CN216799757U

CN216799757U - Liquid phase hydrogenation reaction device and system

Info

Publication number: CN216799757U
Application number: CN202121301766.5U
Authority: CN
Inventors: 袁清; 秦娅; 毛俊义; 朱振兴; 黄涛
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2021-06-10
Filing date: 2021-06-10
Publication date: 2022-06-24
Anticipated expiration: 2031-06-10

Abstract

A liquid phase hydrogenation reaction device and a system, wherein in the liquid phase hydrogenation reaction device, a reactor consists of a hydrogen mixing area (I) at the upper part and a reaction area (II) at the lower part, the bottom of the hydrogen mixing area is communicated with the reaction area, a hydrogenation catalyst is filled in the reaction area, the top of the reactor is provided with a liquid phase inlet (5) and a gas phase outlet (10), the bottom of the reactor is provided with a liquid phase outlet (11) and a flow control valve, and the bottom of the hydrogen mixing area is provided with a gas phase inlet (7); the gas phase inlet and the gas phase outlet are respectively provided with a flow control valve. The liquid phase hydrogenation reaction device provided by the utility model has the advantages of simple structure and simplicity and convenience in 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

Liquid phase hydrogenation reaction device and system

Technical Field

The utility model relates to a reaction device in the field of petrochemical industry, in particular to a hydrocarbon oil continuous hydrogenation reaction device and a hydrocarbon oil continuous hydrogenation reaction system.

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 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 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.

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. 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 processes, and a gas-liquid separation device is arranged in front of the reactor. Different methods can be adopted for the hydrogen pre-mixing process before the reactor, 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 a through hole with an average pore diameter of nanometer size, so as to realize high dispersion of hydrogen and dissolve the hydrogen in the hydrocarbon oil at a higher speed. CN208583196U discloses a novel hydrogen dissolver, which adopts a multi-layer structure, each layer is provided with a dispersing plate, a membrane layer and an overflow baffle, wherein the membrane layer has micropores with nanometer-scale pore diameters. CN109731512A adopts a micro-channel mixer with complex structure to mix hydrocarbon oil and hydrogen.

It is known from the prior art that 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.

SUMMERY OF THE UTILITY MODEL

The utility model aims to solve the technical problem of providing a reaction device for liquid-phase hydrogenation of hydrocarbon oil and a hydrotreating method thereof on the basis of 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 liquid phase hydrogenation reaction device provided by the utility model comprises a reactor, a hydrogen mixing zone I and a reaction zone II, wherein the upper part of the reactor consists of the hydrogen mixing zone I and the lower part of the reactor consists of the hydrogen mixing zone II, the bottom of the hydrogen mixing zone is communicated with the reaction zone, a hydrogenation catalyst is filled in the reaction zone, the top of the reactor is provided with a liquid phase inlet 5 and a gas phase outlet 10, the bottom of the reactor is provided with a liquid phase outlet 11 and a flow control valve, and the bottom of the hydrogen mixing zone is provided with a gas phase inlet 7; the gas phase inlet and the gas phase outlet are respectively provided with a flow control valve.

A liquid phase hydrogenation reaction system is formed by connecting at least two liquid phase hydrogenation reaction devices in series or in parallel.

The application method of the liquid phase hydrogenation reaction device adopts the liquid phase hydrogenation reaction device, the hydrocarbon oil raw material enters the hydrogen mixing zone through the liquid phase inlet in a dispersed phase mode and fully contacts with hydrogen to obtain the hydrogen-dissolved hydrocarbon oil raw material, the stable liquid level height is maintained in the hydrogen mixing zone to ensure that the reaction zone is in a full liquid phase, and the hydrogen-dissolved hydrocarbon oil raw material enters the reaction zone from the bottom of the hydrogen mixing zone, flows downwards to pass through the catalyst bed layer and contacts with the hydrogenation catalyst to react to obtain the hydrocarbon oil hydrogenation product.

The liquid phase hydrogenation reaction device and the liquid phase hydrogenation reaction system provided by the utility model have the beneficial effects that:

compared with the prior art, the liquid phase hydrogenation reaction device provided by the utility model has the advantages of simple structure and convenience in operation. The method is suitable for the original liquid phase hydrogenation of the hydrocarbon oil, and can save a complex circulating hydrogen system, so that the operation is simpler and easier. In the process of mixing hydrogen/dissolving hydrogen, liquid is used as a disperse phase, and gas is used as a continuous phase, so that the resistance in the process of mass and heat transfer can be obviously 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 liquid phase hydrogenation reactor;

FIG. 2 is a schematic process flow diagram of comparative example 1.

Wherein:

I-Hydrogen mixing zone II-reaction zone 1-Hydrocarbon oil feedstock

2-feed pump 3-heat exchanger 4-circulating material pipeline

5-liquid phase inlet 6-reactor 7-gas phase inlet

8. 9, 13-flow control valve 10-gas phase outlet 11-liquid phase outlet

12-liquid phase circulating pump 14-product outlet 15-pipeline

16-liquid level detection device 17 pressure detection device

Detailed Description

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

In a first aspect, the utility model provides a liquid phase hydrogenation reaction device, wherein a reactor consists of an upper hydrogen mixing area I and a lower reaction area II, the bottom of the hydrogen mixing area is communicated with the reaction area, a hydrogenation catalyst is filled in the reaction area, the top of the reactor is provided with a liquid phase inlet 5 and a gas phase outlet 10, the bottom of the reactor is provided with a liquid phase outlet 11 and a flow control valve, and the bottom of the hydrogen mixing area is provided with a gas phase inlet 7; the gas phase inlet and the gas phase outlet are respectively provided with a flow control valve.

Optionally, the hydrogen mixing area is further provided with a pressure detection device and a liquid level detection device, the opening degree of the flow control valve of the gas phase inlet and the gas phase outlet is controlled in a linkage manner with the pressure detection, and the opening degree of the flow control valve of the liquid phase outlet is controlled in a linkage manner with the liquid level of the hydrogen mixing area.

Optionally, the liquid phase inlet is provided with a liquid distributor; the gas phase inlet is provided with a gas distributor; more preferably, the liquid phase inlet is also provided with a pressure spraying device.

Optionally, the hydrogen mixing area is filled with a filler; preferably loaded with lipophilic fillers. The oleophilic filler is selected from polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE) or surface modified metal fillers.

Optionally, the volume ratio of the hydrogen mixing zone to the reaction zone is (0.02-0.3): 1, the height ratio of the hydrogen mixing zone to the reaction zone is (0.05-0.2): 1.

optionally, the diameters of the hydrogen mixing zone and the reaction zone are the same or different, and the ratio of the diameters of the hydrogen mixing zone to the reaction zone (0.5-2): 1.

optionally, the height-diameter ratio of the catalyst bed layer in the reaction zone is (5-50): 1, preferably (8-30): 1.

preferably, the reaction zone is filled with more than two catalyst beds.

Optionally, a circulation pipeline and a circulation 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 utility model, 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 flow control valve in the reaction area and the liquid level of the hydrogen mixing area are controlled in a linkage manner, so that the hydrogen mixing area can maintain a stable liquid level. In the same reactor, the upper part is a hydrogen mixing area, the lower part is a reaction area, the top of the hydrogen mixing area is provided with a liquid phase inlet and a gas phase outlet, the bottom of the hydrogen mixing area is provided with a gas phase outlet, the hydrogen mixing area is provided with a pressure detection device and a liquid level meter, the bottom of the reaction area is provided with a liquid phase outlet, and the reaction area is filled with a hydrogenation catalyst bed layer. 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 top and pass through the hydrogenation catalyst bed layer, and a liquid phase outlet at the bottom of the reaction zone discharges reacted materials. The flow control valve of the liquid phase outlet and the liquid level of the hydrogen mixing area are controlled in a linkage manner, the full liquid phase operation of the reaction area is maintained, and the ratio of the liquid level height of the hydrogen mixing area to the hydrogen mixing area is controlled to be (0.2-1.0): 1.

In the liquid phase hydrogenation reaction device provided by the utility model, the reaction zone is filled with the hydrogenation catalyst, or filled with the hydrogenation catalyst and other types of catalysts, wherein the other types of catalysts comprise but are not limited to protective agents, isomerization catalysts 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 utility model, 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 2.0 mm. 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 utility model, 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 linkage of the hydrogen mixing area so as to control the flow of supplemented hydrogen. The top of the hydrogen mixing area is provided with a gas phase outlet and a flow control valve, and the opening of the flow control valve controls the outflow flow of hydrogen through pressure linkage with the hydrogen mixing area or sets the opening to fix the outflow volume. The pressure in the hydrogen mixing area is higher than that in the reaction area, and the pressure difference is the static pressure difference of the liquid level at the bottom of the hydrogen mixing area. 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 sprayed into liquid drops through the liquid distributor to enlarge the mass transfer surface with hydrogen, the hydrogen is a continuous phase, the liquid is a dispersed phase, preferably, the hydrogen mixing area is filled with filler, and the liquid phase is dispersed through the surface of the filler to provide a larger mass transfer 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 2.0 mm.

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 meet the reaction hydrogen consumption, the liquid phase circulation loop is not required to be arranged.

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, 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.

The utility model provides an application method of a liquid phase hydrogenation reaction device and a system, wherein a hydrocarbon oil raw material enters a hydrogen mixing area in a dispersed phase form to fully contact with hydrogen to obtain a hydrogen-soluble hydrocarbon oil raw material, a stable liquid level height is maintained in the hydrogen mixing area so that the reaction area is operated in a full liquid phase, and the ratio of the liquid level height in the mixing area to the hydrogen mixing area is (0.2-1.0): 1; 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 operating conditions of the reaction zone are as follows: 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^-1Chemical 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 unit mass of feed due to chemical reactions such as olefin saturation, desulfurization, denitrification, deoxidation, demetallization and the like.

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 2.0 mm.

The proportion of the recycled materials is 0.5-10, and more preferably 1-6.

The hydrocarbon oil raw material is one or a mixture of more of C1-C4 light hydrocarbon, naphtha, gasoline, aviation kerosene, diesel oil, VGO and residual oil.

Hydrocarbon oil raw materials pass through the hydrogen mixing zone to complete hydrogen mixing and dissolving and then flow 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 the hydrogen is automatically supplemented according to the dissolving consumption and the liquid phase carrying amount, 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 hydrogen mixing and hydrogen dissolving are completed in the hydrogen mixing zone, materials can enter and exit from the upper part and the lower part in 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.

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 in the reaction zone is preferably interlocked with an outlet line control valve so as to control the liquid level stability of the hydrogen mixing zone.

Preferably, a part of the liquid phase circulating material is returned to the liquid phase inlet of the hydrogen mixing zone to increase the total hydrogen dissolving amount of the liquid phase material flow and reach the required reaction hydrogen consumption level. If the saturated dissolved hydrogen amount of the fresh hydrocarbon oil feed can meet the reaction hydrogen consumption, the proportion of the circulating material can be reduced.

The liquid phase hydrogenation reaction device provided by the utility model is suitable for reaction processes needing hydrogen participation, such as hydrotreating, hydrofining, hydrocracking, hydrogenation saturation, hydroisomerization and the like.

The following describes in detail a specific embodiment of the present invention with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating the utility model, are given by way of illustration and explanation only, not by way of limitation.

FIG. 1 is a schematic flow diagram of a liquid phase hydrogenation reactor. As shown in fig. 1, the hydrogenation reactor 6 is divided into an upper hydrogen mixing zone i and a lower reaction zone ii, both of which share the same cylinder structure. The top of the hydrogen mixing area I is provided with a liquid phase inlet 5 and a gas phase outlet 10, the hydrocarbon oil raw material enters the hydrogen mixing area I from the top through the liquid phase inlet 5 after being pressurized by a booster pump 2 and preheated by a heat exchanger 3 to the reaction temperature from a pipeline 1, and is preferably introduced into the hydrogen mixing area by a liquid distributor in a spraying mode. The bottom of the hydrogen mixing area I is provided with a gas phase inlet 7 and a flow control valve 8, hydrogen enters and fills the hydrogen mixing area I through the gas phase inlet 7, and gas and liquid are in countercurrent contact, preferably, the gas is uniformly distributed through a gas distributor. Preferably, the hydrogen mixing area I is filled with filler, more preferably lipophilic filler, the hydrocarbon oil raw material is further dispersed on the surface of the filler to form a liquid film, the average liquid film thickness is preferably less than 2.0mm, a mass and heat transfer surface is provided for gas-liquid contact, in the hydrogen mixing area I, hydrogen is a continuous phase, the hydrocarbon oil raw material is a dispersed phase, and gas-liquid two-phase countercurrent fully contacts and transfers mass.

After the reaction material passes through the hydrogen mixing zone I to complete hydrogen mixing and dissolving, the reaction material flows to the reaction zone II from top to bottom, a hydrogenation catalyst bed layer is filled in the reaction zone II, and the reaction material is contacted with a hydrogenation catalyst to carry out liquid phase hydrogenation reaction. The bottom of the reaction area II is provided with a liquid phase outlet 11 and a liquid phase outlet flow valve 13, and the reacted liquid phase material is discharged out of the reactor 6 through the liquid phase outlet 11 and the liquid phase outlet flow valve 13 and a product outlet 14. And controlling the opening of the liquid phase outlet flow valve to ensure that the liquid phase reaction material maintains a certain liquid level above the hydrogenation catalyst bed layer so as to ensure the reaction under the condition that the reaction zone II is filled with the liquid phase. A circulating pump 12 and a material circulating pipeline 4 are arranged between the liquid phase outlet 11 and the liquid phase inlet 5, and part of hydrogenated materials return to the hydrogen mixing area I through the circulating pipeline 4 so as to increase the total hydrogen dissolving amount of liquid phase material flow and reach the level required by reaction hydrogen consumption. In the first embodiment as shown in the attached figure 1, the bottom of the hydrogen mixing zone is directly communicated with the top of the reaction zone, the temperature of the hydrogen mixing zone is the same as that of the inlet of the reaction zone, the operating pressure of the hydrogen mixing zone is higher than that of the inlet of the reaction zone so as to maintain the liquid level of the hydrogen mixing zone, and the ratio of the liquid level height to the hydrogen mixing zone is (0.2-1.0): 1. The pressure stability of the hydrogen mixing area is controlled by controlling the opening degree of a gas phase inlet flow control valve 8 and a gas phase outlet flow control valve 9.

The present invention is further illustrated by the following examples. And the utility model is not to be restricted thereby.

Comparative example 1

Comparative example 1 is a hydrogenation and de-olefination process of reformate using a liquid phase hydrogenation mode. The reformate was obtained from Yanshan petrochemical company, Inc., China petrochemical company Limited, and the properties of the feedstock are shown in Table 1. The adopted hydrogenation catalyst has the trade mark of TORH-1 and is produced by ChangLing division of China petrochemical catalyst Co.

The technological process is shown in figure 2, a hydrogenation catalyst bed layer is filled in a hydrogenation reactor 6, and the height-diameter ratio of the reactor is 20. The hydrocarbon oil raw material 1 is subjected to heat exchange by a feeding pump 2 and a heat exchanger 3, then mixed with hydrogen 7 by a static mixer, enters a hydrogenation reactor 6 from the bottom through a pipeline 5, contacts with a hydrogenation catalyst for hydrogenation reaction, and the reacted material is discharged through a product outlet 14. The reaction temperature is 120 ℃, the reaction pressure is 2.0MPa, and the mass space velocity is 10.0h^-1The 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

Example 1a flow of a liquid phase hydrogenation reaction apparatus shown in fig. 1 was employed, in which a reactor 6 was composed of a hydrogen-mixing zone I and a reaction zone II, the hydrogen-mixing zone I and the reaction zone II shared the same cylinder and were disposed up and down, the volume ratio of the hydrogen-mixing zone to the reaction zone was 0.1:1, and the diameter ratio of the two zones was 1: and 1, a Polytetrafluoroethylene (PTFE) corrugated packing and necessary packing support plates, liquid distributors and other members are arranged in the hydrogen mixing zone. The reaction zone II is filled with hydrogenation catalyst, and the height-diameter ratio of the catalyst bed layer is 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 2 mm. The hydrogen feeding and the pressure linkage of the hydrogen mixing area are automatically supplemented. Because the chemical hydrogen consumption of the reaction is low, no liquid phase circulation is set. The liquid level control at the top of the reaction zone II is interlocked with a control valve at the outlet of the reactor. The hydrocarbon oil feedstock, hydrogenation catalyst and reaction conditions were the same as in comparative example 1. The top of the hydrogen mixing zone was controlled at a pressure of 2.05MPa and the liquid level was controlled at a height of 0.5 times the diameter of the hydrogen mixing zone, and the reaction results are shown in Table 2.

As can be seen from table 2, the hydrogenation effect of example 1 is better than that of comparative example 1 under the same reaction conditions.

Comparative example 2

Comparative example 2 is a diesel hydrofinishing process. The process flow is shown in figure 2, the height-diameter ratio of the reactor 6 is 16, and a hydrogenation catalyst bed layer is filled. The hydrocarbon oil raw material 1, the low-pressure degassed circulating oil from the circulating pipeline 11 and new hydrogen 7 are mixed by a static mixer and then enter the reactor 6 from the bottom to contact with a hydrogenation catalyst for hydrogenation reaction, the reacted material is discharged through a product outlet 14, and part of the reacted material returns to the reactor through the circulating pipeline 11. The reaction temperature is 365 ℃, the reaction pressure is 8.0MPa, and the volume space velocity is 1.6h^-1The hydrogen-oil volume ratio is 75, and the circulation ratio is 3: 1. The reaction product properties are shown in table 4.

Wherein, the diesel oil raw material is taken from Yanshan petrochemical company of China petrochemical industry 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

In example 2, the flow of the liquid phase hydrogenation reaction apparatus shown in fig. 1 was used, the diameter of the hydrogen mixing zone I was 0.6 times the diameter of the reaction zone II, the volume ratio of the two was 0.2:1, the liquid phase inlet at the top of the hydrogen mixing zone used a pressure spray device as a liquid distributor, the orifice diameter was 3.5mm, the spray pressure dropped by 0.15MPa, and the liquid phase was dispersed by a spray method.

Diesel raw material and circulating material enter from a liquid phase inlet 5 at the top of the hydrogen mixing zone I, and hydrogen enters the hydrogen mixing zone I from the bottom of the hydrogen mixing zone I from a gas phase inlet 7 and is in countercurrent contact with the diesel raw material. The hydrogen mixing area is provided with pressure detection equipment and liquid level detection equipment, hydrogen feeding adopts flow control, the volume ratio of fed hydrogen to oil is 50, and the hydrogen external discharge capacity is interlocked with the pressure of the hydrogen mixing area; the opening degree of the reactor outlet control valve is linked with the liquid level at the bottom of the hydrogen mixing area, so that the pressure and the liquid level in the hydrogen mixing area are stable, and the liquid phase in the reaction area reacts.

The reaction raw materials, catalysts and other operating conditions used in example 2 were the same as those 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 in the case where the hydrogen oil volume ratio was decreased, as compared with comparative example 2.

TABLE 1 reformate feedstock Properties

TABLE 2 reformate hydrogenation results

Item	Comparative example 1	Example 1
			Aromatic loss in wt%	0.05	0.04
Bromine index of hydrogenated product, mgBr/100g	230	135

TABLE 3 Diesel feedstock Properties

TABLE 4 results of the diesel hydrofining reaction

Item	Comparative example 2	Example 2
			Sulfur content, μ g/g	12	8
Nitrogen content,. mu.g/g	0.4	＜0.2

Claims

1. The liquid phase hydrogenation reaction device is characterized in that a reactor consists of a hydrogen mixing area (I) at the upper part and a reaction area (II) at the lower part, the bottom of the hydrogen mixing area is communicated with the reaction area, a hydrogenation catalyst is filled in the reaction area, the top of the reactor is provided with a liquid phase inlet (5) and a gas phase outlet (10), the bottom of the reactor is provided with a liquid phase outlet (11) and a flow control valve, and the bottom of the hydrogen mixing area is provided with a gas phase inlet (7); the gas phase inlet and the gas phase outlet are respectively provided with a flow control valve.

2. The liquid-phase hydrogenation reactor according to claim 1, wherein said reactor is further provided with a pressure detecting means and a liquid level detecting means, and the opening degrees of the flow control valves of said gas phase inlet and said gas phase outlet are controlled in interlock with the pressure detection, and the opening degree of the flow control valve of said liquid phase outlet is controlled in interlock with the liquid level of the hydrogen-mixing zone.

3. The liquid-phase hydrogenation reaction apparatus according to claim 1 or 2, wherein the liquid-phase inlet is provided with a liquid distributor; the gas phase inlet is provided with a gas distributor.

4. The liquid-phase hydrogenation reaction apparatus according to claim 1 or 2, wherein the hydrogen-mixing zone is filled with a filler.

5. A liquid-phase hydrogenation reaction apparatus as claimed in claim 4, wherein said hydrogen-mixing region is filled with an oleophilic filler.

6. The liquid-phase hydrogenation reaction apparatus according to claim 1 or 2, wherein the volume ratio of the hydrogen-mixing zone to the reaction zone is 0.02 to 0.3: 1, the height ratio of the hydrogen mixing zone to the reaction zone is 0.05-0.2: 1.

7. the liquid-phase hydrogenation reaction apparatus according to claim 1 or 2, wherein the diameter of the hydrogen-mixing zone is the same as or different from that of the reaction zone, and the ratio of the diameter of the hydrogen-mixing zone to that of the reaction zone is 0.5 to 2: 1.

8. the liquid-phase hydrogenation reaction apparatus according to claim 1 or 2, wherein the height-to-diameter ratio of the catalyst bed in the reaction zone is 5 to 50: 1.

9. the liquid-phase hydrogenation reaction apparatus according to claim 8, wherein the ratio of the height to the diameter of the catalyst bed in the reaction zone is from 8 to 30: 1.

10. a liquid-phase hydrogenation reaction apparatus as claimed in claim 1 or 2, wherein said reaction zone is filled with two or more hydrogenation catalyst beds.

11. The liquid-phase hydrogenation reactor as claimed in claim 1 or 2, characterized in that a circulation line and a circulation pump are provided between the liquid-phase outlet of the reaction zone and the liquid-phase inlet of the hydrogen-mixing zone.

12. 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 11 are connected in series or in parallel.