second reactor, wherein set up from top to bottom in the first reactor and dissolve hydrogen section and one section at least catalyst bed, the raw materials entry and the fountain liquid distributor intercommunication of setting in dissolving the hydrogen section at reactor top dissolve the hydrogen section, it is equipped with the gas phase entry to dissolve the hydrogen section, the export of first reactor bottom is through the raw materials entry intercommunication at export flow control valve and second reactor top, still be equipped with make-up hydrogen pipeline intercommunication second reactor, be equipped with the catalyst bed in the second reactor, export intercommunication gas-liquid separation equipment bottom the second reactor.

Preferably, the aspect ratio of the first reactor is 8 to 30:1. wherein the hydrogen dissolving section is 2-10% of the total height of the first reactor. Typically, the height of the hydrogen-solubilizing segment is from 0.5 to 2.0m.

Preferably, the height to diameter ratio of the second reactor is 10 to 40:1.

preferably, the gas phase outlet of the gas-liquid separation device is communicated with the gas phase inlet and the make-up hydrogen pipeline through a pipeline.

Preferably, the bottom of the hydrogen dissolving section is provided with a gas phase inlet, a gas phase inlet flow regulating valve and liquid level detection equipment, and the upper part of the hydrogen dissolving section is provided with pressure detection equipment; the pressure detection equipment adjusts the reaction pressure in a linkage manner through the control system and the gas phase inlet flow regulating valve, and the liquid level detection equipment adjusts the liquid level height in the hydrogen dissolving section in a linkage manner through the control system and the outlet flow regulating valve.

Preferably, two or more catalyst beds are provided in the first reactor, and the intermediate hydrogen line 6 is in communication with an intermediate gas distributor provided between adjacent catalyst beds. More preferably, the first reactor is packed with 2-5 catalyst beds.

Preferably, the middle gas distributor is in a structure that the annular main pipe is communicated with the micro-nano porous pipe through a connecting pipe, the micro-nano porous pipe is uniformly distributed along the circumference of the annular main pipe, and the pore diameter of the micro-nano porous pipe is smaller than 10 micrometers.

Preferably, the micro-nano porous tube is inclined downwards and is positioned below the plane of the annular manifold.

Preferably, the height-diameter ratio of the micro-nano porous tube is 0.3-2.0:1.

the utility model provides an among the hydrocarbon oil hydrogenation reaction unit, pressure measurement equipment pass through control system and the chain regulation reaction pressure of gaseous phase entry flow control valve, liquid level measurement equipment pass through control system and the chain regulation of export flow control valve and dissolve hydrogen section interior liquid level height.

Preferably, the liquid level detection device is arranged at the bottom of the hydrogen dissolving section and is used for detecting the liquid level exceeding the first section of catalyst bed layer at the middle upper part of the first reactor.

Preferably, the gas phase outlet of the gas-liquid separation device is communicated with the hydrogen inlet pipeline through a pipeline.

The utility model provides an application method of hydrocarbon oil hydrogenation reaction device, which adopts the hydrocarbon oil hydrogenation reaction device, the hydrocarbon oil raw material enters into the first reactor from the raw material inlet, and is dispersed into tiny liquid drops through the spray type liquid distributor, and the liquid drops contact with hydrogen in the hydrogen dissolving section to quickly reach hydrogen saturation; the hydrocarbon oil saturated by the hydrogen takes a liquid phase as a continuous phase to contact with a catalyst bed layer to carry out hydrogenation reaction, the reacted hydrocarbon oil and the supplemented hydrogen are mixed and then enter a second reactor, the hydrogen is taken as the continuous phase, the hydrocarbon oil contacts with the catalyst in a trickle mode to carry out further hydrogenation reaction, and a reaction product enters gas-liquid separation equipment from a bottom outlet to carry out gas-liquid separation, so that the hydrocarbon oil after hydrogenation treatment is obtained.

Wherein, the pressure drop of the spray type liquid distributor is 0.1 MPa-1.0 MPa, and the hydrocarbon oil raw material is dispersed into tiny liquid drops with the grain diameter less than 1.0mm through the spray type liquid distributor.

In the first reactor, small bubbles generated by dispersing hydrogen from a middle hydrogen pipeline through a middle distributor and liquid-phase reactants flow from top to bottom into the next section of catalyst bed layer and are dissolved for supplement reaction consumption, generated large bubbles upwards enter the previous section of catalyst bed layer and are in countercurrent contact with liquid-phase reactant flow for mass transfer and reaction, and the residual hydrogen enters a hydrogen dissolving section and is subjected to secondary dissolution and utilization.

Wherein the operating conditions of the first reactor are as follows: the temperature is 150-500 ℃, the pressure is 1.0-25 MPa, the volume ratio of hydrogen to oil is 20-200, and the volume airspeed is 0.2-10 h ^-1 (ii) a The operating conditions of the second reactor were: the temperature is 150-500 ℃, the pressure is 0-2.0 MPa higher than that of the first reactor, the volume ratio of hydrogen oil for supplementing hydrogen is 50-500, and the volume space velocity is 0.1-5.0 h ^-1 (ii) a The total hydrogen consumption of the two reactors in the chemical reaction is 0.5-5.0% (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.

Wherein, the operation conditions of the reactors are used for controlling the first reactor to finish 60 to 95 percent of the total conversion reaction, and the second reactor to finish 5 to 40 percent of the total conversion reaction.

The utility model provides a preferred embodiment of device, the liquid phase entry pipeline and the spray liquid distributor that first reactor top dissolved hydrogen section was equipped with communicate with each other, spray liquid distributor preferably adopt branch tubular structure, liquid sprays and adopts pressure type shower nozzle, the shower nozzle even install on corresponding branch pipe. The beneficial effects of the preferred embodiment are that the spraying liquid phase distributor is adopted to carry out micro-dispersion on the liquid phase hydrocarbon oil raw material, so that a very large gas-liquid mass transfer specific surface is obtained, and the dissolution saturation of hydrogen in hydrocarbon oil is accelerated.

The utility model provides a preferred embodiment of device sets up two sections at least catalyst bed in the first reactor, sets up middle gas distributor between the adjacent catalyst bed, and middle gas distributor adopts the annular tube formula, middle hydrogen pipeline intercommunication annular house steward, evenly distributed on the annular house steward micro-nano perforated pipe as the component of laying gas, it is continuous through the connecting pipe in the middle of component of laying gas and the annular house steward. More preferably, the micro-nano porous pipe gas distribution member has the same direction as the flow direction of the hydrocarbon oil, namely, the inlet end of the connecting pipe connected with the annular main pipe faces upwards, and the outlet end connected with the micro-nano porous pipe gas distribution member faces downwards. The aperture of the micro-nano porous tube is less than 10 microns, and the height-diameter ratio of the porous tube is 0.3-2.0:1, the interval between adjacent micro-nano porous tubes is not less than 200mm.

The preferred embodiment has the beneficial effects that the micro-nano porous tube with the pore diameter smaller than 10 microns disperses the supplementary hydrogen into bubbles with different sizes, wherein the small bubbles and the liquid-phase reactant flow downwards to enter the next section of catalyst bed layer and are dissolved for consumption of the supplementary reaction; the generated large bubbles upwards pass through the previous section of catalyst bed layer and are in countercurrent contact with the liquid phase reaction material for mass transfer and reaction, and the residual hydrogen finally enters the hydrogen dissolving section for secondary dissolution and utilization. The hydrogen utilization rate is improved to the maximum extent by respectively controlling the hydrogen bubbles with different sizes.

The device provided by the utility model in, dissolve hydrogen section lower part and be equipped with the gaseous phase entry and link to each other with gaseous phase entry pipeline, be equipped with flow automatic regulating valve on the gaseous phase entry pipeline, gaseous phase entry pipeline flow regulating valve with pressure measurement equipment chain, through the pressure in the feedback control system regulation reactor.

The utility model provides a preferred embodiment of device, the bottom outlet pipeline of first reactor communicates with each other with the raw materials entry at second reactor top after merging with supplementary hydrogen pipeline, introduces one supplementary hydrogen to the second reactor through supplementary hydrogen pipeline for it is inequality in hydrogen-oil volume ratio and the first reactor in the adjustment second reactor.

The utility model provides an among the device, the different catalyst bed of first reactor is filled with the same or different hydrogenation catalyst, like hydrogenation protective agent and/or hydrogenation catalyst, wherein catalyst filling void fraction is not less than 40% in the first section catalyst bed. The second reactor is the same as or different from the first reactor in the filled hydrogenation catalyst.

The outlet at the bottom of the second reactor is communicated with a gas-liquid separation device, preferably a gas-liquid separation tank. The material flow after the reaction enters gas-liquid separation equipment for gas-liquid separation, and the separated gas phase is led out through a gas phase outlet pipeline for subsequent treatment, or is extracted, or is returned to the reactor as circulating hydrogen; the separated liquid phase product is led out through a liquid phase outlet pipeline and sent to a subsequent unit for product separation and other operations.

The device provided by the utility model when using, fresh hydrocarbon oil raw materials disperse into small liquid drop at first reactor top through fountain liquid distributor, and the liquid drop contacts and reaches the hydrogen saturation fast with hydrogen in dissolving the hydrogen section. The pressure drop of the spray type liquid distributor is 0.1 MPa-1.0 MPa, the diameter of the hydrocarbon oil liquid drop is less than 1.0mm, so that a very large gas-liquid interphase mass transfer surface is obtained, and the liquid drop can reach hydrogen saturation in a very short time.

The bottom of the hydrogen dissolving section is provided with a gas phase inlet and a gas phase inlet flow regulating valve, the feeding flow of the hydrogen is automatically controlled through the gas phase inlet flow regulating valve, and the opening of the regulating valve is interlocked with a measuring signal of the pressure detection equipment.

The liquid drops after being sprayed are converged into a liquid phase main fluid before entering a first section of catalyst bed layer, the height of the liquid level above the first section of catalyst bed layer is measured by liquid level detection equipment, a detection signal is linked with a flow regulating valve on an outlet pipeline at the bottom of a first reactor through a control system, the height of the liquid level is controlled within a required range through the change of the opening degree of the regulating valve, and the height of the liquid level above the catalyst bed layer is preferably controlled to be 0.05-0.2 times of the diameter of the reactor.

The hydrocarbon oil saturated by hydrogen enters a catalyst bed layer as a continuous phase to contact with the catalyst and partially react. Hydrogen introduced through the middle hydrogen pipeline enters the reactor through a middle gas distributor provided with a micro-nano porous pipe, the generated bubbles have the diameter distribution, bubbles with smaller diameters are carried by hydrocarbon material flow and move from top to bottom to enter a lower-section bed layer and are dissolved continuously for complementary reaction consumption, the generated large bubbles move upwards to enter an upper-section bed layer and are in countercurrent contact with hydrocarbon oil, and the rest hydrogen which is not consumed is dissolved and absorbed by fresh hydrocarbon oil feeding material in a hydrogen dissolving section at the top of the reactor and returns to the bed layer to participate in the reaction again.

Mixing the material which is not completely reacted with the supplemented fresh hydrogen, then feeding the mixture into a second reactor for further reaction, feeding the material in the reactor into the reactor and discharging the material from the reactor, wherein the hydrogen is a continuous phase, and the liquid hydrocarbon oil is in contact reaction with a hydrogenation catalyst in a trickle mode.

The hydrotreating operation conditions of the first reactor and the second reactor are different, the hydrogen-oil ratio in the first reactor is low, the liquid phase is used as a reaction continuous phase, the hydrogen-oil ratio in the second reactor is high, and the gas phase is used as a continuous phase. The pressure of the second reactor is 0-2.0 MPa higher than that of the first reactor, and the temperature difference between the two reactors is adjusted by supplementing hydrogen. The reaction conditions are controlled to realize that 60 to 95 percent of the total reaction conversion is completed in the first reactor, and 5 to 40 percent of the total reaction conversion is completed in the second reactor.

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, and is preferably a hydrotreating process of heavier oil products above aviation kerosene, and the hydrogenation reaction can be a reaction process requiring hydrogen participation, such as hydrotreating, hydrofining, hydrocracking, hydrogenation saturation, hydroisomerization and the like.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. It should be understood that the description herein is provided for illustration and explanation of the invention and is not intended to limit the invention.

FIG 1 is the utility model provides a hydrocarbon oil hydrogenation reaction unit's flow schematic diagram, as shown in FIG 1, hydrocarbon oil hydrogenation reaction unit, including the first reactor A and the second reactor B of series connection, set up in the first reactor A and dissolve hydrogen section I, first section catalyst bed II and second section catalyst bed III, dissolve and be equipped with spray liquid distributor 2 in the hydrogen section I, set up middle gas distributor 8 between the adjacent catalyst bed, the preferred micro-nano perforated pipe of gas distributor, link to each other with middle hydrogen pipeline through annular house steward. The top of the first reactor A is connected with a liquid phase inlet 1 and a gas phase inlet pipeline 5, and the gas phase inlet pipeline is provided with a gas phase inlet flow regulating valve 7, a pressure detection device and a liquid level detection device. The pressure detection equipment controls reaction pressure in a linkage manner through a control system and a gas phase inlet flow regulating valve 7, and the liquid level detection equipment controls the height of the liquid level in the hydrogen dissolving section in a linkage manner through the control system and a bottom outlet flow regulating valve 9 of the reactor. The reaction materials enter from top to bottom in the first reactor. The bottom outlet of the first reactor is combined with the make-up hydrogen pipeline 4 through a pipeline 10 and then communicated with the raw material inlet of the second reactor B, and the material flow in the second reactor enters from the top and exits from the bottom.

The application method of the hydrocarbon oil hydrogenation reaction device comprises the steps that a hydrocarbon oil raw material enters a first reactor from a top inlet 1 and is dispersed into tiny liquid drops through a spraying type liquid distributor 2, and the liquid drops are in contact with hydrogen in a hydrogen dissolving section I and quickly reach hydrogen saturation. Hydrogen enters the hydrogen dissolving section through a gas phase inlet pipeline 5, the flow of the hydrogen is controlled through a gas phase inlet flow regulating valve 7, and the opening of the regulating valve is interlocked with a measuring signal of pressure detection equipment in the hydrogen dissolving section I. The sprayed liquid drops are converged into a liquid phase main fluid before entering a first section of catalyst bed layer II, the liquid level height is measured through liquid level detection equipment, a detection signal is interlocked with a flow regulating valve 9 on a bottom outlet pipeline through a control system, and the liquid level height is controlled to be above the first section of catalyst bed layer through the change of the opening degree of the regulating valve. And the hydrocarbon oil saturated by the hydrogen enters the first section of catalyst bed layer II by taking the liquid phase as a continuous phase and is subjected to hydrogenation reaction. And a part of fresh hydrogen enters the reactor through an intermediate hydrogen pipeline 6 and an intermediate gas distributor 8 between beds, wherein generated small bubbles are carried by hydrocarbon material flow and move from top to bottom to enter a second section of catalyst bed layer III and are continuously dissolved and consumed in a complementary reaction, generated large bubbles move upwards to enter a previous section of catalyst bed layer and are in countercurrent contact with hydrocarbon oil, and the rest hydrogen which is not consumed is dissolved and absorbed by fresh hydrocarbon oil feed in a hydrogen dissolving section I and returns to the bed layer to participate in the reaction again. The material at the outlet of the first reactor A is mixed with the make-up hydrogen from the pipeline 4 through the pipeline 10 and then enters the second reactor B for further reaction, the material in the second reactor is fed in and discharged out, the hydrogen is a continuous phase, and the liquid hydrocarbon oil is in contact reaction with the catalyst in a trickle mode. The reaction mass at the outlet of the second reactor enters a gas-liquid separator 12. The separated gas phase is led out through a gas phase outlet pipeline 13 and is subjected to subsequent treatment, or is returned to a hydrogen pipe network as circulating hydrogen; the separated liquid phase is withdrawn via line 14 as hydrotreated hydrocarbon oil.

The present invention will be further described with reference to the following examples. The present invention is not limited thereto.

In the examples and comparative examples:

the diesel fraction was obtained from petrochemical Qingdao petrochemical company, LLC of China, and its properties are shown in Table 1.

The hydrogenation catalyst RS-1000 is produced by catalyst division of China petrochemical Co.

Comparative example 1

Comparative example 1 illustrates the effect of a conventional trickle bed diesel hydrofinishing process.

The reaction flow is shown in figure 4, the height-diameter ratio of the reactor 3 is 20, and a hydrogenation catalyst RS-1000 is filled. The diesel raw material and new hydrogen 2 are mixed and then enter from the top of the reactor 3, flow downwards after passing through the raw material distributor, contact with a hydrogenation catalyst to carry out hydrogenation reaction, the reacted material is discharged through a product outlet pipeline 10 and enters a gas-liquid separation tank 4 to carry out gas-liquid separation, the separated gas phase 5 is unreacted hydrogen, and the liquid phase 6 is hydrofined diesel. The reaction conditions and product properties are shown in Table 2.

Comparative example 2

Comparative example 2 illustrates the effect of a diesel liquid phase hydrofinishing process.

The reaction flow is shown in figure 5, the height-diameter ratio of the reactor 3 is 20, and a hydrogenation catalyst RS-1000 is filled. The diesel raw material and new hydrogen 2 enter from the bottom of the reactor 3 after being mixed by the static mixer 9, and contact with the hydrogenation catalyst to carry out hydrogenation reaction, the liquid phase is a continuous phase, and the reacted material is discharged through the product outlet 10. And the gas-liquid separation is carried out in a gas-liquid separation tank 4, the separated gas phase 5 is unreacted hydrogen, one part of the separated liquid phase is circulated, the circulation ratio is 2, and the other part of the separated liquid phase is taken as a product. The reaction conditions and product properties are shown in Table 2.

Example 1

Example 1 illustrates the utility model provides a hydrogenation reaction unit's application effect.

Adopt the attached figure 1 to show the utility model provides a two segmentation hydrogenation reaction systems, wherein the height to diameter ratio of first reactor is 15, and the top dissolves hydrogen section and sets up fountain liquid distributor, sprays the pressure drop 0.2MPa. The diesel raw material is dispersed into tiny liquid drops through a spray nozzle, new hydrogen coming from a pipeline 5 and residual hydrogen rising from a catalyst bed layer II contact and quickly reach saturation in a hydrogen dissolving section I, then enter the catalyst bed layer II to contact with a hydrogenation catalyst and carry out hydrogenation reaction, and the other path of new hydrogen is supplemented from a micro-nano porous pipe gas distributor 8 between the bed layers II and III.

The distributor structure is shown in fig. 3 and the perforated pipe arrangement is shown in fig. 2.

EXAMPLES the reaction conditions are shown in Table 2, the raw materials, the catalyst and the catalyst used are the same as those in the comparative example, and the catalyst loading in the first reactor and the second reactor B are the same. The reaction results are shown in Table 2.

TABLE 1 Diesel feedstock Properties

TABLE 2 Diesel oil hydrofining reaction results

It can be seen from table 2 that, adopt the utility model provides a hydrocarbon oil hydrogenation method compares with traditional trickle bed and liquid phase hydrogenation, and operating condition mitigatees more, and desulfurization efficiency is higher to the hydrogen use amount is showing and is reducing, and hydrogen utilization ratio is higher.

Claims (10)

1. The utility model provides a hydrocarbon oil hydrogenation reaction unit, a serial communication port, including first reactor and second reactor, wherein set up from top to bottom in the first reactor and dissolve hydrogen section and at least one section catalyst bed, the raw materials entry and the fountain liquid distributor intercommunication of setting in dissolving the hydrogen section at reactor top dissolve the hydrogen section, it is equipped with the gas phase entry to dissolve the hydrogen section, first reactor bottom export is through export flow control valve (9) and the raw materials entry intercommunication at second reactor top, still be equipped with make-up hydrogen pipeline (4) intercommunication second reactor, be equipped with the catalyst bed in the second reactor, second reactor bottom export intercommunication gas-liquid separation equipment (12).

2. The hydrocarbon oil hydrogenation reaction apparatus according to claim 1, wherein the ratio of the height to the diameter of the first reactor is from 8 to 30:1, wherein the hydrogen dissolving section is 2-10% of the total height of the first reactor.

3. The hydrocarbon oil hydrogenation reactor as recited in claim 1, wherein said spray-type liquid distributor main pipe is in the form of a plurality of branch pipes, and pressure-type nozzles are installed at outlets of the corresponding branch pipes.

4. The hydrocarbon oil hydrogenation reaction apparatus according to claim 1, wherein the aspect ratio of the second reactor is 10 to 40:1.

5. the hydrocarbon oil hydrogenation reaction apparatus according to claim 1, wherein the gas phase outlet of the gas-liquid separation device is connected to the gas phase inlet and the make-up hydrogen line via a line.

6. The hydrocarbon oil hydrogenation reaction device according to any one of claims 1 to 5, wherein the bottom of the hydrogen dissolving section is provided with a gas phase inlet, a gas phase inlet flow regulating valve (7) and a liquid level detection device, the upper part of the hydrogen dissolving section is provided with a pressure detection device, the pressure detection device and the gas phase inlet flow regulating valve (7) are linked to adjust the reaction pressure through a control system, and the liquid level detection device and the outlet flow regulating valve (9) are linked to adjust the liquid level height in the hydrogen dissolving section through the control system.

7. A hydrocarbon oil hydrogenation reactor according to claim 6, characterized in that two or more catalyst beds are provided in the first reactor, and the intermediate hydrogen line (6) communicates with an intermediate gas distributor (8) provided between adjacent catalyst beds.

8. The hydrocarbon oil hydrogenation reaction device according to claim 7, wherein the intermediate gas distributor has a structure that the annular main pipe is communicated with the micro-nano porous pipes through connecting pipes, the micro-nano porous pipes are uniformly distributed along the circumference of the annular main pipe, and the pore diameters of the micro-nano porous pipes are smaller than 10 micrometers.

9. The hydrocarbon oil hydrogenation reaction device according to claim 8, wherein the micro-nano porous tubes are inclined downwards and are positioned below the plane of the annular header pipe, and the interval between adjacent micro-nano porous tubes is not less than 200mm.

10. The hydrocarbon oil hydrogenation reaction device according to claim 8 or 9, wherein the aspect ratio of the micro-nano porous tube is 0.3-2.0:1.

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