CN101314120B - A slurry bed reactor and its application - Google Patents

Abstract

A slurry bed loop reactor, comprising a riser and at least one downcomer 3, the riser consists of a reaction zone 1 and a settling zone 2 with enlarged pipe diameter, the top of the settling zone 2 is provided with an exhaust port 13, each The filter medium 4 in the downcomer 3 is divided into a filtrate area 5 and a slurry area 6, wherein the filtrate area 5 communicates with the liquid discharge port 10, and the two ends of the slurry area 6 communicate with the two ends of the riser, and the settling area 2 is divided into The steady flow zone 19 and the flow disturbance zone 20, wherein, the top of the steady flow zone 19 is communicated with the downcomer 3 through the pipeline 16, and the bottom of the steady flow zone 19 is directly communicated with the reaction zone 1 through the opening 18 or the draft tube 17, the present invention The provided slurry bed loop reactor can achieve continuous and efficient separation of solid catalyst particles, liquid products and reaction gases, continuous discharge of gas-liquid-solid three-phase, and separate the settling area into a disturbed flow area and a steady flow area to reduce the pressure caused by the reaction. The disturbance of the settling particles in the settling zone by the rising slurry in the settling zone improves the separation efficiency of the settling zone and reduces the filter load of the downcomer, thereby increasing the processing capacity and separation efficiency of the entire reactor, and prolonging the backwash cycle.

Description

A slurry bed reactor and its application

technical field

The present invention relates to a device and method for separating solid particles from liquid, more specifically, to a device for continuous separation of liquid and solid particles in a slurry bed loop reactor and its application method.

Background technique

The slurry bed reactor is a commonly used gas-liquid (slurry) contact reaction equipment with a very high liquid storage capacity. For the catalytic reaction process with large reaction heat, the use of slurry bed reactor can effectively remove the reaction heat, realize the isothermal operation of the reactor, and ensure the normal operation of the reactor, so it has been widely used in today's chemical process. The slurry bed loop reactor is a high-efficiency heterogeneous reactor developed on the basis of the slurry bed bubbling reactor. In addition to all the advantages of the slurry bed bubbling reactor, the slurry bed loop reactor can also make the internal fluid circulate regularly, thus enhancing the mixing, diffusion and heat transfer between the reactants and mass transfer.

In order to eliminate the influence of diffusion in a slurry bed reactor, catalysts with tens of microns or even finer particles are generally used, but this also brings about the difficulty of separating the reaction products from the catalyst particles. How to effectively realize liquid-solid separation has become a key technology in the process of using slurry bed reaction.

The liquid-solid separation of the catalyst slurry in a slurry bed reactor is generally carried out outside the reactor. The slurry containing the catalyst must be transported by a special pump, and the separated catalyst still needs to be sent back to the reactor in the form of slurry. This process tends to cause breakage of the catalyst particles, thereby causing problems for long-term continuous operation of the reactor.

USP 6068760 and WO 02/097007A2 all disclose the method of using sedimentation technology to realize liquid-solid separation in a slurry bed reactor, the slurry after the reaction is drawn out of the reactor, and after passing through a settling tube, the slurry enters the settling tank for sedimentation. The supernatant liquid is discharged as product, while the lower thick slurry containing a large number of catalyst particles is returned to the reactor for circulation.

The separation method disclosed in EP 1405664A1 is to introduce the reacted slurry directly into the settling tank, the settling tank is provided with a baffle, and the height of the baffle is higher than the liquid level in the settling tank, so the slurry flows through the gap between the baffle and the bottom of the tank Finally, the clear liquid slowly rises and flows out above the settling tank, while the thick slurry containing particles returns to the main body of the reactor at the outlet at the bottom of the settling tank.

CN1433838A discloses a method for setting a separation unit in the reactor main body so that the slurry realizes liquid-solid separation, and proposes to apply a strong magnetic field at the bottom of the settling unit to accelerate the liquid-solid separation speed. However, using a single settling technology to achieve complete liquid-solid separation and obtaining a liquid product with a very small solid content requires a settling device with a large volume to ensure sufficient settling time, which results in most of the area and space of the equipment being covered by the settling device. In addition, the smaller the particle size of the catalyst, the more conducive the reaction is to proceed. At the same time, during the reaction process, due to the wear of the catalyst, a solid powder with a very small particle size will be produced, but the sedimentation technology is suitable for particle sizes of several microns or The separation effect of smaller catalyst particles is not good; due to the considerable diameter of the Fischer-Tropsch synthesis reactor, it is difficult for the magnetic field device to generate a uniform magnetic field in the reactor, and the equipment is heavy and expensive, and it is impossible to demagnetize the magnetized catalyst To prevent the agglomeration of the magnetized catalyst and affect the normal operation of the reactor.

WO 94/16807 discloses a method of using a filter assembly in a reactor to realize liquid-solid separation, but once the catalyst particles block the filter assembly, the regeneration of the filter assembly is difficult, thus it is not suitable for large-scale continuous production.

CN1589957A discloses that a primary separation unit is set inside the reactor, a secondary separation unit is set outside the reactor to realize liquid-solid separation, and a recoil unit is set outside the reactor to realize the continuous operation of filtration, which not only takes up The reaction space in the reactor also leads to complex equipment structure and complicated operation.

US 2005/0027021 discloses a liquid-solid separation system. Liquid-solid separation is achieved by setting a vertically placed filter element outside the reactor. The filter cake deposited on the filter element plays a major role in filtering. By adjusting the slurry flow Speed to adjust the thickness of the filter cake. However, since the size of the space where the element is located is determined by the design, the adjustment range is very limited simply by adjusting the slurry flow rate outside the element to control the filtration rate, and the fine particles are easy to block the filter medium without an effective backwash method, making it difficult to achieve continuous filtration. change.

US 2005/0000861 discloses a filter element that can be placed inside and/or outside the reactor. This element is divided into a coarse filter area and a fine filter area, and the two are coaxial and vertically placed with the same diameter. The upper coarse filter area The catalyst with large particles is blocked outside the filter area, and then returned to the reactor for recycling, while the filtrate after coarse filtration will directly enter the fine filter area below the coarse filter area for further filtration and separation. This liquid-solid separation method requires the help of external power, and does not provide a detailed backwashing method, so it is difficult to achieve continuous and effective separation of liquid and solid.

From the above analysis, it can be seen that simply using the sedimentation method needs to occupy a large area, or even precious reaction space; and it is difficult to realize continuous operation by using the filtration method, and even if continuous operation is realized, the separation efficiency will be reduced due to the high solid content. It also complicates the equipment and increases investment and operating costs.

Contents of the invention

The purpose of the present invention is to provide a slurry bed loop reactor which can realize the continuous separation of gas, liquid and solid three phases simply and effectively.

Another object of the present invention is to provide a method for continuous separation of gas-liquid-solid three-phase in a slurry bed reactor, so that the reaction liquid product can be discharged continuously.

The third object of the present invention is to provide a method for producing liquid hydrocarbons or paraffins by Fischer-Tropsch synthesis using a slurry bed.

The slurry bed loop reactor provided by the present invention includes a riser and at least one downcomer 3. The riser is composed of a reaction zone 1 and a settling zone 2 with enlarged pipe diameter. The top of the settling zone 2 is provided with an exhaust gas port 13, each downcomer 3 is divided into a filtrate zone 5 and a slurry zone 6 by the filter medium 4, wherein the filtrate zone 5 communicates with the liquid outlet 10, and the two ends of the slurry zone 6 communicate with the two ends of the riser, so There are baffles arranged roughly vertically in the settling zone 2, wherein the distance between the upper edge of the baffle and the top of the settling zone accounts for 1/10 to 9/10 of the total height of the settling zone, and the settlement The part above the upper edge of the baffle in the zone is the gas-liquid separation zone, and the part of the settling zone below the upper edge is divided into a turbulent flow zone 20 and a steady flow zone 19 by the baffle plate, wherein the turbulent flow Zone 20 is adjacent to reaction zone 1 and is directly communicated with reaction zone 1, and the top of described steady flow zone 19 is directly communicated with described disturbed flow zone, and the bottom of described steady flow zone 19 is connected with reaction zone 18 or draft tube 17. Zone 1 is directly connected, and the downcomer 3 is in communication with the upcomer via a connecting tube 16 at the upper part of the steady flow zone 19 . And the range where the connecting pipe 16 is connected to the position of the steady flow area is in the range of 1/10 to 9/10 of the vertical distance between the upper edge of the baffle and the opening 18 or the connection position between the draft tube 17 and the baffle , preferably in the range of 1/3 to 2/3.

In the reactor provided by the present invention, the shape of the baffle plate may be a flat plate, an arc, a cylinder, a truncated cone, a funnel or other suitable shapes, or a combination of the above shapes. And the "approximately vertically arranged" means that at least a part of the baffle is tangent to the vertical plane, and the baffle divides a part of the settling zone into two or more substantially horizontal distribution space.

A preferred arrangement of the baffles in the above-mentioned reactor is as follows: the disturbed flow zone 20 and the steady flow zone 19 are separated by a cylindrical baffle, and the bottom of the baffle is in contact with the inner wall of the riser. connect. The flow disturbance zone 20 is located inside the cylindrical baffle, and the steady flow zone 19 surrounds the disturbance zone 20, which is formed by the cylindrical baffle and the outer wall of the settlement zone 2. ring area. The bottom of the steady flow zone 19 communicates with the lower part of the reaction zone 1 through the opening 18 or the draft tube 17 . Wherein the diameter of the bottom of the cylindrical baffle can be the same as or different from the diameter of other parts of the baffle, that is, the "cylindrical" not only includes a standard cylindrical shape, but also a truncated cone, or other similar shape, or a combination of the above shapes.

Another preferred arrangement of the baffles in the above reactor is as follows: the disturbed flow zone 20 and the steady flow zone 19 in the reactor are separated by a conical cylindrical baffle, and the conical cylindrical baffle The plate is fixed on the inner wall of the riser by brackets 21 . The steady flow zone 19 is located inside the conical cylindrical baffle, and the disturbance zone 20 surrounds the steady flow zone, that is, the conical cylindrical baffle and the settlement zone 2 The ring-shaped area enclosed by the outer wall. The steady flow zone 19 communicates with the lower part of the reaction zone 1 through the guide tube 17 at the bottom of the conical cylinder. "Cylindrical" as used herein refers to a shape that can generally be thought of as a cone with the apex pointing down, i.e. "funnel" combined with "cylindrical" as defined above The shape of wherein the upper edge of the tapered portion is combined with the lower edge of the cylindrical portion. Of course, the "tapered cylindrical shape" also includes a simple "funnel shape". The term "bracket" here refers to a device that can physically fix the baffle to the inner wall of the riser, and leave enough space between the baffle and the inner wall to allow fluid to pass freely.

In the above reactor provided by the present invention, the slurry flowing from the reaction zone 1 enters the settling zone 2 through the disturbance zone 20 . The gas-liquid (slurry) separation is completed here, and the gas is discharged from the reactor through the exhaust port 13 at the top. Coarse particles can be directly returned to the reaction zone 1 by gravity settling in the disturbance zone 20, or after flowing into the steady flow zone 19 with the slurry, they are enriched at the bottom of the steady flow zone 19 by gravity settling, and then contain more The particle slurry can be returned to the reaction zone 1 through the tube wall opening 18 or the draft tube 17, preferably to the lower part of the reaction zone through the draft tube 17. Typically, during normal operation, the slurry carrying a large number of air bubbles rises from the reaction zone 1 to the disturbance zone 20 above it, and the liquid level is basically flush with the edge of the baffle plate, and the liquid in the steady flow zone 19 is on the other side of the baffle plate. The surface is flush with the upper edge of the baffle or slightly lower than the upper edge of the baffle. During the process of the slurry overflowing from the turbulence zone 20 to the steady flow zone 19, most of the bubbles will leave the slurry and enter the upper gas-liquid separation due to the smooth flow. Zone, because the expansion of the space in the gas-liquid separation zone will reduce the velocity of the gas, reducing the liquid droplets entrained in the bubbles. The slowing down of the slurry flow rate in the steady flow zone makes the solid particles therein settle to the bottom of the steady flow zone 19, and the slurry enriched with solid particles will return to the reaction zone through the opening 18 or the draft tube 17 at the bottom of the steady flow zone 19 to continue to participate in the reaction . The slurry that excludes air bubbles and larger solid particles will enter the filter part through the downcomer 16 for solid-liquid separation.

In the reactor provided by the present invention, the pipe diameter ratio of the reaction zone 1 at the lower part of the riser and the settling zone 2 is 1:1.1-10.0, preferably 1:1.2-3.0.

In the reactor provided by the present invention, the filtrate zone 5 in the downcomer 3 communicates with the liquid outlet 10, and the liquid outlet 10 can be connected to a backwashing system for flushing the filter element through a valve 9, wherein the liquid outlet is preferably The feed port is located at the lower end of the filtrate area; the pipeline 7 connecting the downcomer 3 and the lower end of the riser can be provided with a solid feed port 11 and a solid feed port 12 .

In the reactor provided by the present invention, the lower part of the riser is the reaction zone 1 of the reactor, and the settling zone 2 and the downcomer 3 at the upper part of the riser are the separation zones of the reactor. Wherein, the reactor comprises at least one downcomer 3 . When there are multiple downcomers 3, at least one of the downcomers can be switched to work.

In the reactor provided by the present invention, the filter medium can be in the form of an internal filter tube. When the form of an internal filter tube is adopted, the communication mode between the settling area 2 and the downcomer 3 through the pipeline 16 can be communicated with the internal filter tube (As shown in Figure 1), also can be communicated with the outer tube of downcomer 3 (as shown in Figure 4), when communicating with internal filter tube, connect liquid outlet 10 on the outer tube, in downcomer 3, The liquid passes through the wall of the inner filter tube in a radial direction from the inside to the outside, and is finally drawn out as a product through the pipeline; at the same time, the upper part of the outer tube is connected to the gas enrichment zone at the top of the settling zone 2 through the pipeline 8 to maintain pressure balance and prevent gas from Accumulated in the downcomer. When the ascending pipe communicates with the outer pipe of the descending pipe 3, the filter pipe is connected to the liquid outlet 10. In the descending pipe 3, the liquid passes through the pipe wall of the inner filter pipe radially from the outside to the inside, and finally passes through the pipeline as a product. lead out.

The interior of the outer tube of each downcomer 3 contains at least one filter tube. When a downcomer 3 contains multiple filter tubes: at least two filter tubes can be connected in parallel on a liquid collection tray to form a filter unit for use, as shown in Figure 5 and Figure 6, and Figure 5 shows multiple filter tubes The top view of the filter unit with tubes connected in parallel on the liquid collection tray, Figure 6 is a side view of the filter unit with multiple filter tubes connected in parallel on the liquid collection tray; a combination of multiple filter units can also be used. The form of filter unit and filter unit combination can effectively save space and improve filter efficiency.

When adopting the combined form of multiple filter units, the combined distribution of filter units in the outer tube has the following forms: vertically place multiple filter units along the axial direction (accompanying drawing 7); or distribute multiple filter units in parallel along the radial direction (accompanying drawing 8); Or place multiple sets of multiple filtering units distributed in parallel in a radial form along the axial direction (accompanying drawing 9). Each filter unit can be equipped with an independent backwash system, or each filter unit can be connected to a common backwash system through pipelines.

In the reactor provided by the present invention, the solid feeding port 11 and the solid feeding port 12 are used to process the catalyst more flexibly. When the catalyst particles in the reactor need to be replaced due to deactivation or wear and tear, they can be discharged through the solid discharge port 11, or fresh catalyst can be replenished through the solid feed port 12.

In the reactor provided by the present invention, there is no limit to the material of the filter medium 4, and sintered metal mesh microporous filter material, sintered metal powder microporous filter material, metal microporous membrane material, sintered metal fiber microporous material, microporous filter material can be used. Porous ceramic materials, ceramic membrane materials or other types of filter materials. The pore size range of the filter medium can vary depending on the type of catalyst particles used, the scale of the reactor, and the type of reaction performed, for example, it can be within the range of microfiltration, ultrafiltration, nanofiltration, etc.

In the application method of the reactor provided by the present invention, the raw material enters the reactor from the feed port 14, and mixes with the slurry in the riser reaction zone 1, and the mixed slurry reacts in the reaction zone 1 while flowing upwards, from the reaction zone 1 The nozzle at the upper end first flows to the disturbance zone 20 of the settling zone 2, and then overflows from the disturbance zone 20 to the steady flow zone 19. Liquid separation, the gas is discharged from the reactor through the exhaust port 13 on the top, and the coarser particles are settled by gravity, and are directly returned to the reaction zone 1 from the disturbed flow zone 20, or settled to the bottom of the steady flow zone 19, and then passed through The opening 18 or the guide pipe 17 returns to the reaction zone 1, and the slurry containing finer particles enters the downcomer 3 from the upper part of the steady flow zone 19 through the connecting inclined tube 16; the main body of the slurry is axially downward in the slurry zone 6 Part of the liquid is driven by the pressure difference on both sides of the filter medium 4 and enters the filtrate zone 5 through the filter medium 4, and is finally drawn out as a product. The solid catalyst particles continue to flow down with the main body of the slurry and return to the riser through the pipeline 7 Continue to participate in the reaction.

In the method provided by the present invention, the draft tube 17 introduces the slurry enriched in catalyst particles into the lower part of the reaction zone, and the high density inside it and the lower density in the reaction zone 1 due to the large number of air bubbles form a density difference. New form of internal circulation. This form of internal circulation will make the catalyst in the bed more evenly distributed with the natural circulation of the slurry. In addition, the arrangement of the guide tube reduces the circulation volume of the downcomer and improves the filtering effect in the downcomer.

In the method provided by the present invention, the superficial gas velocity of the gas entering the reactor in the reaction zone 1 at the lower part of the riser is 0.01-1.0 m/s, preferably 0.04-0.5 m/s. Wherein the superficial gas velocity refers to the air velocity of the empty pipe in the riser of the air flow. Controlling the gas velocity within this range can make the slurry agitate and mix evenly, and provide the driving force for the circulation of the slurry between the riser and the downcomer 3, Maintain the reaction pressure in the reactor. The relatively high pressure inside the reactor and the low pressure in the filtrate zone 5 of the downcomer 3 form a pressure difference on both sides of the filter medium 4, pushing the separated gas slurry through the filter medium 4 to achieve solid-liquid separation.

In the method provided by the present invention, as the reaction proceeds, the pressure difference on both sides of the filter medium 4 rises with the thickening of the filter cake. When the pressure difference is higher than the first set value, the backwashing system starts to work. At this time, the liquid After the discharge port, the valve 15 is closed, and the liquid discharge port 10 is connected to the backflush pipeline through the valve 9. The backwash medium is backwashed by the external reverse pressure difference, and the filter medium 4 is reversely flushed with the removal of the filter cake. The difference continues to decrease, and when it is lower than the second set value, the flushing process ends, and at this time, the valve 9 behind the liquid outlet 10 is closed, and the system returns to the normal operating state.

Among them, the first setting value of the pressure difference when starting the backwashing system is 0.1-1.0Mpa, and the second setting value of the pressure difference when the backwashing is closed is 0.05-0.8Mpa. According to different filter materials, the filter pressure difference range is also different. Similarly, different materials correspond to different backwash pressures. For the same filter element and equipment, the first setting value must be greater than the second setting value. For the filtration process of normal operation, the pressure difference range between both sides is 0.05-1.0MPa. The start and end of the backwash process can be performed automatically or manually.

Wherein said backwash medium can be gas or liquid, preferably product clear liquid or reaction tail gas, more preferably product clear liquid.

In the method provided by the present invention, without affecting the reaction process, the finer catalyst particles can be selectively removed from the solid feeding port 11, and part of the fresh catalyst can be replenished through the solid feeding port 12.

The application of the method provided by the invention in the production of liquid hydrocarbons or paraffin by Fischer-Tropsch synthesis is characterized in that the raw material is synthesis gas, the active component of the catalyst contains Fe and/or Ba, and the operating conditions in the riser reaction zone 1 are: temperature 200-300°C, preferably 230-280°C, pressure 1.0-5.5Mpa, preferably 1.7-3.5Mpa, raw material space velocity relative to catalyst mass 1.0-8.0Nlg ^-1 h ^-1 , preferably ^{2.0-5.0Nlg- 1h -1} .

The slurry bed loop reactor provided by the invention can realize the continuous and efficient separation of solid catalyst particles, liquid products and reaction gases, and the gas-liquid-solid three-phase continuous discharge; the settling area is divided into a turbulent flow area and a quasi-static settling area to reduce The airflow rising from the reaction zone disturbs the settled particles in the settling zone, thereby improving the separation efficiency of the settling zone, reducing the load of the downcomer filter, thereby increasing the processing capacity and separation efficiency of the entire reactor, and prolonging the life of the reactor. Backwash cycle. The reactor of the present invention and its application method are suitable for the chemical reaction process of gas-liquid-solid three-phase reaction and need to separate the liquid product from the slurry, such as the hydrogenation and dehydrogenation process of hydrocarbon oil using a suspended bed or slurry bed reactor and the Fischer-Tropsch synthesis process.

Description of drawings

Fig. 1 is the loop reactor schematic diagram that the lower part of the steady flow zone communicates with the reaction zone through the opening;

Fig. 2 is the schematic diagram that the lower part of the steady flow zone communicates with the reaction zone through the draft tube;

Fig. 3 is the schematic diagram that the settlement zone is divided into a steady flow zone and a flow disturbance zone by a conical cylinder;

Fig. 4 is the schematic diagram of the slurry bed loop reactor that the settling zone communicates with the outer pipe of the downcomer through the pipeline;

Fig. 5 is a top view schematic diagram of a plurality of inner pipes connected in parallel with a liquid collection tray as a filter unit;

Fig. 6 is a schematic side view of a plurality of inner pipes connected in parallel with a liquid collection tray as a filter unit;

Fig. 7 is a schematic diagram of a plurality of filter units arranged axially along the downcomer;

Fig. 8 is a schematic diagram of a plurality of filter units radially arranged along the downcomer;

Fig. 9 is a schematic diagram of a plurality of filter units arranged radially and axially in the downcomer;

10 is a schematic diagram of the loop reactor used in Example 1.

Detailed ways

The method for continuously separating liquid and solid particles in the Fischer-Tropsch synthesis process using the slurry bed loop reactor provided by the present invention will be specifically described below in conjunction with the accompanying drawings, but the present invention is not limited thereby.

As shown in accompanying drawing 2: the lower part of the riser of the loop reactor is a slurry bed reaction zone 1, and the reactant synthesis gas enters the reactor from the lower feed port 14 of the riser, and mixes with the slurry in the riser reaction zone 1, Mixing, contact with the catalyst particles in the slurry, complete the chemical reaction during the rising process, the product and excess reactants rise to the upper part of the reactor together with the catalyst, and flow from the upper end of the reaction zone 1 to the disturbance zone 20 of the settlement zone 2 , then overflows from the turbulent flow zone 20 to the steady flow zone 19, the slurry flow rate decreases, and the gas-liquid separation is carried out in the gas-liquid separation zone of the turbulent flow zone 20, the steady flow zone 19 and the upper part, and the gas is discharged from the top exhaust port 13 out of the reactor, the coarser particles rely on gravity to settle, and return directly to the reaction zone 1 from the disturbance zone 20, or settle to the bottom of the steady flow zone 19, and then return to the reactor through the opening 18 or the draft tube 17. In the reaction zone 1, the slurry containing finer particles enters the downcomer 3 from the upper part of the steady flow zone 2 through the connecting inclined pipe 16; the main body of the slurry flows axially downward in the slurry zone 6, and a part of the liquid flows in the filter medium 4 Driven by the pressure difference on both sides, it enters the filtrate zone 5 through the filter medium 4 and is finally drawn out as a product. The solid catalyst particles continue to flow down with the main body of the slurry and return to the riser through the pipeline 7 to continue to participate in the reaction.

The solid particles are blocked on the inner wall of the filter tube. Due to the scouring effect of the liquid flow, part of the filter cake on the inner wall of the filter tube continues to fall off and returns to the reaction zone 1 of the riser with the downward flow of the slurry, and some of the filter cake that is not easy to fall off It will stay on the inner wall of the filter tube. With the continuous thickening of the filter cake, the pressure difference between the inner and outer tubes will rise. When the pressure difference is higher than the first set value of 0.1-1.0Mpa, the backwashing system will start to work. At this time, the valve 15 behind the liquid discharge port 10 is closed, and the valve 9 is opened. Under the push of the external reverse pressure difference, the backwash medium is introduced into the outer pipe 5 and passes through the filter pipe radially from outside to inside, and adheres to the inside of the filter pipe. The filter cake on the wall is backflushed into the slurry and returns to the riser as the slurry flows down. When the pressure difference between the inner and outer pipes is lower than the second set value of 0.05-0.8Mpa, the flushing process is over, at this time the valve 9 on the backwash medium introduction pipe is closed, the valve 15 behind the liquid discharge port and the valve on the connecting pipe 8 is turned on and the system returns to normal operation.

The specific embodiment of the slurry bed loop reactor shown in accompanying drawing 3 is basically the same as the embodiment of the reactor shown in accompanying drawing 2, and difference is: in riser, conical cylinder and settling zone 2 outer walls surround The annular area formed is the turbulent flow area 20, here, the coarser particles can be directly returned to the reaction area 1 by gravity sedimentation, and the area inside the conical cylinder is the steady flow area 19, where more and finer particles are enriched. The coarse particle slurry returns directly to the lower part of the reaction zone 1 through the bottom of the steady flow zone 19 and the guide tube 17 .

The following examples further illustrate the method provided by the present invention, but do not limit the present invention thereby.

Comparative example 1

Comparative Example 1 illustrates the separation effect of a loop reactor without baffles in the settling zone.

Using the slurry bed loop reactor shown in Figure 10, the pipe diameter ratio of the riser settling zone and the reaction zone is 1.5: 1, and the filter tube adopted in the downcomer is a sintered porous metal filter tube. The diameter is 50mm, the length is 1000mm, and the average pore diameter is 1μm. The particle size range of the catalyst used is 1-100 μm, the raw material is synthesis gas, and the pressure difference between the inner and outer tubes of the downcomer is greater than 0.5 MPa. The backwash system starts to operate, and the product clear liquid is introduced into the outer pipe by the pump, and enters the inner pipe through the filter pipe wall, washes the filter cake into the slurry, and returns to the riser with the slurry flowing down. This process lasts for several seconds. When the pressure difference between the inner and outer pipes is lower than 0.1MPa, the backwash system is closed and the slurry bed reactor returns to normal operation. During this process, the flow rate of the clear liquid drawn from the pipeline 10 is: 60L/h, the backwash cycle is 48 hours, the content of solid particles in the liquid product is less than 5μg/ml, and the maximum diameter of the particles is 2μm. The separation efficiency is above 99%.

The separation efficiency is calculated by the following formula:

η=(S _m -S _f )/S _m

Wherein: S _m = solid content in raw material (slurry before filtration); S _f = solid content in product (clear liquid drawn from filtrate area).

Examples 1 to 3 illustrate the separation effect of the loop reactor with baffles in the settling zone 2, which divides the settling zone into a disturbed flow zone, a steady flow zone and a gas-liquid separation zone.

Example 1

挡板底部开有6个

的孔；下降管外管尺寸为内过滤管材质为金属微孔膜，该滤管尺寸为

平均孔径1.0μm。Using the reactor shown in Figure 1, the flow disturbance zone 20 and the steady flow zone 19 are separated by a cylindrical baffle, and the bottom of the steady flow zone 19 communicates with the reaction zone through the opening at the bottom of the baffle. where the size of the reaction zone is The diameter of the expansion section of the settlement zone is 150mm, and the height is 1000mm; the size of the cylindrical baffle is

There are 6 openings at the bottom of the baffle

hole; the size of the outer tube of the downcomer is The inner filter tube is made of metal microporous membrane, and the size of the filter tube is

The average pore size is 1.0 μm.

The composition of the catalyst was: 20.3% by weight of Co ₂ O ₃ , 76.1% by weight of SiO ₂ , and 3.6% by weight of MgO. The preparation method is to impregnate the SiO ₂ microsphere carrier with a solution containing Co(NO ₃ ) ₃ and Mg(NO ₃ ) ₂ , let it stand for 24 hours, then dry it at 120°C, and bake it at 400°C for 6 hours to obtain a particle size range of 1 ~100 μm catalyst.

The catalyst loading is 15% (volume percentage). The raw material is synthesis gas (the molar ratio of H ₂ :CO is 2:1), the space velocity relative to the mass of the catalyst is 2.0NLg ^-1 h ^-1 , and the pressure is 3.0MPa and the temperature is 200-220℃. catalyst contact reaction. When the pressure difference between the inner and outer pipes of the downcomer is greater than 0.5MPa, the backwashing system starts to operate, and the product clear liquid is introduced into the outer pipe by a pump, and enters the inner pipe through the filter pipe wall, and the filter cake is washed into the slurry, and then The slurry flows down the return riser. This process lasts for several seconds. When the pressure difference between the inner and outer pipes is lower than 0.1MPa, the backwash system is closed and the slurry bed reactor returns to normal operation. After the clear liquid is fractionated, the product distribution is as follows: 6.3% by weight of dry gas, 3.6% by weight of liquefied gas, 13.4% by weight of naphtha, 30.7% by weight of diesel oil, and 46% by weight of hard wax.

During this process, the flow rate of the clear liquid drawn from the pipeline 10 is 1.7 L/h, the backwashing period is 120 hours, and the single-pass conversion rate of CO in the syngas is 92.4%. The content of solid particles in the liquid product is less than 3 μg/ml, and the maximum diameter of the particles is 1 μm. The separation efficiency was 99.5%.

Example 2

沉降区扩大段管径为450mm，高为1000mm；圆筒状挡板尺寸为导流管共6根，尺寸分别为

和

交错排列；下降管外管尺寸为

内过滤管材质为金属微孔膜，平均孔径为0.2μm，如图6所示7根并联，每根的尺寸为

Using the reactor shown in FIG. 2 , the disturbed flow zone 20 and the steady flow zone 19 are separated by a cylindrical baffle, and the bottom of the steady flow zone 19 communicates with the lower part of the reaction zone through a draft tube 17 . where the size of the reaction zone is

The diameter of the expansion section of the settlement zone is 450mm, and the height is 1000mm; the size of the cylindrical baffle is There are 6 guide tubes in total, and the sizes are

and

Staggered arrangement; the outer tube size of the downcomer is

The inner filter tube is made of metal microporous membrane with an average pore size of 0.2 μm. As shown in Figure 6, 7 pieces are connected in parallel, and the size of each piece is

160 liters of slurry containing solid particles is preliminarily introduced into the reactor, the particle size range of the slurry is 1-100 μm, and the superficial gas velocity after air is introduced into the reactor is 0.06 m/s. The clear liquid drawn from line 10 returns to the reactor from the bottom. When the pressure difference between the inner and outer pipes of the downcomer is greater than 0.5MPa, the backwashing system starts to operate, and the product clear liquid is introduced into the outer pipe by a pump, and enters the inner pipe through the filter pipe wall, and the filter cake is washed into the slurry, and then The slurry flows down the return riser. This process lasts for several seconds. When the pressure difference between the inner and outer pipes is lower than 0.1MPa, the backwash system is closed and the slurry bed reactor returns to normal operation.

During this process, the clear liquid flow rate drawn from the pipeline 10 is: 210L/h, the backwash cycle is 100 hours, the solid particle content in the liquid product is less than 5μg/ml, and the maximum particle diameter is 1μm. The separation efficiency was 99.9%.

Example 3

沉降区扩大段管径为450mm，高为1500mm；带有导流管的漏斗状挡板大口尺寸为

导流管尺寸为下降管外管尺寸为

内过滤管材质为金属微孔膜，平均孔径为1μm，如图6所示7根并联，每根的尺寸为

Adopt the reactor as shown in accompanying drawing 3, described disturbance area 20 and steady flow area 19 are separated by conical cylindrical baffle, and described conical cylindrical baffle is fixed in described riser by bracket 21 On the wall, the bottom of the steady flow zone 19 communicates with the lower part of the reaction zone through a draft tube 17 . where the size of the reaction zone is

The pipe diameter of the expansion section of the settlement area is 450mm, and the height is 1500mm;

The size of the duct is The outer tube size of the downcomer is

The inner filter tube is made of metal microporous membrane with an average pore size of 1 μm. As shown in Figure 6, 7 pieces are connected in parallel, and the size of each piece is

Introduce 160 liters of slurry containing solid particles into the reactor in advance. The particle size range in the slurry is 1 to 100 μm. Seconds, the clear liquid drawn from the pipeline 10 returns to the reactor from the bottom. When the pressure difference between the inner and outer pipes of the downcomer is greater than 0.5MPa, the backwashing system starts to operate, and the product clear liquid is introduced into the outer pipe by a pump, and enters the inner pipe through the filter pipe wall, and the filter cake is washed into the slurry, and then The slurry flows down the return riser. This process lasts for several seconds. When the pressure difference between the inner and outer pipes is lower than 0.1MPa, the backwash system is closed and the slurry bed reactor returns to normal operation.

During this process, the clear liquid flow rate drawn from the pipeline 10 is: 250L/h, the backwash cycle is 100 hours, the solid particle content in the liquid product is less than 5μg/ml, and the maximum particle diameter is 1μm. The separation efficiency was 99.9%.

Claims (16)

1. slurry bed circulatory flow reactor, comprise tedge and at least one down-comer (3), it is characterized in that tedge is made up of the decanting zone (2) that reaction zone (1) and caliber enlarge, the top of decanting zone (2) is provided with exhaust outlet (13), be filtered medium (4) in the every down-comer (3) and be divided into filtrate district (5) and slurries district (6), wherein filtrate district (5) are communicated with liquid outlet opening (10), the two ends in slurries district (6) are connected with the two ends of tedge respectively, has the baffle plate that roughly vertically is provided with in the described decanting zone (2), the top edge of wherein said baffle plate accounts for 1/10～9/10 of described decanting zone total height apart from the distance at the top of described decanting zone, the decanting zone above part of inherent described baffle plate top edge is a gas-liquid separation zone, the decanting zone then is divided into turbulent flow area (20) and current stabilization district (19) by described baffle plate in this part below top edge, described turbulent flow area (20) is close to reaction zone (1) and directly is communicated with reaction zone (1), and the top in described current stabilization district (19) directly is communicated with described turbulent flow area, bottom, described current stabilization district (19) directly is communicated with reaction zone (1) through perforate (18) or mozzle (17), and described down-comer (3) is communicated with described tedge through tube connector (16) on the top in described current stabilization district (19), and described tube connector (16) connects 1/10 to 9/10 scope of position, current stabilization district (19) in the vertical distance of described baffle plate top edge and described perforate (18) or mozzle (17) and baffle plate link position.

2. according to the reactor of claim 1, it is characterized in that described turbulent flow area (20) and described current stabilization district (19) are separated by cylindrical baffle, and described baffle plate bottom is connected with the inwall of described tedge, described turbulent flow area (20) is positioned at described cylindrical baffle inside, described current stabilization district is looped around described cylindrical baffle outside, and bottom, described current stabilization district (19) is passed cylindrical wall by mozzle (17) and directly is communicated with reaction zone (1) bottom.

3. according to the reactor of claim 2, it is characterized in that the diameter of the diameter of described cylindrical baffle bottom and these other parts of baffle plate is identical or different.

4. according to the reactor of claim 1, it is characterized in that described turbulent flow area (20) and described current stabilization district (19) are separated by tapered cylinder shape baffle plate, described tapered cylinder shape baffle plate is fixed on the inwall of described tedge by support (21), described current stabilization district (19) is positioned at described tapered cylinder shape baffle interior, and described turbulent flow area (20) is positioned at tapered cylinder shape baffle plate outside, and described current stabilization district (19) directly is communicated with the bottom of reaction zone (1) by the mozzle (17) of tapered cylinder shape baffle plate bottom.

5. according to claim 1,2,3 or 4 reactor, it is characterized in that the caliber ratio of tedge lower reaction zone (1) and decanting zone, top (2) is 1: 1.1～10.

6. according to claim 1,2,3 or 4 reactor, it is characterized in that described liquid outlet opening (10) connects backwashing system through valve (9).

7. according to claim 1,2,3 or 4 reactor, it is characterized in that the pipeline (7) that connects down-comer (3) and tedge lower end is provided with solid drain hole (11) and solid feed inlet (12).

8. the application process of the reactor of claim 1～5, it is characterized in that raw material enters reactor by charging aperture (14), mix with the slurries in the tedge reaction zone (1), mixed slurries react in reaction zone (1), upwards flow simultaneously, at first flow to the turbulent flow area (20) of decanting zone (2) from reaction zone (1) the upper end mouth of pipe, again by turbulent flow area (20) overflow to current stabilization district (19), in described turbulent flow area (20), the gas-liquid separation zone on current stabilization district (19) and top carries out gas-liquid separation, gas is discharged reactor from the exhaust outlet (13) at top, thicker particle relies on gravitational settling, directly turn back in the reaction zone (1) by described turbulent flow area (20), perhaps be deposited to bottom, current stabilization district (19), get back in the reaction zone (1) via perforate (18) or mozzle (17) again, contain more fine grain slurries and enter the down-comer (3) from top, current stabilization district (19) through connecting inclined tube (16); The slurries main body flows downward in slurries district (6) vertically, and wherein a part of liquid enters filtrate district (5) by filter medium (4) under the promotion of filter medium (4) both sides pressure reduction, and finally draw as product, solid particle then continues to flow downward with the slurries main body and turns back to continuation participation reaction in the tedge by pipeline (7).

9. according to the method for claim 8, it is characterized in that the superficial gas velocity of gas feed in tedge reaction zone (1) is 0.01～1.0 meter per second.

10. according to the method for claim 9, it is characterized in that described superficial gas velocity is 0.04～0.5 meter per second.

11. method according to claim 8, it is characterized in that when filter medium layer both sides pressure reduction is higher than first setting value, backwashing system is started working, the upper end in filtrate district this moment (5) and the connection of decanting zone (2) are cut off, and liquid outlet opening (10) and recoil pipeline are communicated with backwash medium back flush filter medium (4), when pressure reduction is lower than second setting value, flushing process finishes, and this moment, liquid outlet opening and backwash pipeline disconnected, and system returns to normal operating state.

12. according to the method for claim 11, it is characterized in that the scope of described first setting value is 0.1～1.0Mpa, the scope of described second setting value is 0.05～0.8Mpa.

13., it is characterized in that described backwash medium is gas or liquid according to the method for claim 11.

14., it is characterized in that described backwash medium is product clear liquid or reaction end gas according to the method for claim 13.

15., it is characterized in that described backwash medium is the product clear liquid according to the method for claim 14.

16. the method for claim 9 is in the synthetic application of producing in liquid hydrocarbon or the paraffin of Fischer-Tropsch, it is characterized in that raw material is a synthesis gas, the activity of such catalysts component contains Fe and/or Co, operating condition in the tedge reaction zone (1) is: temperature is 200～300 ℃, pressure is 1.0～5.5Mpa, is 1.0～8.0Nlg with respect to catalyst quality raw material air speed ^-1h ^-1

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