WO2020155503A1 - Bottom type residual oil hydrogenation emulsification bed micro-interface enhanced reaction device and method - Google Patents

Abstract

A bottom type residual oil hydrogenation emulsification bed micro-interface enhanced reaction device and method, comprising a reactor body (1), at least one bubble breaker (1-1, 1-2) provided below the reactor body (1), a gas-liquid separator (2), a circulation pump (3), and a heat exchanger (4).A gas material and a liquid material are first fed into the breakers (1-1, 1-2); the gas is broken into micron-sized bubbles which are violently mixed with the liquid to form a gas-liquid emulsion which then enters the reactor body (1); because of low-speed and difficult coalescence characteristics of microbubbles, a gas-liquid emulsification bed reaction system is formed in the reactor body (1); after the reaction is completed, the reaction material enters the gas-liquid separator (2) for gas and liquid separation; the feed liquid is conveyed by the circulation pump (3); after the feed liquid passes through the heat exchanger (4), a portion of the feed liquid is extracted, and the remaining enters the breakers (1-1, 1-2) for bubble breaking.

Description

Bottom-mounted residue hydro-emulsified bed micro-interface strengthening reaction device and method Technical field

The invention relates to a bottom-mounted residual oil hydro-emulsified bed micro-interface strengthening reaction device and method.

Background technique

Residues can be divided into many types due to different crude oil producing areas and refining processes. Generally, they can be divided into two categories: atmospheric residues and vacuum residues. The main components of residual oil include saturated hydrocarbons, aromatic hydrocarbons, gums and asphaltenes. Under the action of high temperature, high pressure and catalyst, the residual oil can be deeply hydrogenated to obtain light fuel oil products through a series of complex physical and chemical changes such as ring opening and cracking.

With the increasing demand for light oil products in various countries around the world, the requirements for environmental protection have become stricter, and people have paid more attention to the hydrogenation technology of residual oil. Traditional residual oil hydrogenation generally uses a suspended bed hydrogenation reactor. Although the reactor has strong adaptability to raw materials and simple operation, it is controlled by mass transfer, so the hydrogenation reaction efficiency is low. The fundamental reason is that the bubble size in the reactor is relatively large (generally 3-10mm), so the mass transfer area of the gas-liquid phase boundary is small (generally 100-200m2/m3), which limits the mass transfer efficiency. Therefore, high temperature (above 470°C) and high pressure (above 20MPa) operations have to be used in engineering to increase the solubility of hydrogen to increase the mass transfer rate, thereby strengthening the reaction process. However, high temperature and high pressure produce a series of side effects: high energy consumption and production cost, high investment intensity, short equipment operation cycle, many failures, poor intrinsic safety, etc., which bring challenges to industrialized mass production.

The bubble diameter (Sauter diameter) d32 is the key parameter that determines the size of the phase boundary area and the core factor that determines the gas-liquid reaction rate. When d32 gradually decreases, the volumetric mass transfer coefficient gradually increases; especially when d32 is less than 1mm, the volumetric mass transfer coefficient increases rapidly with the decrease of d32 in an exponential form. Therefore, reducing d32 to the nano-micron level can greatly enhance the gas-liquid reaction. Bubbles with a diameter of 1μm≤d32<1mm can be called microbubbles, and bubbles with a diameter of 50nm≤d32<1μm can be called nanobubbles. The phase interface formed by microbubbles and nanobubbles is called nano-micro interface. If there are both nanobubbles and microbubbles in the system, the system is called a nano-micro interface system. According to the Yang-Laplace equation, the internal pressure of the bubble is inversely proportional to its radius, so nano-microbubbles are also beneficial to increase the internal pressure of the bubble and increase the solubility of the gas. Therefore, in the gas-liquid reaction process, the nano-micro interface system can enhance the gas-liquid mass transfer, thereby accelerating the gas-liquid reaction. Nano-micro bubbles have the characteristics of rigidity, good independence, and are not easy to coalesce. Therefore, the gas-liquid of the nano-micro bubble system is fully mixed to obtain a system containing a large number of nano-micro bubbles, and a higher phase boundary area is formed in the reactor, thereby accelerating reaction speed.

Summary of the invention

The purpose of the present invention is to provide a bottom-mounted residual oil hydro-emulsified bed micro-interface strengthening reaction device and method, which uses a small micron bubble breaker to transfer the pressure energy of the gas and the kinetic energy of the liquid to the bubbles and finally transform them into the surface energy of the bubbles The device forms small micron-sized bubbles through the interaction of fluid turbulent microstructures and mechanical microstructures, and forms a micro-interface or nano-micro interface gas-liquid reaction system.

The present invention specifically adopts the following technical solutions to achieve the above technical objectives:

A micro-interface strengthening reaction device for residual oil hydrogenation emulsified bed, comprising:

The main body of the reactor; the top of which is provided with a gas-liquid discharge port;

At least one bubble breaker; arranged at the lower part of the reactor main body; the bubble breaker is provided with an air inlet, a liquid inlet and a discharge port, and the discharge port is connected to the reactor main body;

A gas-liquid separator; a gas-liquid discharge port connected to the main body of the reactor; an exhaust port is provided at the top of the gas-liquid separator, and a liquid outlet is provided at the bottom;

Circulating pump; connected to the liquid outlet of the gas-liquid separator;

Heat exchanger; connected to the outlet pipeline of the circulating pump; the heat exchanger is provided with a liquid discharge port, the liquid discharge port is respectively connected with the liquid discharge pipeline and the circulating liquid pipeline, and the circulating liquid pipeline is connected with air bubbles Liquid inlet of the breaker.

The bubble breaker of the present invention is divided into pneumatic, hydraulic and gas-liquid linkage types according to the energy input mode or the gas-liquid ratio. The pneumatic bubble breaker is driven by gas, and the input gas volume is much larger than the liquid volume; the hydraulic bubble breaker The device is driven by liquid, and the input gas volume is generally less than the amount of liquid. The gas-liquid linkage bubble breaker is driven by gas and liquid. When multiple bubble breakers are used, pneumatic and hydraulic bubble breakers can be connected in series to form a set of bubble breakers. A reaction system can combine multiple bubble breakers in series or in parallel.

The bubble breaker of the present invention can be installed below the main body of the reactor, that is, the down-mounted type, and the gas-liquid emulsion enters the main body from bottom to top. The feature of the down-mounted type is that it can form a flat plug flow emulsified bed reaction system, which is beneficial to the improvement of product selectivity.

As a further improvement of the present invention, a deflector tube is vertically arranged in the reactor. The deflector can promote the full mixing of gas and liquid.

The present invention also provides a method for using the above-mentioned device to carry out the micro-interface strengthening reaction of the residual oil hydro-emulsified bed, which includes:

Pour gas and liquid materials into the air inlet and liquid inlet of the bubble breaker respectively;

The bubble breaker breaks the material into a micron-sized bubble system, thus forming a gas-liquid emulsification system, and then enters the main body of the reactor to form a flat plug flow to continue the reaction;

The material after the reaction enters the gas-liquid separator from the gas-liquid outlet for gas-liquid separation, the gas is discharged from the exhaust port, and the liquid enters the circulating pump from the liquid outlet, and part of it is extracted after passing through the heat exchanger, and part of the bubble breaks. The device is used for bubble breaking.

As a further improvement of the present invention, the method further includes the gas-liquid emulsification system and the solid powder catalyst in the main body of the reactor to form a gas-liquid solid pseudo-emulsification system. Preferably, the catalyst is a carbon-supported iron-based catalyst, which accounts for 0.2 to 1% of the mass of the input liquid raw material (ie, residual oil, residual oil-coal tar mixed oil, etc.).

As a further improvement of the present invention, the volume ratio of the gas material and the liquid material entering the bubble breaker is 500-1800:1.

As a further improvement of the present invention, the reaction pressure in the bubble breaker is 1-12 MPa.

As a further improvement of the present invention, the reaction temperature in the bubble breaker is 440°C to 470°C.

As a further improvement of the present invention, the air velocity of the bubble breaker is 0.6 to 1.5 h ^-1 .

As a further improvement of the present invention, the micron-sized bubble system formed in the bubble breaker has an average bubble diameter of 10 μm to 500 μm. For the 100nm-100μm bubble system, it contains both nanobubbles and microbubbles, which can form a nano-micro interface, which can obtain an effect equivalent to that of a 10μm-500μm micro-interface on the basis of lower air pressure and temperature.

In the reaction system of the present invention, in order to ensure that the system in the bubble breaker enters the reactor, the operating temperature and pressure of the bubble breaker are slightly higher than the operating temperature and pressure in the reactor. When the size of the bubbles in the bubble breaker is small, it is more conducive to the progress of the reaction. The operating temperature and pressure in the reactor can be further reduced.

The device and method of the present invention are suitable for gas-liquid reaction systems. The bubble size of the gas-liquid system is reduced from the traditional 3-10mm to 100nm-500μm by using the bubble breaker, thereby greatly increasing the gas holdup of the system and the mass transfer area of the gas-liquid phase boundary, accelerating the multiphase reaction process, and improving the gas Utilization rate, improve the environmental problems caused by excessive emissions, and solve the problems of high temperature, high pressure, high material consumption and energy consumption, high investment, high risk in the traditional gas-liquid reaction process, thereby reducing equipment investment costs and operating costs.

The reaction system of the present invention has relatively small bubbles, resulting in slower gas-liquid separation, so a dedicated high-efficiency gas-liquid separator (such as a suspension separator) needs to be installed after the reactor to realize the separation of microbubbles and liquid.

The device and method of the present invention are not only suitable for the hydrogenation of medium and low pressure high space velocity residual oil, but also for the hydrogenation of mixed oil of medium and low pressure high space velocity residual oil and coal tar, as well as pulverized coal-residue, pulverized coal-tar, and pulverized coal -Catalytic oil slurry and other highly difficult mixed solid-liquid systems, low pressure and high space velocity hydrogenation reaction to prepare light fuel oil or other specific petroleum products.

Compared with the traditional gas-liquid reactor, the present invention has the following advantages:

1. Low energy consumption. Traditional fixed-bed gas-liquid reactors use high pressure to increase the solubility of gaseous raw materials in liquid raw materials to enhance mass transfer. In the present invention, the gas is broken into a small micron-scale bubble system of 100nm-500μm to form an emulsified bed, which can greatly increase the area of the phase boundary between the gas and liquid phases and achieve the effect of enhancing mass transfer. Therefore, the pressure can be appropriately lowered, thereby reducing energy consumption.

2. Low gas-liquid ratio. In order to ensure that the liquid raw materials can fully react in the traditional gas-liquid reactor, the gas-liquid ratio is generally controlled at 2000-3000:1. This method greatly enhances the mass transfer, so the gas-liquid ratio can be greatly reduced, which not only reduces the material consumption of the gas, but also reduces the energy consumption of the subsequent gas cycle compression. Due to the enhancement of mass transfer and reaction in this method, the hydrogen-to-oil ratio can be greatly reduced, which not only reduces the material consumption of hydrogen, but also reduces the energy consumption of cyclic compression.

3. Flexible process configuration, high production safety, low product cost per ton, and strong market competitiveness.

Description of the drawings

Fig. 1 is a schematic diagram of the structure of a bottom-mounted residual oil hydro-emulsified bed micro-interface strengthening reaction device in Example 1;

2 is a schematic diagram of the structure of a bottom-mounted residual oil hydro-emulsified bed micro-interface strengthening reaction device in Example 2;

3 is a schematic diagram of the structure of a bottom-mounted residual oil hydro-emulsified bed micro-interface strengthening reaction device in Example 3;

4 is a schematic diagram of the structure of a bottom-mounted residual oil hydro-emulsified bed micro-interface strengthening reaction device in Example 4;

In the picture: 1 reactor body; 2 gas-liquid separator; 3 circulating pump; 4 heat exchanger; 1-1 hydraulic breaker; 1-2 pneumatic bubble breaker; 1-3 gas raw material pipeline; 1 -4 Air inlet pipeline of hydraulic bubble breaker; 1-5 primary emulsion pipeline; 1-6 air inlet pipeline of pneumatic bubble breaker; 1-7 liquid raw material pipeline; 1-8 gas-liquid discharge pipeline ; 1-9 gas-liquid linkage bubble breaker; 1-10, deflector tube; 2-1 liquid outlet pipe; 2-2 exhaust pipe; 3-1 outlet pipe; 4-1 liquid discharge pipe Road; 4-2 circulating fluid pipeline.

detailed description

The specific embodiments of the present invention will be described in further detail below in conjunction with the accompanying drawings. The following examples are used to illustrate the present invention, but do not limit the scope of the present invention.

Example 1

A bottom-mounted residue hydro-emulsified bed micro-interface strengthening reaction device as shown in Figure 1, including a reactor main body 1; a gas-liquid discharge port is provided on the top of the reactor and connected to gas-liquid discharge pipelines 1-8;

A set of bubble breakers; consists of a hydraulic bubble breaker 1-1 and a pneumatic bubble breaker 1-2 in series. The pneumatic bubble breaker 1-2 is equipped with an air inlet, which is connected to the gas raw material pipeline 1-3; the liquid inlet is connected to the liquid raw material pipeline 1-7; the hydraulic bubble breaker 1-1 is equipped with an inlet Liquid port, connected to circulating fluid pipeline 4-2; Air inlet, connected to hydraulic bubble breaker air inlet pipeline 1-4;

Gas-liquid separator 2; connected to gas-liquid discharge pipelines 1-8; gas-liquid separator 2 is provided with an exhaust port on the top, connected to the exhaust pipeline 2-2, and a liquid outlet at the bottom, connected to the liquid outlet pipeline 2-1;

Circulating pump 3; connect the liquid outlet line 2-1;

The heat exchanger 4 is connected to the outlet pipe 3-1 of the circulating pump 3; the heat exchanger 4 is provided with a liquid discharge port, which is connected to the liquid discharge pipe 4-1 and the circulating liquid pipe 4-2.

Hydrogen and atmospheric residual oil enter the bubble breaker through gas raw material pipelines 1-3 and liquid raw material pipelines 1-7 at a volume ratio of 600:1. The residual oil is sent to the pneumatic bubble breaker 1-2 from the liquid raw material pipeline 1-7; the hydrogen entering from the gas raw material pipeline 1-3 is divided into two ways, one way is through the pneumatic bubble breaker intake pipeline 1-6 It is sent into the pneumatic bubble breaker 1-2 as the breaking driving force, and the other way enters the hydraulic bubble breaker 1-1 through the air bubble breaker air inlet pipe 1-4, and is in the bubble breaker 1-1. The circulating liquid sent from the circulating liquid pipeline 4-2 is broken into primary emulsion, and the obtained primary emulsion enters the pneumatic bubble breaker 1-2 through the primary emulsification pipeline 1-5. In the bubble breaker 1-2, hydrogen After fully mixing with residual oil to form 100μm～500μm microbubbles and gas-liquid emulsification system, it enters the reactor body 1 to form a flat plug flow to continue the reaction. After the emulsification system stops in the reactor body for 2.5h, it passes through the top gas-liquid discharge pipe Route 1-8 enters the gas-liquid separator 2, the separated gas is sent to the subsequent treatment through the exhaust pipe 2-2, and the obtained liquid enters the circulating pump 3 through the liquid outlet pipe 2-1. After the liquid sent by the circulating pump 3 enters the heat exchanger 4 through the outlet pipe 3-1, part of it is sent to the subsequent processing by the liquid discharge pipe 4-1, and the rest is sent to the circulating liquid pipe 4-2 as the bubble breaking power To the hydraulic bubble breaker 1-1.

The reaction pressure is 4MPa, the reaction temperature is 440°C, a carbon-supported iron-based catalyst is used, and the space velocity is controlled to 0.6h ^-1 . The final light oil yield is 80%, which is basically the same as the yield of a traditional suspended bed reactor at 18MPa and 480°C.

Example 2

The device structure of Example 2 is shown in FIG. 2, and the difference from Example 1 is that the flow deflector 1-10 is provided in the reactor body 1.

Hydrogen and atmospheric residual oil enter the bubble breaker through gas raw material pipelines 1-3 and liquid raw material pipelines 1-7 at a volume ratio of 900:1. The residual oil is sent to the pneumatic bubble breaker 1-2 from the liquid raw material pipeline 1-7; the hydrogen entering from the gas raw material pipeline 1-3 is divided into two ways, one way is through the pneumatic bubble breaker intake pipeline 1-6 It is sent into the pneumatic bubble breaker 1-2 as the breaking driving force, and the other way enters the hydraulic bubble breaker 1-1 through the air bubble breaker air inlet pipe 1-4, and is in the bubble breaker 1-1. The circulating liquid sent from the circulating liquid pipeline 4-2 is broken into primary emulsion, and the obtained primary emulsion enters the pneumatic bubble breaker 1-2 through the primary emulsification pipeline 1-5. In the bubble breaker 1-2, hydrogen After fully mixing with residual oil to form 400nm～200μm microbubbles and gas-liquid emulsification system, it enters the reactor body 1 to form a flat plug flow to continue the reaction. After the emulsification system stops in the reactor body for 2.5h, it passes through the top gas-liquid discharge pipe Route 1-8 enters the gas-liquid separator 2, the separated gas is sent to the subsequent treatment through the exhaust pipe 2-2, and the obtained liquid enters the circulating pump 3 through the liquid outlet pipe 2-1. After the liquid sent by the circulating pump 3 enters the heat exchanger 4 through the outlet pipe 3-1, part of it is sent to the subsequent processing by the liquid discharge pipe 4-1, and the rest is sent to the circulating liquid pipe 4-2 as the bubble breaking power To the hydraulic bubble breaker 1-1.

The reaction pressure is 1MPa, the reaction temperature is 450°C, a carbon-supported iron-based catalyst is used, and the space velocity is controlled to 0.8h ^-1 . The final light oil yield was 80%.

Example 3

The device structure of Embodiment 3 is shown in Fig. 3, and the difference from Embodiment 1 is that the bubble breaker uses gas-liquid linkage bubble breaker 1-9.

The mixture of 30% mass fraction residual oil and 70% coal tar and fresh hydrogen enter the bubble breaker 1 through the gas raw material pipeline 1-3 and the liquid raw material pipeline 1-7 at a volume ratio of 1:1800. 9 in. The pressure is maintained at 12MPa, the temperature is controlled at 470°C, the carbon-supported iron-based catalyst is used, and the space velocity is 1.5h ^-1 . In the bubble breaker 1-9, the circulating fluid sent through the circulating fluid pipeline 4-2 is broken into a 10μm-100μm microbubble gas-liquid system, and then enters the reactor body 1 to form a flat plug flow to continue the reaction, and the emulsification system stops. After staying in the main body of the reactor for 2.5 hours, it enters the gas-liquid separator 2 through the top gas-liquid discharge pipe 1-8, and the separated gas is sent to the subsequent treatment through the exhaust pipe 2-2, and the liquid obtained is passed through the liquid discharge pipe Road 2-1 enters circulating pump 3. After the liquid sent by the circulating pump 3 enters the heat exchanger 4 through the outlet pipe 3-1, part of it is sent to the subsequent processing by the liquid discharge pipe 4-1, and the rest is sent to the circulating liquid pipe 4-2 as the bubble breaking power To the gas-liquid linkage bubble breaker 1-9, the final light oil yield is 83%.

Example 4

The device structure of Embodiment 4 is shown in Fig. 4, and the difference from Embodiment 3 is only that the air bubble breaker adopts a pneumatic air bubble breaker 1-2.

Hydrogen and atmospheric residual oil enter the bubble breaker through gas raw material pipelines 1-3 and liquid raw material pipelines 1-7 respectively at a volume ratio of 1000:1. In the bubble breaker 1-2, hydrogen and residual oil are fully mixed to form 10μm-200μm microbubbles and a gas-liquid emulsification system, then enter the reactor body 1 to form a flat plug flow to continue the reaction, and the emulsification system stops in the reactor body for 2.5 After h, it enters the gas-liquid separator 2 through the top gas-liquid discharge line 1-8, the separated gas is sent to the subsequent treatment through the exhaust line 2-2, and the obtained liquid enters the circulation through the liquid outlet line 2-1 Pump 3. After the liquid sent by the circulating pump 3 enters the heat exchanger 4 through the outlet pipe 3-1, part of it is sent to the subsequent processing by the liquid discharge pipe 4-1, and the rest is sent to the circulating liquid pipe 4-2 as the bubble breaking power To pneumatic bubble breaker 1-2.

The reaction pressure is 10MPa, the reaction temperature is 455°C, a carbon-supported iron-based catalyst is used, and the space velocity is controlled to 1.0h ^-1 . The final light oil yield was 84%.

Example 5

Example 5 and Example 4 use the same device, and hydrogen and atmospheric residue are respectively fed into the bubble breaker through gas raw material pipelines 1-3 and liquid raw material pipelines 1-7 at a volume ratio of 500:1. In the bubble breaker 1-2, hydrogen and residual oil are fully mixed to form 100nm-100μm microbubbles and a gas-liquid emulsification system. After entering the reactor body 1 to form a flat plug flow to continue the reaction, the emulsification system stops in the reactor body for 2.5 After h, it enters the gas-liquid separator 2 through the top gas-liquid discharge line 1-8, the separated gas is sent to the subsequent treatment through the exhaust line 2-2, and the obtained liquid enters the circulation through the liquid outlet line 2-1 Pump 3. After the liquid sent by the circulating pump 3 enters the heat exchanger 4 through the outlet pipe 3-1, part of it is sent to the subsequent processing by the liquid discharge pipe 4-1, and the rest is sent to the circulating liquid pipe 4-2 as the bubble breaking power To pneumatic bubble breaker 1-2.

The reaction pressure is 6MPa, the reaction temperature is 455°C, a carbon-supported iron-based catalyst is used, and the space velocity is controlled to 0.4h ^-1 . The final light oil yield was 83%.

Claims (10)

1. A bottom-mounted residue hydro-emulsified bed micro-interface strengthening reaction device, which is characterized in that it comprises:

   The main body of the reactor; the top of which is provided with a gas-liquid discharge port;

   At least one bubble breaker; arranged at the lower part of the reactor main body; the bubble breaker is provided with an air inlet, a liquid inlet and a discharge port, and the discharge port is connected to the reactor main body;

   A gas-liquid separator; a gas-liquid discharge port connected to the main body of the reactor; an exhaust port is provided at the top of the gas-liquid separator, and a liquid outlet is provided at the bottom;

   Circulating pump; connected to the liquid outlet of the gas-liquid separator;

   Heat exchanger; connected to the outlet pipeline of the circulating pump; the heat exchanger is provided with a liquid discharge port, the liquid discharge port is respectively connected with the liquid discharge pipeline and the circulating liquid pipeline, and the circulating liquid pipeline is connected with air bubbles Liquid inlet of the breaker.
2. The device according to claim 1, wherein the bubble breaker is a gas-liquid linkage bubble breaker, a pneumatic bubble breaker, a hydraulic bubble breaker, or a series combination thereof.
3. The device according to claim 1, characterized in that, a deflector tube is vertically arranged in the reactor.
4. A method for using the device as claimed in any one of claims 1 to 3 to carry out a micro-interface strengthening reaction in a residual oil hydro-emulsion bed, characterized in that it comprises:

   Pour gas and liquid materials into the air inlet and liquid inlet of the bubble breaker respectively;

   The bubble breaker breaks the material into a micron-sized bubble system, thus forming a gas-liquid emulsification system, and then enters the main body of the reactor to form a flat plug flow to continue the reaction;

   The material after the reaction enters the gas-liquid separator from the gas-liquid outlet for gas-liquid separation, the gas is discharged from the exhaust port, and the liquid enters the circulating pump from the liquid outlet, and part of it is extracted after passing through the heat exchanger, and part of the bubble breaks. The device is used for bubble breaking.
5. The method according to claim 4, further comprising: the gas-liquid emulsification system and the solid powder catalyst in the main body of the reactor form a gas-liquid solid pseudo-emulsification system.
6. The method according to claim 4, wherein the volume ratio of the gas material and the liquid material entering the bubble breaker is 500-1800:1.
7. The method according to claim 4, wherein the reaction pressure in the bubble breaker is 1-12 MPa.
8. The method according to claim 4, wherein the reaction temperature in the bubble breaker is 440°C to 470°C.
9. The method according to claim 4, wherein the air velocity of the bubble breaker is 0.4 to 1.5 h ^-1 .
10. The method according to claim 4, wherein the micron-sized bubble system formed in the bubble breaker has an average bubble diameter of 100 nm-500 μm.

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