Oil product hydrogenation device and oil product hydrogenation method

Abstract

The invention provides an oil product hydrogenation device and an oil product hydrogenation method. The oil product hydrogenation device comprises a hydrogenation reactor, wherein the hydrogenation reactor is provided with a reaction cavity; a feed port is formed in the bottom of the reaction cavity, a discharge port is formed in the top of the reaction cavity, and the reaction cavity is provided with at least two bed layers; the hydrogenation reactor is respectively provided with an independent gas cavity corresponding to each bed layer of the reaction cavity, and each gas cavity is provided with a gas inlet; wherein one reaction chamber bed layer is correspondingly provided with one gas chamber, and the gas chambers are mutually independent; the reaction cavity penetrates through each gas cavity, and the wall surface of the part, positioned in the gas cavity, of the reaction cavity is made of a hydrogen-permeable and oil-impermeable material. The oil product hydrogenation device can be suitable for hydrogenation of high-hydrogen-consumption oil products, and low-cost and high-efficiency hydrogenation treatment of the high-hydrogen-consumption oil products can be realized.

Description

Technical Field

[0001] The invention belongs to the technical field of petrochemical industry, and particularly relates to an oil product hydrogenation device and an oil product hydrogenation method. Background Art

[0002] At present, the oil hydrogenation process is becoming increasingly important in the refining industry. Common oil hydrogenation processes include diesel hydrocracking to produce ethylene cracking materials, diesel hydrocracking tail oil hydroisomerization to produce lubricating oil base oil, etc.

[0003] Oil hydrogenation processes mostly use traditional trickle bed hydrogenation, but traditional trickle bed hydrogenation has problems such as large mass transfer resistance, large investment, and high energy consumption. As a result, the liquid phase hydrogenation process was born. In the liquid phase hydrogenation process, the liquid phase is always the continuous phase in the reactor, and the hydrogen is the dispersed phase. The liquid phase hydrogenation reactor uses a reactor with a similar structure to the trickle bed reactor. Since the circulating hydrogen system is cancelled, it has the characteristics of low investment, low energy consumption, and low operating cost. However, due to the limited hydrogen solubility of oil products, liquid phase hydrogenation is only suitable for hydrogenation reactions with a chemical hydrogen consumption of no more than 0.6wt%, which limits the application of liquid phase hydrogenation technology in the hydrogenation process of high hydrogen consumption oil products.

[0004] Based on this, if enhanced hydrogen mixing equipment is added to the liquid phase hydrogenation or an enhanced hydrogen mixing reactor is used, the mixing effect of hydrogen in the oil can be enhanced through a specially structured static mixer or dynamic mixer, so that the hydrogen bubbles can reach an ultra-stable state at the micron level and the amount of dissolved hydrogen in the liquid far exceeds the actual chemical hydrogen consumption. In this way, it is possible to use the liquid phase hydrogenation process to hydrogenate high hydrogen consumption oil products.

[0005] Therefore, it is very necessary to develop an oil product hydrogenation device and a supporting method that has a simple system structure, a long operating cycle, and is easy to improve using existing devices and can adapt to the hydrogenation of high hydrogen consumption oil products. Summary of the invention

[0006] The purpose of the present invention is to provide an oil product hydrogenation technology solution that can be applicable to the hydrogenation of high hydrogen consumption oil products, which can achieve low-cost and high-efficiency hydrogenation treatment of high hydrogen consumption oil.

[0007] In order to solve the above problems, the present invention provides the following two technical solutions.

[0008] In a first aspect, the present invention provides an oil product hydrogenation device, the device comprising a hydrogenation reactor, the hydrogenation reactor being provided with a reaction chamber; the reaction chamber being provided with a feed inlet at the bottom and a discharge outlet at the top, the reaction chamber being provided with at least two bed layers;

[0009] The hydrogenation reactor is provided with independent air cavities corresponding to each bed layer of the reaction chamber, and each air cavity is provided with an air inlet; wherein one air cavity is provided corresponding to one bed layer of the reaction chamber, and each air cavity is independent of each other;

[0010] The reaction chamber passes through each of the gas chambers, and the wall surface of the reaction chamber located inside the gas chamber is made of a hydrogen-permeable and oil-impermeable material, so that the gas in the gas chamber enters the reaction chamber through the wall surface made of hydrogen-permeable and oil-impermeable material and mixes with the fluid in the reaction chamber.

[0011] The oil hydrogenation device provided by the first aspect of the present invention is used to carry out a hydrogenation reaction. In the hydrogenation reactor, the reaction chamber and the gas chamber are used to cooperate to achieve the mixing of the crude oil with hydrogen in the reaction chamber, and the catalyst in the reaction chamber is used directly to carry out the hydrogenation reaction after the hydrogenation. The oil hydrogenation equipment provided by the first aspect of the present invention is used to carry out oil hydrogenation, and the crude oil and hydrogen are synchronously mixed and hydrogenated in the reaction chamber. On the one hand, the cooperation between the reaction chamber and the gas chamber is used to achieve the full mixing of hydrogen and crude oil, and on the other hand, the turbulence of the fluid after hydrogenation caused by long-distance transportation or variable-diameter transportation is avoided, as well as the enlargement, unevenness, or precipitation of hydrogen bubbles caused by hydrogenation.

[0012] According to a preferred embodiment of the first aspect, the hydrogen-permeable and oil-impermeable product is made of perovskite ceramics, tungsten bronze ceramics or pyrochlore ceramics;

[0013] Furthermore, the material of the hydrogen-permeable and oil-impermeable product is perovskite ceramic;

[0014] Perovskite ceramics, tungsten bronze ceramics, and pyrochlore ceramics can all be used as wall materials for the part of the reaction chamber located inside the gas chamber, and can achieve hydrogen permeability but oil impermeability in the hydrogen mixing operation using the reaction chamber and the gas chamber in combination; among them, perovskite ceramics have the best effect, and the use of perovskite ceramics can better achieve full mixing of hydrogen and oil. Perovskite ceramic materials have good density, uniform and regular pore arrangement, and easy control of pore size. Using perovskite ceramic materials as hydrogen permeability but oil impermeability materials for hydrogen mixing with crude oil can make the size of hydrogen bubbles distributed in the crude oil more uniform.

[0015] According to a preferred embodiment of the first aspect, the ratio of the cross-sectional area of ​​each bed layer in the reaction chamber perpendicular to the extension direction of the reaction chamber to the area of ​​the wall of the bed layer located in the gas cavity of the reaction chamber and made of a hydrogen-permeable and oil-impermeable material is 1:10-1:50.

[0016] According to a preferred embodiment of one aspect thereof, the ratio of the length of each bed layer of the reaction chamber located in the gas cavity along the extension direction of the reaction chamber to the length of the bed layer of the reaction chamber along the extension direction of the reaction chamber is not less than 9:10.

[0017] According to a preferred embodiment of one aspect thereof, the air cavity corresponding to each bed layer of the reaction chamber is located at the root of the bed layer of the reaction chamber.

[0018] According to a preferred embodiment of the first aspect, the hydrogenation reactor further includes a hydrogenation reaction catalyst arranged in the part of the reaction chamber located in the gas cavity; in this preferred embodiment, the oil and gas can react on the catalyst just after mixing. At this time, the hydrogen-oil interface area is close to the maximum, and the contact area with the active center of the catalyst is large, which helps to improve the reaction effect.

[0019] According to a preferred embodiment of the first aspect, the oil product hydrogenation unit comprises a plurality of (at least two) hydrogenation reactors connected in series;

[0020] For example, the oil hydrogenation unit includes two hydrogenation reactors connected in series, the discharge port of the first hydrogenation reactor is connected to the feed port of the second hydrogenation reactor; the fluid obtained by the hydrogenation and hydrogenation reaction in the first hydrogenation reactor enters the second hydrogenation reactor for hydrogenation and hydrogenation reaction.

[0021] According to a preferred embodiment of the first aspect, the oil product hydrogenation device further includes a gas-liquid separator, the feed port of the gas-liquid separator is connected to the discharge port of the hydrogenation reactor, and the gas-liquid separator is used to separate the gas and liquid of the product after the hydrogenation reaction; more preferably, the oil product hydrogenation device further includes a liquid product storage tank, the liquid product storage tank is connected to the liquid phase outlet of the gas-liquid separator, and the liquid product obtained after gas-liquid separation enters the liquid product storage tank for storage.

[0022] The oil product hydrogenation device provided in the first aspect of the present invention has a hydrogenation reactor with a special structure, and the liquid and gas materials are fed in a relatively vertical position. The contact area between the raw oil and the hydrogen is large, and the hydrogen bubbles and the liquid are fully mixed, which achieves a significant increase in the amount of hydrogen dissolved in the oil product. The amount of hydrogen dissolved in the oil product can reach 3-4 times the saturated hydrogen dissolved, which lays the foundation for realizing high hydrogen consumption, low cost, and high efficiency hydrogenation treatment. The oil product hydrogenation device provided in the first aspect of the present invention has a simple structure. A new hydrogenation device can be built or an old trickle bed hydrogenation device can be transformed. The equipment has a low cost of laying and is easy to promote industrialization. The oil product hydrogenation device provided in the first aspect of the present invention is simple to operate, the degree of hydrogen bubble aggregation is low, it can adapt to different acid and alkali environments and temperature environments, and can adapt to various oil product hydrogen mixing. The oil product hydrogenation device provided in the first aspect of the present invention is widely used and can be applied to the hydrogenation treatment of various distillate oils, such as low-quality diesel hydrogenation refining, jet fuel hydrogenation refining, naphtha hydrogenation refining, crude paraffin hydrogenation refining, lubricating oil base oil hydrogenation pretreatment and other processes, and can be used to produce high-quality diesel, jet fuel, naphtha, paraffin (a kind of wax oil), lubricating oil base oil. The oil product hydrogenation device provided in the first aspect of the present invention can operate stably for a long period of time, reduce operating costs, and has broad application prospects.

[0023] In a second aspect, the present invention provides an oil product hydrogenation method, which is performed using the oil product hydrogenation device provided in the first aspect of the present invention, and the method comprises:

[0024] Pass hydrogen into the air cavity corresponding to the first bed layer of the reaction chamber in the hydrogenation reactor, pass the preheated crude oil into the reaction chamber of the hydrogenation reactor, the hydrogen in the air cavity corresponding to the first bed layer of the reaction chamber enters the first bed layer of the reaction chamber through the wall surface of the first bed layer of the reaction chamber that is permeable to hydrogen and impermeable to oil products, mixes with the crude oil in the first bed layer of the reaction chamber, and undergoes hydrogenation reaction under the action of the catalyst, and the hydrogenation reaction product of the first bed layer of the reaction chamber enters the second bed layer of the reaction chamber; Pass hydrogen into the air cavity corresponding to the second bed layer of the reaction chamber in the hydrogenation reactor, the hydrogen in the air cavity corresponding to the second bed layer of the reaction chamber enters the second bed layer of the reaction chamber through the wall surface of the second bed layer of the reaction chamber that is permeable to hydrogen and impermeable to oil products, mixes with the hydrogenation reaction product from the first bed layer of the reaction chamber in the second bed layer of the reaction chamber, and undergoes hydrogenation reaction under the action of the catalyst; and so on until the hydrogenation reaction is completed in the last bed layer of the reaction chamber; wherein the first bed layer of the reaction chamber, the second bed layer of the reaction chamber, and the last bed layer of the reaction chamber are named in sequence along the direction from the feed inlet to the discharge outlet of the reaction chamber;

[0025] The product obtained from the hydrogenation reaction is subjected to gas-liquid separation to obtain refined oil products.

[0026] According to a preferred embodiment of the second aspect, the method comprises:

[0027] Pass hydrogen into the air cavity corresponding to the first bed layer of the reaction chamber in the first hydrogenation reactor, pass the preheated crude oil into the reaction chamber of the first hydrogenation reactor, the hydrogen in the air cavity corresponding to the first bed layer of the reaction chamber enters the first bed layer of the reaction chamber through the wall surface of the first bed layer of the reaction chamber that is permeable to hydrogen and impermeable to oil products, mixes with the crude oil in the first bed layer of the reaction chamber, and undergoes hydrogenation reaction under the action of the catalyst, and the hydrogenation reaction product of the first bed layer of the reaction chamber enters the second bed layer of the reaction chamber; Pass hydrogen into the air cavity corresponding to the second bed layer of the reaction chamber in the first hydrogenation reactor, the hydrogen in the air cavity corresponding to the second bed layer of the reaction chamber enters the second bed layer of the reaction chamber through the wall surface of the second bed layer of the reaction chamber that is permeable to hydrogen and impermeable to oil products, mixes with the hydrogenation reaction product from the first bed layer of the reaction chamber in the second bed layer of the reaction chamber, and undergoes hydrogenation reaction under the action of the catalyst; and so on until the hydrogenation reaction is completed in the last bed layer of the reaction chamber; wherein the first bed layer of the reaction chamber, the second bed layer of the reaction chamber, and the last bed layer of the reaction chamber are named in sequence along the direction from the feed inlet to the discharge outlet of the reaction chamber;

[0028] Pass hydrogen into the air cavity corresponding to the first bed layer of the reaction chamber in the second hydrogenation reactor, pass the hydrogenated product of the first hydrogenation reactor into the reaction chamber of the second hydrogenation reactor, the hydrogen in the air cavity corresponding to the first bed layer of the reaction chamber enters the first bed layer of the reaction chamber through the wall surface of the first bed layer of the reaction chamber that is permeable to hydrogen and impermeable to oil products, mixes with the feedstock oil in the first bed layer of the reaction chamber, and undergoes hydrogenation reaction under the action of the catalyst, and the hydrogenation reaction product of the first bed layer of the reaction chamber enters the second bed layer of the reaction chamber; pass hydrogen into the air cavity corresponding to the second bed layer of the reaction chamber in the second hydrogenation reactor, the hydrogen in the air cavity corresponding to the second bed layer of the reaction chamber enters the second bed layer of the reaction chamber through the wall surface of the second bed layer of the reaction chamber that is permeable to hydrogen and impermeable to oil products, mixes with the hydrogenation reaction product from the first bed layer of the reaction chamber in the second bed layer of the reaction chamber, and undergoes hydrogenation reaction under the action of the catalyst; and so on until the hydrogenation reaction is completed in the last bed layer of the reaction chamber; wherein the first bed layer of the reaction chamber, the second bed layer of the reaction chamber, and the last bed layer of the reaction chamber are named in sequence along the direction from the feed inlet to the discharge outlet of the reaction chamber;

[0029] And so on until the hydrogenation reaction is completed in the last hydrogenation reactor;

[0030] The product obtained by the hydrogenation reaction is subjected to gas-liquid separation to obtain a refined oil product;

[0031] In the second technical solution, a single-stage hydrogenation process can be used for hydrogenation refining (i.e., using one hydrogenation reactor) or a one-stage series hydrogenation process can be used for deep hydrogenation refining (i.e., using multiple hydrogenation reactors connected in series in sequence).

[0032] According to a preferred embodiment of the second aspect, when the feedstock oil is wax oil, the oil product hydrogenation method is a wax oil hydrogenation method; the hydrogen partial pressure in the hydrogenation reactor (i.e., the hydrogen pressure in the gas cavity) is 7.0 MPa-15.0 MPa, the reaction temperature of the hydrogenation reaction in the hydrogenation reactor is 300°C-390°C, and the volume space velocity is 0.5 h -1 -1.5h -1 , the volume ratio of hydrogen to oil is 10:1-50:1.

[0033] According to a preferred embodiment of the second aspect, the catalyst may be a commonly used hydrogenation catalyst according to the type of the feedstock oil.

[0034] The oil product hydrogenation method provided in the second aspect of the present invention is carried out using the oil product hydrogenation device provided in the first aspect of the present invention, and hydrogen and feedstock oil are mixed and reacted with the aid of a hydrogenation reactor with a special structure. During the reaction process, there is no need to circulate the oil product, no need to supplement hydrogen, the operating pressure is low, the temperature is low, and the hydrogen-to-oil ratio is low, which can greatly reduce investment costs and operating costs. The oil product hydrogenation method provided by the present invention is suitable for various types of oil product hydrofining, and has a simple process flow, stable operation, good product properties, and broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 Schematic diagram of the structure of the hydrogenation reactor in Example 1. DETAILED DESCRIPTION

[0036] In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be construed as limiting the applicable scope of the present invention.

[0037] Example 1

[0038] This embodiment provides an oil product hydrogenation device.

[0039] The device includes:

[0040] Hydrogenation reactor (structure such as Figure 1 As shown), gas-liquid separator and liquid product storage tank;

[0041] The hydrogenation reactor comprises a reaction chamber 11; a feed inlet is provided at the bottom of the reaction chamber 11 and a discharge port is provided at the top; the reaction chamber 11 is provided with two bed layers, which are the first bed layer and the second bed layer in order from the feed inlet to the discharge port;

[0042] The hydrogenation reactor is provided with independent air cavities 12 corresponding to each bed layer of the reaction chamber 11, and each air cavity 12 is provided with an air inlet 121; wherein one air cavity 12 is provided corresponding to one bed layer and each air cavity 12 is independent of each other;

[0043] The reaction chamber 11 passes through each gas chamber 12, and the wall surface of the reaction chamber 11 located in the gas chamber 12 is made of perovskite ceramic, which is a hydrogen-permeable and oil-impermeable material, so that the gas in the gas chamber 12 enters the reaction chamber 11 through the perovskite ceramic wall surface and mixes with the fluid in the reaction chamber 11 and undergoes a hydrogenation reaction in the reaction chamber 11; the bottom surface of the gas chamber 12 is flush with the bottom surface of the bed layer of the corresponding reaction chamber 11 (that is, the gas chamber 12 corresponding to each bed layer of the reaction chamber 11 is located at the root of the bed layer of the reaction chamber 11); wherein the reaction chamber 11 is cylindrical, with a diameter of 100 mm and a height of 100 cm for one bed layer, the gas chamber 12 is cylindrical, with a diameter of 102 mm and a height of 90 cm, and the height of the air inlet 121 from the bottom of the gas chamber 12 is 50 cm;

[0044] The gas-liquid separator is provided with a feed port, a gas stripping gas inlet, a gas phase outlet, and a liquid phase outlet. The feed port of the gas-liquid separator is connected to the discharge port of the hydrogenation reactor. The gas-liquid separator is used to separate the gas and liquid of the product after the hydrogenation reaction; the liquid phase product storage tank is connected to the liquid phase outlet of the gas-liquid separator, and the liquid phase product obtained after the gas-liquid separation enters the liquid phase product storage tank for storage; the gas phase outlet of the liquid phase product storage tank is used to discharge the gas obtained after the gas-liquid separation.

[0045] Example 2

[0046] This embodiment provides an oil product hydrogenation device.

[0047] The difference between the oil product hydrogenation device provided in this embodiment and the oil product hydrogenation device provided in Example 1 is that two hydrogenation reactors connected in series are provided, namely a first hydrogenation reactor and a second hydrogenation reactor, the discharge port of the first hydrogenation reactor is connected to the feed port of the second hydrogenation reactor, and the discharge port of the second hydrogenation reactor is connected to the feed port of the gas-liquid separator.

[0048] Example 3

[0049] This embodiment provides an oil product hydrogenation method, which is performed using the oil product hydrogenation device provided in Example 1 of the present invention, and comprises:

[0050] The paraffin wax was preheated to a desired temperature (280° C.) using a heating furnace to obtain preheated paraffin wax.

[0051] The hydrogen is introduced into the air cavity corresponding to the first bed layer of the reaction chamber in the hydrogenation reactor, and the preheated paraffin is introduced into the reaction chamber of the hydrogenation reactor. The hydrogen in the air cavity corresponding to the first bed layer of the reaction chamber enters the first bed layer of the reaction chamber through the wall surface of the first bed layer of the reaction chamber that is permeable to hydrogen and impermeable to oil products, mixes with the paraffin in the first bed layer of the reaction chamber, and undergoes a hydrogenation reaction under the action of a catalyst. The hydrogenation reaction product of the first bed layer of the reaction chamber enters the second bed layer of the reaction chamber; the hydrogen is introduced into the air cavity corresponding to the second bed layer of the reaction chamber in the hydrogenation reactor, and the hydrogen in the air cavity corresponding to the second bed layer of the reaction chamber enters the second bed layer of the reaction chamber through the wall surface of the second bed layer of the reaction chamber that is permeable to hydrogen and impermeable to oil products, The second bed layer is mixed with the hydrogenation reaction product from the first bed layer of the reaction chamber in the second bed layer of the reaction chamber and subjected to hydrogenation reaction under the action of the catalyst; wherein the first bed layer of the reaction chamber is filled with 50 mL of SD-2 paraffin hydrogenation reaction catalyst (see Table 1), and the second bed layer of the reaction chamber is filled with 100 mL of SD-2 paraffin hydrogenation reaction catalyst (see Table 1); wherein the reaction conditions are: the hydrogen partial pressure (i.e., the pressure of the gas chamber) is 10 MPa, the reaction system pressure (i.e., the pressure of the reaction chamber) is 10 MPa, the reaction temperature of the hydrogenation reaction is 315°C, and the hydrogen-to-oil volume ratio (i.e., the volume flow rate ratio of the hydrogen gas introduced into the gas chamber to the fluid introduced into the reaction chamber) is 20:1;

[0052] The product obtained from the hydrogenation reaction is separated into gas and liquid, and the separated liquid product, i.e. the refined oil product, enters the liquid product storage tank for storage.

[0053] The properties of the paraffin wax used and the properties of the refined oil obtained are shown in Table 2.

[0054] As can be seen from Table 2, after the paraffin is hydrogenated using the technical solution provided by the present invention, the indicators such as the Saibot color and light stability representing the aromatic content are significantly improved.

[0055] Example 4

[0056] This embodiment provides an oil hydrogenation method, which is carried out using the oil hydrogenation device provided in Example 1 of the present invention.

[0057] The difference between the oil hydrogenation method provided in this embodiment and the oil hydrogenation method provided in Example 3 is that the hydrogen-to-oil volume ratio (i.e., the volume flow rate ratio of the hydrogen gas introduced into the gas chamber to the fluid introduced into the reaction chamber) is 10:1.

[0058] The properties of the paraffin wax used and the properties of the refined oil obtained are shown in Table 2.

[0059] As can be seen from Table 2, after the paraffin is hydrogenated using the technical solution provided by the present invention, the indicators such as the Saibot color and light stability representing the aromatic content are significantly improved.

[0060] Example 5

[0061] This embodiment provides an oil hydrogenation method, which is carried out using the oil hydrogenation device provided in Example 1 of the present invention.

[0062] The difference between the oil hydrogenation method provided in this embodiment and the oil hydrogenation method provided in Example 4 is that the hydrogen-to-oil volume ratio (i.e., the volume flow rate ratio of the hydrogen gas introduced into the gas chamber to the fluid introduced into the reaction chamber) is 50:1.

[0063] The properties of the paraffin wax used and the properties of the refined oil obtained are shown in Table 2.

[0064] As can be seen from Table 2, after the paraffin is hydrogenated using the technical solution provided by the present invention, the indicators such as the Saibot color and light stability representing the aromatic content are significantly improved.

[0065] Example 6

[0066] This embodiment provides an oil product hydrogenation method, which is performed using the oil product hydrogenation device provided in Example 1 of the present invention, and comprises:

[0067] The intermediate base heavy distillate oil (coker gas oil) was preheated to a desired temperature (350°C) using a heating furnace to obtain a preheated feedstock oil.

[0068] The hydrogen is introduced into the air cavity corresponding to the first bed layer of the reaction chamber in the hydrogenation reactor, and the preheated raw oil is introduced into the reaction chamber of the hydrogenation reactor. The hydrogen in the air cavity corresponding to the first bed layer of the reaction chamber enters the first bed layer of the reaction chamber through the wall surface of the first bed layer of the reaction chamber that is permeable to hydrogen and impermeable to oil products, mixes with the raw oil in the first bed layer of the reaction chamber, and undergoes a hydrogenation reaction under the action of a catalyst. The hydrogenation reaction product of the first bed layer of the reaction chamber enters the second bed layer of the reaction chamber; the hydrogen is introduced into the air cavity corresponding to the second bed layer of the reaction chamber in the hydrogenation reactor, and the hydrogen in the air cavity corresponding to the second bed layer of the reaction chamber enters the second bed layer of the reaction chamber through the wall surface of the second bed layer of the reaction chamber that is permeable to hydrogen and impermeable to oil products, The bed layer is mixed with the hydrogenation reaction product from the first bed layer of the reaction chamber in the second bed layer of the reaction chamber and subjected to hydrogenation reaction under the action of the catalyst; wherein the first bed layer of the reaction chamber is filled with 50 mL of PHT-01 wax oil hydrogenation reaction catalyst (see Table 1), and the second bed layer of the reaction chamber is filled with 50 mL of PHT-01 wax oil hydrogenation reaction catalyst (see Table 1); wherein the reaction conditions are: the hydrogen partial pressure (i.e., the pressure of the gas chamber) is 14 MPa, the reaction system pressure (i.e., the pressure of the reaction chamber) is 14 MPa, the reaction temperature of the hydrogenation reaction is 380°C, and the hydrogen-to-oil volume ratio (i.e., the volume flow rate ratio of the hydrogen gas introduced into the gas chamber to the fluid introduced into the reaction chamber) is 40:1;

[0069] The product obtained from the hydrogenation reaction is separated into gas and liquid, and the separated liquid product, i.e. the refined oil product, enters the liquid product storage tank for storage.

[0070] The properties of the heavy distillate oil used and the properties of the refined oil obtained are shown in Table 3.

[0071] It can be seen from Table 3 that after the heavy distillate oil is hydrogenated by adopting the technical solution provided by the present invention, the sulfur and nitrogen contents in the heavy distillate oil are significantly reduced.

[0072] Example 7

[0073] This embodiment provides an oil product hydrogenation method, which is performed using the oil product hydrogenation device provided in Example 2 of the present invention, and comprises:

[0074] The intermediate base heavy distillate oil (coker gas oil) was preheated to a desired temperature (350°C) using a heating furnace to obtain a preheated feedstock oil.

[0075] The hydrogen is introduced into the air cavity corresponding to the first bed layer of the reaction chamber in the hydrogenation reactor, and the preheated raw oil is introduced into the reaction chamber of the hydrogenation reactor. The hydrogen in the air cavity corresponding to the first bed layer of the reaction chamber enters the first bed layer of the reaction chamber through the wall surface of the first bed layer of the reaction chamber that is permeable to hydrogen and impermeable to oil products, mixes with the raw oil in the first bed layer of the reaction chamber, and undergoes a hydrogenation reaction under the action of a catalyst. The hydrogenation reaction product of the first bed layer of the reaction chamber enters the second bed layer of the reaction chamber; the hydrogen is introduced into the air cavity corresponding to the second bed layer of the reaction chamber in the hydrogenation reactor, and the hydrogen in the air cavity corresponding to the second bed layer of the reaction chamber enters the second bed layer of the reaction chamber through the wall surface of the second bed layer of the reaction chamber that is permeable to hydrogen and impermeable to oil products, The bed layer is mixed with the hydrogenation reaction product from the first bed layer of the reaction chamber in the second bed layer of the reaction chamber and subjected to hydrogenation reaction under the action of the catalyst; wherein the first bed layer of the reaction chamber is filled with 50 mL of PHT-01 wax oil hydrogenation reaction catalyst (see Table 1), and the second bed layer of the reaction chamber is filled with 50 mL of PHT-01 wax oil hydrogenation reaction catalyst (see Table 1); wherein the reaction conditions are: the hydrogen partial pressure (i.e., the pressure of the gas chamber) is 14 MPa, the reaction system pressure (i.e., the pressure of the reaction chamber) is 14 MPa, the reaction temperature of the hydrogenation reaction is 380°C, and the hydrogen-to-oil volume ratio (i.e., the volume flow rate ratio of the hydrogen gas introduced into the gas chamber to the fluid introduced into the reaction chamber) is 40:1;

[0076] The hydrogen is introduced into the air cavity corresponding to the first bed layer of the reaction chamber in the second hydrogenation reactor, and the product after hydrogenation in the first hydrogenation reactor is introduced into the reaction chamber of the second hydrogenation reactor. The hydrogen in the air cavity corresponding to the first bed layer of the reaction chamber enters the first bed layer of the reaction chamber through the wall surface of the first bed layer of the reaction chamber that is permeable to hydrogen and impermeable to oil products, mixes with the feedstock oil in the first bed layer of the reaction chamber, and undergoes hydrogenation reaction under the action of the catalyst. The hydrogenation reaction product of the first bed layer of the reaction chamber enters the second bed layer of the reaction chamber; the hydrogen is introduced into the air cavity corresponding to the second bed layer of the reaction chamber in the second hydrogenation reactor, and the hydrogen in the air cavity corresponding to the second bed layer of the reaction chamber enters the second bed layer of the reaction chamber through the wall surface of the second bed layer of the reaction chamber that is permeable to hydrogen and impermeable to oil products. The hydrogenation reaction product from the first bed of the reaction chamber is mixed with the hydrogenation reaction product from the second bed of the reaction chamber and subjected to hydrogenation reaction under the action of the catalyst; wherein the first bed of the reaction chamber is filled with 50 mL of PHT-01 wax oil hydrogenation reaction catalyst (see Table 1), and the second bed of the reaction chamber is filled with 50 mL of PHT-01 wax oil hydrogenation reaction catalyst (see Table 1); wherein the reaction conditions are: the hydrogen partial pressure (i.e., the pressure of the gas chamber) is 14 MPa, the reaction system pressure (i.e., the pressure of the reaction chamber) is 14 MPa, the reaction temperature of the hydrogenation reaction is 378°C, and the hydrogen-to-oil volume ratio (i.e., the volume flow rate ratio of the hydrogen gas introduced into the gas chamber to the fluid introduced into the reaction chamber) is 40:1;

[0077] The product obtained from the hydrogenation reaction is separated into gas and liquid, and the separated liquid product, i.e. the refined oil product, enters the liquid product storage tank for storage.

[0078] The properties of the heavy distillate oil used and the properties of the refined oil obtained are shown in Table 3.

[0079] It can be seen from Table 3 that after the heavy distillate oil is hydrogenated by adopting the technical solution provided by the present invention, the sulfur and nitrogen contents in the heavy distillate oil are significantly reduced.

[0080] Example 8

[0081] This embodiment provides an oil product hydrogenation method, which is performed using the oil product hydrogenation device provided in Example 1 of the present invention, and comprises:

[0082] The wax oil is preheated to a desired temperature (350° C.) using a heating furnace to obtain preheated wax oil.

[0083] The hydrogen is introduced into the air cavity corresponding to the first bed layer of the reaction chamber in the hydrogenation reactor, the preheated wax oil is introduced into the reaction chamber of the hydrogenation reactor, the hydrogen in the air cavity corresponding to the first bed layer of the reaction chamber enters the first bed layer of the reaction chamber through the wall surface of the first bed layer of the reaction chamber that is permeable to hydrogen and impermeable to oil products, mixes with the wax oil in the first bed layer of the reaction chamber, and undergoes a hydrogenation reaction under the action of a catalyst, and the hydrogenation reaction product of the first bed layer of the reaction chamber enters the second bed layer of the reaction chamber; the hydrogen is introduced into the air cavity corresponding to the second bed layer of the reaction chamber in the hydrogenation reactor, the hydrogen in the air cavity corresponding to the second bed layer of the reaction chamber enters the second bed layer of the reaction chamber through the wall surface of the second bed layer of the reaction chamber that is permeable to hydrogen and impermeable to oil products, The bed layer is mixed with the hydrogenation reaction product from the first bed layer of the reaction chamber in the second bed layer of the reaction chamber and subjected to hydrogenation reaction under the action of the catalyst; wherein the first bed layer of the reaction chamber is filled with 50 mL of PHT-01 wax oil hydrogenation reaction catalyst (see Table 1), and the second bed layer of the reaction chamber is filled with 100 mL of PHT-01 wax oil hydrogenation reaction catalyst (see Table 1); wherein the reaction conditions are: the hydrogen partial pressure (i.e., the pressure of the gas chamber) is 8 MPa, the reaction system pressure (i.e., the pressure of the reaction chamber) is 8 MPa, the reaction temperature of the hydrogenation reaction is 380°C, and the hydrogen-to-oil volume ratio (i.e., the volume flow rate ratio of the hydrogen gas introduced into the gas chamber to the fluid introduced into the reaction chamber) is 20:1;

[0084] The product obtained from the hydrogenation reaction is separated into gas and liquid, and the separated liquid product, i.e. the refined oil product, enters the liquid product storage tank for storage.

[0085] The properties of the wax oil used and the properties of the refined oil obtained are shown in Table 5.

[0086] Comparative Example 1

[0087] This comparative example provides a method for hydrogenating an oil product.

[0088] The difference between the oil product hydrogenation method provided in this comparative example and the oil product hydrogenation method provided in Example 3 is:

[0089] (1) The oil product hydrogenation devices used are different. The hydrogenation reactor in the oil product hydrogenation device used in this comparative example is a conventional trickle bed reactor;

[0090] (2) The reaction temperature of the hydrogenation reaction was 330°C, and the volume ratio of hydrogen to oil was 300:1.

[0091] The properties of the paraffin wax used and the properties of the refined oil obtained are shown in Table 4. As can be seen from Table 4, in order to achieve a hydrofining effect close to that of Example 3 in this comparative example, the volume of hydrogen oil needs to be greatly increased and the reaction temperature needs to be increased.

[0092] Comparative Example 2

[0093] This comparative example provides a method for hydrogenating an oil product.

[0094] The difference between the oil product hydrogenation method provided in this comparative example and the oil product hydrogenation method provided in Example 3 is:

[0095] (1) The oil hydrogenation device used is different. The hydrogenation reactor in the oil hydrogenation device used in this comparative example includes a ceramic membrane hydrogen mixer and a conventional trickle bed reactor connected by pipelines; wherein the ceramic membrane hydrogen mixer includes a shell and an alumina tubular ceramic membrane disposed in the shell, and the ceramic membrane hydrogen mixer is provided with a feed inlet and a discharge inlet connected to the flow channel of the alumina tubular ceramic membrane, and an air inlet connected to the space between the shell and the alumina tubular ceramic membrane. Since the ceramic membrane hydrogen mixer cannot be loaded with catalyst, the conventional trickle bed reactor is loaded with 150 ml of SD-2 paraffin hydrogenation reaction catalyst;

[0096] (2) The reaction temperature of the hydrogenation reaction is 320°C.

[0097] The properties of the paraffin wax used and the properties of the refined oil obtained are shown in Table 4. As can be seen from Table 4, the hydrogenation effect of this comparative example is far inferior to that of Example 3.

[0098] Comparative Example 3

[0099] This comparative example provides a method for hydrogenating an oil product.

[0100] The difference between the oil hydrogenation method provided in this comparative example and the oil hydrogenation method provided in Example 8 is that the first bed layer of the reaction chamber is not loaded with catalyst, and the second bed layer of the reaction chamber is loaded with 150 mL of PHT-01 wax oil hydrogenation reaction catalyst (see Table 1).

[0101] See Table 5 for the properties of refined oil products.

[0102] As can be seen from Table 5, the first bed is loaded with catalyst and reacts directly after mixing with hydrogen, so as to avoid the reduction of reaction effect due to the collision and enlargement of bubbles caused by the energy dissipation of bubbles in long-distance transmission.

[0103] Experimental Example 1

[0104] In this experimental example, perovskite ceramic material (average pore diameter of 50 μm), tungsten bronze ceramic material (average pore diameter of 50 μm), and pyrochlore ceramic material (average pore diameter of 50 μm) were used as the hydrogen-permeable and oil-impermeable materials for the wall surface of the reaction chamber 11 of the hydrogenation reactor in Example 1 located in the gas chamber 12, and the oil hydrogenation method provided in Example 3 was used to carry out oil hydrogenation. The particle size of the hydrogen bubbles in the material in the first bed layer was tested at different time periods. Specifically, the particle size of the hydrogen bubbles in the material was determined by CT scanning after freezing with liquid nitrogen. The results are shown in Table 6.

[0105] It can be seen from Table 6 that the hydrogen bubble particle size generated by using the perovskite ceramic material as the wall material of the reaction chamber located in the gas cavity is relatively uniform.

[0106] Table 1

[0107]

[0108] Table 2

[0109]

[0110]

[0111] Table 3

[0112] project Heavy distillates Example 6 Refined Oil Example 7 Refined Oil <![CDATA[Density (20 °C), g / cm 3 > 0.9004 0.8978 0.8965 Sulfur content, μg / g 7145.1 140 25 Nitrogen content, μg / g 1165.0 11.3 6.4

[0113] Table 4

[0114]

[0115] Table 5

[0116] project Wax oil (raw material) Comparative Example 3 Example 8 Reaction pressure, MPa / 8 8 Reaction temperature,℃ / 380 380 Total nitrogen content, μg / g 3636 1482.5 381.0 Denitrification rate, % / 59.23 89.52 Total sulfur content, μg / g 16770 2300.0 396.0 Desulfurization rate, % / 86.29 97.64

[0117] Table 6

[0118] serial number Time min Perovskite ceramic materials Tungsten Bronze Ceramic Material Pyrochlore ceramic materials 1 initial 48.34 49.19 49.58 2 30 48.54 53.51 51.85 3 60 50.08 39.14 51.56 4 90 49.87 37.16 53.78 5 120 49.24 37.16 48.85 6 150 50.39 37.68 51.31 7 180 50.07 56.56 52.84

[0119] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. An oil product hydrogenation device, wherein: The device comprises a hydrogenation reactor, which is provided with a reaction chamber; a feed inlet is provided at the bottom of the reaction chamber, a discharge port is provided at the top, and the reaction chamber is provided with at least two beds; The hydrogenation reactor is provided with independent air cavities corresponding to each bed layer of the reaction chamber, and each air cavity is provided with an air inlet; wherein one air cavity is provided corresponding to one bed layer of the reaction chamber, and each air cavity is independent of each other; The reaction chamber passes through each of the gas chambers, and the wall surface of the reaction chamber located inside the gas chamber is made of a material that is permeable to hydrogen but not permeable to oil.

2. The device according to claim 1, wherein: The material of the hydrogen-permeable and oil-impermeable product is perovskite ceramic, tungsten bronze ceramic or pyrochlore ceramic.

3. The device according to claim 2, wherein: The material of the hydrogen-permeable and oil-impermeable product is perovskite ceramic.

4. The device according to claim 3, wherein: The ratio of the cross-sectional area of ​​each bed layer in the reaction chamber perpendicular to the extension direction of the reaction chamber to the area of ​​the wall of the bed layer located in the gas cavity of the reaction chamber and made of a material that is permeable to hydrogen but not permeable to oil is 1:10-1:

50.

5. The device according to claim 1 or 4, wherein: The ratio of the length of each bed layer in the reaction chamber located in the gas cavity along the extension direction of the reaction chamber to the length of the bed layer in the reaction chamber along the extension direction of the reaction chamber is not less than 9:

10.

6. The device according to claim 1, wherein: The hydrogenation reactor further comprises a hydrogenation reaction catalyst arranged in the portion of the reaction chamber located in the gas chamber.

7. The device according to claim 1, wherein: The air cavity corresponding to each bed layer in the reaction chamber is located at the root of the bed layer in the reaction chamber.

8. The device according to claim 1, wherein: The oil product hydrogenation unit comprises at least two hydrogenation reactors connected in series; and / or The oil product hydrogenation device comprises a gas-liquid separator, and the feed inlet of the gas-liquid separator is connected to the discharge outlet of the hydrogenation reactor.

9. A method for hydrogenating an oil product, the method being carried out using the oil product hydrogenation device according to any one of claims 1 to 8, the method comprising: Pass hydrogen into the air cavity corresponding to the first bed layer of the reaction chamber in the hydrogenation reactor, pass the preheated crude oil into the reaction chamber of the hydrogenation reactor, the hydrogen in the air cavity corresponding to the first bed layer of the reaction chamber enters the first bed layer of the reaction chamber through the wall surface of the first bed layer of the reaction chamber that is permeable to hydrogen and impermeable to oil products, mixes with the crude oil in the first bed layer of the reaction chamber, and undergoes hydrogenation reaction under the action of the catalyst, and the hydrogenation reaction product of the first bed layer of the reaction chamber enters the second bed layer of the reaction chamber; Pass hydrogen into the air cavity corresponding to the second bed layer of the reaction chamber in the hydrogenation reactor, the hydrogen in the air cavity corresponding to the second bed layer of the reaction chamber enters the second bed layer of the reaction chamber through the wall surface of the second bed layer of the reaction chamber that is permeable to hydrogen and impermeable to oil products, mixes with the hydrogenation reaction product from the first bed layer of the reaction chamber in the second bed layer of the reaction chamber, and undergoes hydrogenation reaction under the action of the catalyst; and so on until the hydrogenation reaction is completed in the last bed layer of the reaction chamber; wherein the first bed layer of the reaction chamber, the second bed layer of the reaction chamber, and the last bed layer of the reaction chamber are named in sequence along the direction from the feed inlet to the discharge outlet of the reaction chamber; The product obtained from the hydrogenation reaction is subjected to gas-liquid separation to obtain refined oil products.

10. The method according to claim 9, wherein: The method includes: When the feedstock oil is wax oil, the hydrogen partial pressure in the hydrogenation reactor is 7.0MPa-15.0MPa, the reaction temperature of the hydrogenation reaction in the hydrogenation reactor is 300℃-390℃, and the volume space velocity is 0.5h -1 -2.0h -1 , the volume ratio of hydrogen to oil is 10:1-50:1.

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